Assessing Occupational Exposure to Flame Retardants and Plasticizers

Assessing occupational exposure to flame retardants

and plasticizers using silicone passive samplers and

other measurement methods

Linh Viet Nguyen

A thesis submitted in conformity with the requirements for the degree of Doctor of Philosophy

Department of Physical & Environmental Science University of Toronto Scarborough

Assessing occupational exposure to flame retardants

and plasticizers using silicone passive samplers and

other measurement methods

Linh Viet Nguyen PhD. Thesis Department of Physical and Environmental Sciences University of Toronto Scarborough 2021 Abstract Occupational exposure to the complex mixtures of semi-volatile organic compounds

(SVOCs), including flame retardants (FRs) and plasticizers, used in personal care products and electronic and electrical equipment is a serious concern. This thesis documents occupational exposure to FRs and plasticizers in e-waste facilities and nail salons using silicone passive samplers and other measurement methods, including dust collection and active air sampling. The thesis advances the understanding of the use of silicone passive samplers for measuring SVOC exposure in personal exposure monitoring and assessment.

Three silicone passive sampler configurations (brooches, wristbands and armbands) accumulated detectable amounts of FRs and plasticizers within a relatively short deployment time

(~8 hours) in both e-waste and nail salon environments. Among these samplers, silicone brooches showed the strongest correlations with active air samplers for most compounds. The correlations between brooches and active air samplers were stronger in e-waste facilities than in nail salons.

This thesis found that silicone brooches and wristbands can be useful for indicating internal exposure to SVOCs with relatively long biological half-lives, like decabromodiphenyl ether

(BDE-209), but their uses for compounds with relatively short half-lives, like organophosphate esters (OPEs), is unclear. Overall, results suggest that silicone brooches and wristbands are valuable screening tools for qualitative exposure studies, but are not reliable for quantitative exposure measurement.

The thesis contains the first reports of FR and plasticizer exposure at elevated levels in

Canadian e-waste recycling facilities and nail salons. Higher exposures via air and dust to FRs were found in formal e-waste facilities in Ontario and Quebec compared to previous studies in formal and informal facilities across the globe. E-waste workers in an Ontario facility were exposed to FRs in respirable particles, raising concerns for worker health in e-waste environment.

Exposure to some OPEs in nail salons at relatively high levels was an unexpected finding as these chemicals are known to be FRs and have not been reported to be used in personal care products.

Results presented here call attention to FRs and plasticizers exposure among workers in e-waste facilities and nail salons where these chemicals are, largely, not addressed by current occupational exposure limits.

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Acknowledgements This PhD journey not only serves the purpose of starting a career, but also helps me to grow. I feel extremely grateful for all the help, support, advice, and encouragement from many people.

First, I would like to express deep gratitude to my supervisors, Profs Miriam Diamond and Victoria Arrandale, who are my role models for successful women in sciences. I truly appreciate the wise guidance, incredible patience, great insights, and endless support I received from them throughout this journey. I am very thankful for their amazing support to turn around the sudden disappointment at the Ontario e-waste facility into the successful Quebec e-waste study. Further, I am particularly grateful to Miriam for her constant reminder of big pictures in every project, and to Victoria for accompanying me on early morning sampling in Ontario e-waste facility.

My heartfelt gratitude goes to two other members of my thesis supervisory, Prof. Tracy Kirkham and Dr. Liisa Jantunen who generous with their wisdom, time, guidance, and insights that helped to shape my thesis. Particularly, thanks to Tracy for her guidance in R and the strategies to work with a large occupational dataset and to Liisa for her endless help with lab issues from sample preparation to troubleshooting the GC/MS.

Thanks to Prof. Jeffrey Siegel who served in the departmental defence and thoughtfully reviewed my thesis, and Prof. Eric Liberda who served in the external defence and provide constructive review for my thesis.

Huge thanks for endless help and tremendous support of administrative and technical staff from both Department of Physical and Environmental Sciences (Elaine Pick, Julie Quenneville and Shelley Eisner) and Department of Earth Sciences (Silvanna Papaleo, Natasha Shaw, Riaz Ahmed and Dr.. Mike Gorton).

A special thank goes to my great collaborators in Indiana University (Drs. Marta Venier, William Stubbings, Jiehong Guo and Kevin Romanak), Research Centre for Toxic Compounds in the Environment (Dr. Lisa Melymuk), Institut de recherche Robert-Sauvé en santé et en sécurité du travail (Dr. Sabrina Gravel, Prof. France Labrèche), Université de Montréal (Profs. Marc-André Verner, Bouchra Bakhiyi and Joseph Zayed), St. Michael’s Hospital (Dr. D.Linn Holness) and Ontario Health (Sheila Kalenge). I am particularly appreciated Sabrina and France for their wonderful support with the Quebec e-waste sampling and Sheila for her endless support in Toronto nail salon sampling.

I cannot acknowledge in a few words Dr. Joseph Okeme for his extravagant friendship and support. I also thank to selfless help and support of current and past members of Diamond group (Dr. Yuchao Wan, Tim Rogers, Garthika Navaranjan, Sam Athey, Sara Vaezafshar, Jacob Kvasnicka, Sarah Bernstein and Rachelle Robitaille; Drs. Congqiao Yang, Atousa Abdollahi, Jasmine Katharina Schuster, Prof. Yan Wang). I also want to thank my undergraduate assistants for their support (Emily Palaganas, Adriana Shu-yin and Matthew Tulio) who helped with cleaning glassware and preparing samples.

I am also thankful to friends in departments (Dr. Man-Yin Tsang; Alice Alex, Erin Seagren and Clara Thaysen), and outside the academic world (Xiaoke Zeng and, Nguyen Thi Ngoc Bich, Nguyen Ngoc Ha, Diep Nguyen) for their friendship and support.

This journey can not be started without the inspiration and motivation from the late Prof. Huw Taylor, Prof. Andrew Cundy and Dr. Rosa Busquets who are great scientists with the pure love for improving the quality of life with their scientific knowledge.

The thesis is dedicated to my parents, extended family in Vietnam and my partner (-in-crime) who always love and believe in me and offer their great patience for listening to all scientific and nonsense random stories throughout this up-and- down journey.

Finally, I would like to thank my first meditation teacher Bhikkhuni Thich Nu Hang Lien, who introduced me to Vipassana meditation. The tool helped me to focus on the main issues and quickly accept the constant changes without attaching negativity feeling and thought to random blockages and obstacles arising throughout the journey.

Once again, I am deeply thankful for all blessings, help, advice, knowledge, opportunities, and friendship I received from all of you during this 5-year journey. Thank you!

Table of Contents ABSTRACT ...... II ACKNOWLEDGEMENTS ...... IV LIST OF TABLES ...... VIII LIST OF FIGURES ...... IX LIST OF ABBREVIATIONS ...... X CHAPTER 1 – INTRODUCTION AND LITERATURE REVIEW ...... 1

1.1 MOTIVATION ...... 1 1.2 FLAME RETARDANTS AND PLASTICIZERS...... 2 1.2.1 Background ...... 2 1.2.2 Exposure pathways to FRs and plasticizers ...... 5 1.3 MEASUREMENT OF EXPOSURE TO FRS AND PLASTICIZERS ...... 8 1.3.1 Active air sampling ...... 9 1.3.2 Passive sampling ...... 10 1.4 OCCUPATIONAL EXPOSURE MEASUREMENTS TO FRS AND PLASTICIZERS ...... 13 1.4.1 Electronic waste recycling facilities ...... 13 1.4.2 Nail salons ...... 15 1.5 STRUCTURE OF THESIS ...... 16 REFERENCES ...... 21 CHAPTER 2 - EXPOSURE OF CANADIAN ELECTRONIC WASTE DISMANTLERS TO FLAME RETARDANTS...... 44

ABSTRACT ...... 44 2.1 INTRODUCTION ...... 45 2.2 MATERIALS AND METHODS ...... 49 2.2.1 Study Location ...... 49 2.2.2 Sampling Strategy ...... 50 2.2.3 Pre-cleaning, Extraction and Analysis ...... 52 2.2.4 Quality Assurance and Quality Control (QA/QC) ...... 53 2.2.5 Exposure Estimates ...... 53 2.2.6 Data Analysis ...... 54 2.3 RESULTS AND DISCUSSION ...... 55 2.3.1 Air Concentrations ...... 55 2.3.2 Dust Concentrations ...... 62 2.3.3 Occupational Exposure to Flame Retardants ...... 63 2.3.4 Comparison of exposure with recommended doses ...... 67 2.3.5 Strengths and Limitations ...... 69 2.4 IMPLICATIONS ...... 70 REFERENCES ...... 71 CHAPTER 3 – THE USE OF SILICONE PASSIVE SAMPLERS FOR MEASURING EXPOSURE OF E-WASTE WORKERS TO FLAME RETARDANTS ...... 91

ABSTRACT ...... 91 3.1 INTRODUCTION ...... 92 3.2 MATERIALS AND METHODS ...... 95 3.2.1 Study design ...... 95

3.2.2 Sampling strategy ...... 96 3.2.3 Extraction and analysis ...... 99 3.2.4 Quality Assurance and Quality Control (QA/QC) ...... 99 3.2.5 Estimation and evaluation of silicone brooch sampling rates ...... 100 3.2.6 Data Analysis ...... 101 3.3 RESULTS AND DISCUSSION ...... 103 3.3.1 Levels of FRs in personal passive samplers...... 103 3.3.2 Comparison of personal silicone passive samplers with active air samples ...... 107 3.3.3 Correlation between FRs in silicone samplers and biomonitoring data ...... 109 3.3.4 Evaluation of sampling rates of silicone brooch ...... 112 3.3.5 Strengths and Limitations ...... 113 REFERENCES ...... 115 CHAPTER 4 – OCCUPATIONAL EXPOSURE OF CANADIAN NAIL SALON WORKERS TO FRS AND PLASTICIZERS INCLUDING PHTHALATES AND ORGANOPHOSPHORUS ESTERS (OPES) ...... 135

ABSTRACTS ...... 135 4.1 INTRODUCTION ...... 136 4.2 MATERIALS AND METHODS ...... 139 4.2.1 Study design ...... 139 4.2.2 Sampling strategy ...... 139 4.2.3 Extraction and chemical analysis ...... 141 4.2.4 Quality Assurance and Quality Control (QA/QC) ...... 142 4.2.5 Data Analysis ...... 143 4.3 RESULTS AND DISCUSSION ...... 144 4.3.1 Levels of phthalates and OPEs in active air samplers and silicone samplers ...... 144 4.3.2 Relationships between air concentrations and services performed ...... 150 4.3.3 Comparison of active air samplers and silicone passive samplers ...... 154 4.4 STRENGTHS AND LIMITATIONS ...... 155 ACKNOWLEDGMENTS ...... 156 REFERENCES ...... 156 CHAPTER 5 - CONCLUSIONS ...... 175

5.1 SUMMARY OF CONTRIBUTIONS ...... 175 5.2 DETAILED DISCUSSION OF CONTRIBUTIONS TO ENVIRONMENTAL AND EXPOSURE SCIENCE ...... 176 5.2.1 Documenting current exposure levels of FRs in e-waste facilities ...... 176 5.2.2 Documenting current exposure levels of plasticizers in nail salons ...... 177 5.2.3 Advancing our understanding of the use of silicone passive samplers as a promising measurement tool in occupational exposure monitoring and assessment...... 178 5.2.4 Updating the sampling rates of silicone samplers for assessing SVOC exposure in indoor environments ...... 181 5.3 PROPOSED MAIN FACTORS INFLUENCING PERSONAL EXPOSURE MEASUREMENTS OF PASSIVE SAMPLERS ...... 182 5.3.1 Sampler characteristics ...... 183 5.3.2 Chemical emission sources ...... 183 5.3.3 Personal characteristics ...... 184 5.3.4 Indoor environment characteristics ...... 185 5.4 OVERALL STRENGTHS AND LIMITATIONS ...... 186 5.4.1 Strengths ...... 186 5.4.2 Limitations ...... 187 5.5 OVERALL CONCLUSIONS ...... 188

5.6 RECOMMENDATIONS FOR FUTURE WORK ...... 189 REFERENCES ...... 190 APPENDICES ...... 227

APPENDIX 1: SUPPORTING INFORMATION FOR CHAPTER 2 ...... 227 APPENDIX 2: SUPPORTING INFORMATION FOR CHAPTER 3 ...... 261 APPENDIX 3: SUPPORTING INFORMATION FOR CHAPTER 4 ...... 300

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List of Tables

Table 2.1. Summary of 13 halogenated and organophosphorus flame retardants measured in air and dust in an e-waste dismantling facility in Ontario, Canada. Detection frequencies for all target compounds in air and dust samples were 100%...... 58 Table 2.2. Comparison of concentrations of 13 halogenated and organophosphorus flame retardants measured in air and dust reported for indoor e-waste handling facilities in a Canadian facility and in various countries………………………………………………………………….59 Table 2.3. Estimated occupational exposure of male and female workers in a Canadian e-waste recycling facility via air inhalation, dermal absorption and dust ingestion. Details of exposure factors and calculations are provided in section 2.5, and Tables S4 and S5……………………..64 Table 3.1. Detection frequencies (DF), geometric mean (GM), median, minimum (Min) and maximum (Max) concentrations (ng dm-2 h-1) of 27 FRs detected in more than 60% of paired silicone brooches, wristbands and armbands…………………………………………………...104 Table 3.2. Correlations between concentrations (ng m-3 for personal active air samplers and ng dm-2 h-1 for silicone brooches, wristbands and armbands) of FRs with detection frequencies >60% in paired sample matrices as indicated by Spearman’s correlation coefficients (rho). Numbers in bold indicate a statistically significant correlation with p-value < 0.05………………………...108 Table 3.3. Spearman’s rank correlation coefficients (rho) and p-values (p) for OPEs levels measured in brooches (n = 45) and wristbands (n = 28) with OPE metabolites in their paired specific-gravity-corrected urine samples (n = 45)………………………………………….…...111 Table 4.1. Detection frequencies (DF), median, minimum and maximum values of selected 9 phthalates and 4 OPEs collected by active air samplers, silicone brooches and wristbands from nail salon technicians in Canada. Only compounds with detection frequencies > 70% in more than 2 samples types are presented…………………………………………………………………..147 Table 4.2. Spearman’s correlation coefficients (rho) and p-values (p) for the concentrations of selected phthalates and OPEs with detection frequencies >70% in paired sample matrices. Numbers in bold are statistically significant with p-value < 0.05……………………………….153 Table 5.1. Summary of generic sampling rates (m3 day -1 dm-2) of silicone passive samplers used for measuring SVOCs exposure via air in various indoor environments………………………..181

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List of Figures

Figure 2.1. Average concentrations (n = 2) of Ʃ8 HFRs and Ʃ5 OPEs on size-segregated air particles (10 fractions, 0.056 - 18µm) collected by a MOUDI sampler at a central workplace from a Canadian e-waste recycling facility………………………………………………………...….60 Figure 3.1. Log-transformed BDE-209 in blood plasma versus (a) log-transformed BDE-209 in brooch (n = 45), (b) log-transformed BDE-209 in wristband (n = 28), and (c) log-transformed BDE-209 in armband (n=9). Rho is Spearman’s rank correlation coefficient and p is the probability values………………………………………………………………………………………...... 110 Figure 4.1. Boxplots for concentrations of selected phthalates with detection frequencies >70% in air collected by active air samplers according to number of services performed for each worker- day (including any services, manicure, pedicure, artificial nails and others). The horizontal line in the boxes is the median, the top and bottom of the boxes are 75th and 25th percentiles, respectively. The top and bottom whiskers are the maximum and minimum values, respectively. ▲Any services included at least one of the following services: manicure, pedicure, artificial nail and other services. *Other services included eyebrows/eyelash service, waxing, facial service and massage……………………………………………………………………………………...…152 Figure 4.2. Boxplots for concentrations of selected phthalates with detection frequencies >70% in air collect by active air samplers according to number of services performed for each worker- day (including any services, manicure, pedicure, artificial nails and others). The horizontal line in the boxes is the median, the top and bottom of the boxes are 75th and 25th percentiles, respectively. The top and bottom whiskers are the maximum and minimum values, respectively. ▲Any services included at least one of the following services: manicure, pedicure, artificial nail and other services. *Other services included eyebrows/eyelash service, waxing, facial service and massage…………………………………………………………………………………..…….153 Figure 5.1. Main factors proposed to influence the exposure measurements collected using passive samplers……………………………………………………………………………..... 182

List of Abbreviations

ASE: Accelerated solvent extractor

ECNI: Electron capture chemical ionization

GC: Gas chromatography

GC-MS: Gas chromatography mass spectrometry

KOA: Octanol-air partition coefficient n: Sample size

NHFRs: Novel halogenated flame-retardants

NCI: Negative chemical ionization

NSERC: Natural Sciences and Engineering Research Council of Canada

OPEs: Organophosphate esters

PAEs: Phthalate esters

PAHs: Polycyclic aromatic hydrocarbons

PBDEs: Polybrominated diphenyl ethers

PDMS: Polydimethylsiloxane

QA/QC: Quality Assurance and Quality Control

Rs: Sampling rates

Rs′: Sampling rates normalized to surface area

SVOCs: Semivolatile organic compounds

Chapter 1 – Introduction and literature review

1.1 Motivation

People are exposed to a complex mixture of natural and anthropogenic hazardous chemicals through both occupational exposure and interactions with the ambient environment.

Flame retardants (FRs) and plasticizers are two groups of semi-volatile organic compounds

(SVOCs) in this complex mixture to which people are exposed. Environmental exposure to both

FRs and plasticizers has been associated with a range of adverse human health effects including neurodevelopmental and reproductive effects (Braun et al., 2014; Factor-Litvak et al., 2014;

Harley et al., 2010; North et al., 2014).

A first step towards minimizing exposures to hazardous SVOCs is documenting levels to which people are exposed. For inhalation, active air samplers have been considered to be the “gold standard” however they are cumbersome to deploy, intrusive and relatively expensive to operate.

Passive samplers have emerged as a convenient, unobtrusive and cheaper alternative to active samplers, but knowledge of which routes of exposure they actually sample for and how best to deploy passive samplers for obtaining the reliable and comparable concentrations to the traditional air sampling methods is incomplete.

The challenge in effectively measuring levels of SVOCs, such as FRs and plasticizers, with passive samplers coupled with the lack of information on occupational exposure in e-waste handling facilities and nail salons, provided the motivation for my thesis. My doctoral research aimed to provide the first Canadian data on occupational exposures to FRs and plasticizers in e- waste facilities and nail salons. The thesis also aimed to develop robust, convenient and reliable personal passive sampling devices including silicone rubber (polydimethyl siloxane or PDMS)

1 brooches, armbands and wristbands, as well as to test their use in the exposure assessments of workers in e-waste handling facilities and nail salons. These personal passive samplers were tested in case studies for measuring FRs and plasticizers exposure in workplace settings over a short deployment time of 8 hours. The ultimate goal of the research was to develop a robust passive measurement method and to measure exposures, thereby contributing to a better understanding of exposure pathways of e-waste dismantlers and nail salon workers. The hope is that the information gained can be used to improve exposure monitoring, leading to reductions in exposure and improvements in the health and safety of workers.

1.2 Flame retardants and plasticizers

1.2.1 Background

Flame retardants (FRs) including polybrominated diphenyl ethers (PBDEs), novel flame retardants (NFRs), and organophosphorus esters (OPEs) are added to materials to meet flammability standards (Zota et al., 2008). FRs are commonly used in the manufacturing of many household products such as furniture, electronics and building materials (Abbasi et al. 2015; Van

Der Veen and de Boer 2012). Polybrominated diphenyl ethers (PBDEs) are one group of FRs that have been widely used since the 1970s (Abbasi et al., 2015). The production of two PBDE commercial mixtures, penta- and octa-PBDE, was banned by European Union in 2003 and voluntarily phased out in 2004 in the United States because of their environmental ubiquity and toxicity (Venier et al., 2012). In Canada, the production and use of these two mixtures in new products was prohibited in 2008 (Government of Canada, 2012) . The deca-BDE mixture was phased out in North America, Europe and Japan for similar reasons (it is still used extensively in

China for the Chinese market).

There is increasing evidence that many FRs can have several adverse health effects.

Endocrine disruption effects of many FRs have been documented in vitro (Hill et al., 2018; Li et al., 2010), in vivo (Lilienthal et al., 2006; Pinson et al., 2016), and in newborns and children

(Jacobson et al., 2016; Vuong et al., 2018). Human exposure to PBDEs at ambient levels has been related to several neurodevelopmental outcomes such as reduced IQ and externalizing behavior problems (Lam et al., 2017; Vuong et al., 2017), abnormal migration of testes (Goodyer et al.,

2017) and alterations in timing to puberty (Holmes et al., 2014). In response to controls implemented for PBDEs, industry has shifted to using alternative FRs, such as novel halogenated flame retardants (NHFRs) and organophosphate ester (OPEs) which are also used as plasticizers.

Widespread human exposure to those replacement FRs is currently apparent (Gravel et al., 2020;

Okeme et al., 2018d; Ospina et al., 2018; Vykoukalová et al., 2017; Yang et al., 2018). Various toxicity and epidemiological studies reported that exposure to some OPEs is associated with reproductive adverse effects, such as poor outcomes of in vitro fertilization (Carignan et al., 2018,

2017), degradation of semen quality (Meeker et al., 2013; Meeker and Stapleton, 2009) and increase in risk of papillary thyroid cancer in adult (Hoffman et al., 2017b). However, there are still little information exists regarding the toxicity and exposure potential of the replacement FRs.

Plasticizers such as phthalate esters (PAEs) and some OPEs are widely used to provide elasticity, transparency and durability to plastics (Graham, 1973; Rakkestad et al., 2007). Around

80% of those plasticizers are di(2-ethylhexyl) phthalate (DEHP), diisononyl phthalate (DiNP), diisodecyl phthalate (DiDP) and di-2-propyl heptyl phthalate (DPHP) (Godwin, 2017). Phthalates are also used as plasticizers and solvents in cosmetics and personal care products, waxes, lubricants, packaging and building materials (Koniecki et al., 2011; Snedeker, 2014; Veen and

Boer, 2012; Young et al., 2018). Lighter molecular weight phthalates containing carbon chain lengths of C1-4 (e.g., dimethyl, dietyl, dipentyl and dibutyl phthalate or DMP, DEP, DPP and

DBP, respectively) are used as solvents with applications in cosmetics, creams, fragrances and etc. (Godwin, 2010). Exposure to DEHP, diisobutyl phthalate (BiBP), DiNP and benzyl butyl phthalate (BzBP) hasmoderate to strong associations with adverse male reproductive effects with endocrine modulation as the mode of action (Radke et al., 2018). Other human adverse health outcomes related to phthalates exposure are low birth weights (Lenters et al., 2016) and asthma

(Wallner et al., 2016) as well as atopic dermatitis (Kim et al., 2017). The literature for these other outcomes is inconsistent (Ait et al., 2014; Bornehag and Nanberg, 2010; Callesen et al., 2014).

DEHP has been classified as a potential human carcinogen by the International Agency for

Research on Cancer (IARC Working Group on the Evaluation of Carcinogenic Risks to Humans,

2013) and a presumed or suspected reproductive hazard to humans by the U.S. National

Academies of Sciences (National Academies of Sciences Engineering and Medicine, 2017).

Because of those adverse health effects, European Union classified DBP, BzBP and DEHP as reproductive toxicants in 2014, and after 2019, their use has been restricted to less than 0.1% by weight in children’s toys, cosmetic and electronic products (European Commission, 2014). In the US, the use of di-n-butyl phthalate (DnBP), BzBP and DEHP in childcare products and DiNP in mouthing toys has been limited to no more than 0.1%, starting in 2018 (Consumer Product

Safety Commission, 2008). In Canada, DEHP was added to Cosmetic Ingredient Hotlist as a prohibited ingredient which should not be present in cosmetic products as of 2019 (Government of Canada, 2019). Concentrations of DEHP, DnBP and BzBP were also limited to 0.1% in child care articles in Canada (Goverment of Canada, 2017). The same level for DiNP and DiDP was set

4 for their use in vinyl toys and other products that could be mouthed by a child under 4 years old

(Goverment of Canada, 2017).

1.2.2 Exposure pathways to FRs and plasticizers

Exposure to SVOCs (including FRs and plasticizers) can occur during the manufacturing, use and/or disposal of products containing these chemicals in occupational and ambient environments (Fisher et al., 2019; Philippat et al., 2016; Yang et al., 2020a). The risk of exposure to these compounds from ambient environments is generally lower than in occupational settings that can contain many emission sources. For example, the exposure to FRs via outdoor soils surrounding electronic waste sites (Ma et al., 2009) is much lower than from indoor dust levels of

FRs reported from electronic waste recycling sites where electronic waste is dismantled and proceesed (Muenhor et al., 2010; Wu et al., 2016; Zheng et al., 2015).

Human exposure to FRs and plasticizers occurs through inhalation, dermal absorption, and ingestion pathways (including dietary and non-dietary ingestion) because these compounds partition between different phases in the air, surfaces (including skin) and settled dust (Gong et al., 2016; Mäkinen et al., 2009; Tue et al., 2013; Weschler and Nazaroff, 2008). In order to reduce exposures, there is a need to evaluate the potential sources and exposure pathways of SVOCs (e.g.,

FRs and plasticizers).

Inhalation exposure can occur through breathing of contaminants emited from diffuse sources into air (Xu et al., 2010). In the indoor environment, inhalation is an important pathway for exposure to SVOCs, particularly to more volatile SVOCs such as some polychlorinated biphenyls (PCBs) and OPEs (Marek et al., 2017; Schreder et al., 2016; Tran et al., 2017). Since

SVOCs have vapour pressures ranging from 10-9 to 10 Pa (10-14 to 10-4 atm) at 25℃ and boiling

5 points less than 100℃ (Bidleman, 1988; Weschler and Nazaroff, 2008), SVOCs in air are present in both gas and particle phases. In a study assessing multiple exposure pathway to phthalates,

Giovanoulis et al. ( 2018) found that inhalation is more important for lower molecular weight phathalates and negligible for higher molecular weight phthalates. This difference in pathways is due to SVOCs with higher molecular weights (e.g., DEHP, BDE-209, etc) sorbing to dust and surfaces while SVOCs with lower molecular weights (e.g., DEP, BDE-47, etc.) are more likely to be found in the gas phase (Okeme et al., 2016b; Saini et al., 2015; Tran et al., 2017). Inhalable

SVOCs in both gas and particle phases can deposit in the human respiratory tract and become bioaccessible (Wei et al., 2018).

Inhalation of airborne particles is also a function of particle size (Richman et al., 2018).

Particles desorb a fraction of their SVOCs when travelling along the human respiratory tract from the head region to tracheobronchial and then aveolar region of the lung (Liu et al., 2017; Richman et al., 2018). Fine particles with an aerodynamic diameter of less than 2.5 µm (PM2.5) pose higher risks to respiratory health effects than coarse particles with diameters ranging from 2.5 to 10 µm in diameter (PM10) (Lippmann, 1998; Schwartz and Neas, 2000). Long-term exposure to particulate matter is associated with cardiovascular and respiratory diseases (Pelucchi et al., 2009;

Pope III, 2002). Several studies have reported the size distribution of SVOCs (e.g, PAHs, PCBs,

PBDEs, etc.) in ambient air (Allen et al., 1996; Delgado-Saborit et al., 2014; Okonski et al., 2014).

Only a few studies have reported indoor air levels of SVOCs in different size fractions, particularly in PM2.5 (Cao et al., 2014; Kim et al., 2015; Richman et al., 2018). Better knowledge of the distribution of SVOCS according to particles size in indoor environment is crucial to improve the understanding of human exposure and the potential for adverse health effects from inhaling these particles.

Unlike inhalation, dermal absorption has received the minimal attention as a human exposure pathway. Dermal absorption of SVOCs, including FRs and plasticizers, can occur following direct air-to-skin partitioning (Andersen et al., 2018; Weschler and Nazaroff, 2014,

2012), adherence of dust to the skin (Giovanoulis et al., 2018; Guo and Kannan, 2011), and from transfer from clothing containing the contaminants (Morrison et al., 2016; Saini et al., 2016).

Further, SVOCs such as phthalates, which are used in personal care products, can be directly absorbed through skin after application (Koniecki et al., 2011; Romero-Franco et al., 2011).

Several studies have reported dermal absorption as an negligible pathway compared to inhalation and ingestion pathways for many SVOCs (e.g., PBDEs, NHFRs, phthalates, etc.), in both non- occupational (e.g., home, school, office, etc.) and occupational environments (e.g., e-waste recycling facilities) (Giovanoulis et al., 2018; Tue et al., 2013; Yang et al., 2020a). However, the importance of dermal absorption pathway may be underestimated because of the assumptions of various factors (e.g exposed surface areas, the role of clothing) in dermal absorption calculations and a lack of information of SVOCs uptake across skin (e.g, NHFRs).

The oral pathway, including from diet, hand-to-mouth transfer and dust ingestion, is commonly considered as the dominant pathway of exposure to SVOCs in many indoor environments (Giovanoulis et al., 2018; Nguyen et al., 2019; Tue et al., 2013; Yang et al., 2020a).

Many of food products (e.g, poultry, meat, fish, etc.) have been reported as a contributor to exposure of FRs and plasticizers (Fraser et al., 2009; Schettler, 2006; Shi et al., 2009). Dietary ingestion is an important route of exposure to SVOCs (e.g PBDEs) in non-occupational environments (e.g. homes) (Fromme et al., 2016; Tue et al., 2013). However, diet was found to be negligible for exposure to PBDEs at workplaces (e.g., e-waste facilities) where workers processed and handled sources with high levels of PBDEs (Tue et al., 2013). Further, dust

7 ingestion has been found to be the main exposure pathway to FRs in dusty e-waste recycling facilities (Muenhor et al., 2010; Nguyen et al., 2019; Tue et al., 2013) while diet had the largest contribution to total daily intake of those compounds in less dusty environment such as homes

(Tue et al., 2013). Hand-to-mouth has been considered as the main source of exposure in toddlers or young childer due to their tendency to pick up dust and their frequent hand to mouth contact

(Stapleton et al., 2008b). However, in the study that assessed human residential exposure to phthalates among Canadian adults, Yang et al. (2020a) found that hand-to-mouth contributed to nearly 15% to total exposure, higher than dermal absorption (<1%) and inhalation (2 %), but lower than dust ingestion (82%).

Ingestion of house and workplace dust containing SVOCs has been reported as the dominant pathway of human exposure in various indoor environments (Giovanoulis et al., 2018;

Nguyen et al., 2019; Tue et al., 2013; Yang et al., 2020a). Nguyen et al. (2019) and Tue et al.

(2013) reported that dust ingestion contributed to >60% of total exposure to FRs among Canadian and Vietnamese e-waste dismantlers, respectively. Further, in the OEHS-Homes study, Yang et al. (2020a) found that dust ingestion of phthalates contributed most (82%) to non-dietary pathways. Health risks are potentially higher for workers who work in the dusty workplaces such as e-waste recycling facilities than homes since dust concentrations and the concentrations of hazardous compounds in that dust are higher in these environments than in non-occupational environments (Tue et al., 2013).

1.3 Measurement of exposure to FRs and plasticizers

Studies of exposure to FRs and plasticizers have considered potential non-dietary routes of exposure: inhalation, dust ingestion, dermal uptake and hand-to-mouth transfer. Methods have

8 been developed to investigate each of these exposure pathways separately, but it would be advantageous to develop a sampler that could consider multiple routes of exposure at the same time. Measuring exposure pathways helps to identify the main route of exposure. This information can be used to then reduce exposures. The sampling can be conducted at stationary and personal levels depending on the research questions, by using active and passive sampling approaches.

1.3.1 Active air sampling

The first step in estimating inhalation exposure to chemical hazards in an occupational setting is often to measure the air concentrations of these compounds in workplaces. Active air sampling is the most commonly used technique to assess the exposure of airborne compounds

(Gravel et al., 2019c; Mäkinen et al., 2009; Rosenberg et al., 2011). Since the volume of air sampled is known, active sampling can provide quantitative estimates of inhalation exposure to gas- and particle-phase chemicals. Stationary air samplers have been used in many studies, however, personal samplers are more representative of an individual’s exposure as they are mobile monitors that move with the person, sampling in the breathing zone throughout the sampling period (Bohlin et al., 2007; Cherrie, 2003). A person’s activities create a personal cloud or the

“Pig Pen” effect of contaminants in close proximity to one’s body, may lead to increased exposure

(Allen et al., 2007; Rodes et al., 1991). The most popular personal samplers are active air devices consisting of an air pump with a filter to capture particle-sorbed chemicals and an absorption tube to capture gas-phase chemicals. This type of samplers has been used for measuring the air levels of FRs and plasticizers in work environments (Mäkinen et al., 2009; Rosenberg et al., 2011) but is more cumbersome, relatively expensive to operate and requires energy (a power source).

1.3.2 Passive sampling

Passive air samplers (PAS) offer an alternative to active sampling that avoids some of these challenges. PAS devices, collect gas-phase chemicals due to advection and molecular diffusion, and particle-sorbed chemical by impaction (P. Bohlin et al., 2014; Shoeib and Harner,

2002). PAS do not require electricity, frequent calibration or maintenance, there is also no noise generated, and they are low cost (Bohlin et al., 2010b; Okeme et al., 2018a). Further, PAS are less obtrusive to wear compared to personal active air samplers, particularly when workers perform heavy and mobile work activities. However, the accuracy of PAS can be a drawback of this technique since the passive sampler-derived air concentrations are only accurate within a factor of 2-3 compared to corresponding active air samplers (Harner et al., 2006; Shoeib and Harner,

2002). PAS also require longer deployment time to achieve analytical detection. Further, PAS cannot distinguish between gas- and particle-phase compounds. Hence, PAS need to be calibrated against active air samplers to derive uptake rates of gas- and particle phase compounds (Bohlin et al., 2010b; Okeme et al., 2016b; Saini et al., 2015; Shoeib and Harner, 2002), In addition, PAS can also be calibrated by using depuration comounds (Gioia et al., 2006; Gouin et al., 2005;

Moeckel et al., 2009), but this method is restricted to gas-phase uptake (Moeckel et al., 2009).

Further, sampling effiency for particles using PAS is still not well studied.

Types of PAS for measuring SVOCs exposure

Bohlin et al. (2010a) introduced mini-polyurethane foam (mini-PUF) as a personal passive sampler for collecting SVOCs during a working day at an alloy industrial site and a coke plant.

Results suggested that the estimated air concentrations collected from mini-PUF were within 2 –

150 % from the corresponding active sampler during an 8-hour deployment. No other studies have

10 tested the mini-PUF to date. The design of mini-PUF, without a housing to protect the sampler, may reduce the robustness of this sampling technique since the samplers may be damaged during the intensive work activities.

Silicone rubber or polydimethylsiloxane (PDMS) has been introduced to measure SVOCs in air. PDMS has the greatest efficiency for gas- vs particle-phase SVOCs (Okeme et al. 2016).

Okeme and Yang et al. (2018) found that PDMS and PUF-derived air concentrations, when deployed, as stationary samplers, were not statistically different for gas-phase SVOCs. The silicone brooch were introduced as a promising personal passive air sampler to capture personal exposure to SVOCs over a total deployment time of approximately 24 hours (Okeme et al., 2018a).

While the brooch design looks promising, it has only been tested in a pilot study with small sample size. All PBDEs and NFRs were less than limit of detection when the brooch was deployed in home and office environments (Okeme et al., 2018b). Hence, further study is needed to quantify the range of inter-individual variability and to test the use of brooch to measure other groups of

SVOCs (such as PBDEs and NFRs).

Silicone rubber has also been used as a wristband sampler to assess human exposure to

SVOCs. O’Connell et al. (2014) used silicone wristbands to qualitatively assess exposure of roofers to PAHs. Commercial silicone wristbands were also used to measure personal exposure to organophosphate FRs and plasticizers (Hammel et al., 2016). Hammel et al. (2016) found that silicone wristbands may be an improved sampling method for estimating exposure to OPEs over a long time period such as a week or more and can capture inhalation exposure to some compounds compared to hand wipes. The US nail salon study of Craig et al. (2019) reported that silicone wristbands (n = 10) were able to collect a few phthalates and OPEs during 8-hour working period.

However, since this was a pilot study, the sample size was small to confirm the reliability and

11 robustness of the technique using wristbands as a tool for assessing occupational exposures to

SVOCs.

Relationships between levels of SVOCs in silicone passive samplers and biomarkers

Previous studies have found moderately significant correlation between levels of some

SVOCs accumulated on wristbands and their biomarkers in serum (Hammel et al., 2018) and urine

(Craig et al., 2019; Dixon et al., 2018; Hammel et al., 2016). Hammel et al. (2018) found that the relationship between levels of BDE-47, -99, -100, and -153 on wristbands and in respective serum biomarkers were moderately significant. Decabromodiphenyl ethane (BDE-209) were found in all wristbands in the study of Hammel et al. (2018). However, no correlation between BDE-209 levels on wristbands and serum biomarkers were reported because of the low detection frequency

(17%) of BDE-209 in serum. In a five-day study at home environments (Hammel et al., 2016) , only tris(1-chloro-2-isoprpyl) phosphate (TCIPP) and tris(1,3-dichloroisopropyl)phosphate

(TDCIPP) levels on wristbands were significantly correlated to their corresponding urinary metabolites. However, there were no correlations between levels of triphenyl phosphate (TPhP) and mono-substituted isopropyl triphenyl phosphate (mono-ITP) and their urinary metabolites.

The lack of correlation was partly due to these two compounds originating from pathways and sources poorly captured by wristbands such as diet. Using wristbands to measure occupational exposure in short deployment time within 8 hours can potentially minimize the influence of diet on levels of OPE metabolites but accumulating sufficient chemical mass in 8 hours can be problematic (Craig et al., 2019). These uncertainties point to research gaps in the use of silicone wristbands in assessing occupational exposure to SVOCs.

1.4 Occupational exposure measurements to FRs and plasticizers

Two occupational environments were selected to assess the performance of the PAS in measuring FRs and plasticizers, namely electronic waste or e-waste recycling facilities for FRs and nail salons for plasticizers. These occupational environments were chosen because of the concern of the relatively high levels of FRs and plasticizers exposure in these settings compared to ambient and non-occupational settings and a lack of exposure data about occupational exposure of those chemicals in Canada. They are also very different occupational environments, offering an opportunity to assess the versatility of the silicone PAS.

1.4.1 Electronic waste recycling facilities

The mass of e-waste produced globally is increasing dramatically and is expected to reach

120 million tonnes annually by 2050 (UNEP, 2019). National numbers have suggested that the amount of e-waste processed across Canada increased seven times in the period of 2002-2012 from 10,250 to 71,300 tonnes/y (Statistics Canada, 2016). One occupational hazard when handling e-waste is FRs which are added into electronic and electrical equipment such as motherboards, transistors, capacitors and battery casings (Abbasi et al., 2016, 2015; Hazrati and Harrad, 2006;

UNEP, 2010; Vojta et al., 2017). Given the prevalence of FRs in electronic devices, it is likely that e-waste workers could receive higher exposures to these compounds compare to workers in other workplaces (Gravel et al., 2019c; Sjödin et al., 2001).

Twenty years ago, the Swedish occupational study done by Sjödin et al. (2001) found that exposure of workers to airborne FRs (personal sampling) in e-waste facilities was at least an order of magnitude higher than those in other workplaces such as a circuit board factory and a computer repair business. Along that line, the study of Gravel et al. (2019c) in Quebec reported that workers 13 in e-waste recycling facilities were exposed to at least two times higher air concentrations of FRs compared to those in commercial recycling facilities. E-waste workers, who manually dismantle older and some newer electronics, are at risk of exposure to both PBDEs and replacement FRs

(Gravel et al., 2019c; Stubbings et al., 2019a). Recently, Beaucham et al. (2018) found that dismantlers working in the shredder/sorter area of a US e-waste facility were exposed to higher levels of FRs than workers in other locations in the facility. Similarly, Gravel et al. (2019) reported that workers doing manual dismantling and baler operation were exposed to some of the highest concentrations of PBDEs and chlorinated FRs compared to workers performed other tasks such as forklift operating, manual handling and supervision.

Most studies of FR exposure via air and dust in e-waste facilities have been done in the informal e-waste facilities at low- and middle-income countries such as China (Xu et al., 2015;

Zheng et al., 2015), Pakistan (Iqbal et al., 2017) , Bangladesh (Wang et al., 2020), Nigeria (Sindiku et al., 2015), Thailand (Muenhor et al., 2010) and Vietnam (Tue et al., 2013). Only few studies have been conducted to examine occupational exposure of e-waste recycling workers in formal e- waste facilities in developed countries, notably in Finland, Sweden, US and Canada (Beaucham et al., 2018; Gravel et al., 2019c; Rosenberg et al., 2011; Sjödin et al., 2001). Evidence is now showing that exposure to some FRs can be associated with changes in hormone levels (Gravel et al., 2020) and oxidative stress levels (Lu et al., 2017) of e-waste workers in formal and informal e-waste sites. Further, although FRs such as PBDEs have been prohibited for in use new products under regional and national regulations as well as Stockholm Convention (Blum et al., 2019), recent studies (Beaucham et al., 2018; Gravel et al., 2019c; Stubbings et al., 2019b) found that e- waste worker continue to handle older products and thus are exposed to elevated levels of banned and persistent FRs .

1.4.2 Nail salons

Nail salons have become prevalent in North America. Most of them are small businesses employing nail technicians from vulnerable population (e.g., new immigrants, mostly woman)

(Federman et al., 2006; UCLA Labor Center, 2018). The numbers of licensed nail technicians in the US grew three times from 35,500 in 1987 to 104,020 in 2017 (Federman et al., 2006; United

States Department of Labor, 2017). Toronto Public Health estimated there were approximately

1400 licensed establishments in the City of Toronto alone providing nail services in 2019 (City of

Toronto, 2019).

Nail technicians are at increased risk of skin and respiratory diseases related to workplace exposures (Cahill et al. 2015; Pesonen et al. 2015; Quach et al 2013). Some phthalates and triphenyl phosphate (TPhP) are known ingredients of nail polish (Koniecki et al., 2011;

Mendelsohn et al., 2016). Exposure to these compounds have been associated with adverse reproductive and development effects (Carignan et al. 2017; Factor-Litvak et al. 2014b). A recent pilot study in US nail salons showed that the urinary metabolites levels of phthalates and among nail technicians were lower than among the US adult population from the National Health and

Nutrition Examination Survey (NHANES) (Craig et al., 2019). However, previous studies found levels of phthalates in beauty salons were the highest from among various microenvironments such as homes, offices, kindergartens, etc. (Tran et al., 2017; Tran and Kannan, 2015). Little information exists regarding the exposure potential of plasticizers in nail salons. No studies of the exposure of nail salon workers to FRs and plasticizers have been conducted in Canada.

1.5 Structure of thesis

The ultimate goal of the research was to develop a robust passive measurement method to improve exposure monitoring, and to measure exposures in order to provide evidence that can inform reductions in exposure and improvements in worker health. To achieve that goal, my thesis research address four research questions (RQs):

➢ RQ1: What are levels of FR exposure via non-dietary pathways to workers in Canadian

electronic waste (e-waste) recycling FRs?

➢ RQ2: What are levels of FRs and plasticizers exposure via air non-dietary pathways to

workers in nail salons?

➢ RQ3: Are levels of FRs and plasticizers in personal passive samplers comparable to those

levels in the reference personal active air samplers?

➢ RQ4: Are levels of FRs in personal passive samplers associated with levels of these

compounds and their metabolites in biological samples?

This thesis is organized into five chapters, with the first presenting the introduction and the last as conclusions and recommendations for future work. The research is presented in three chapters of which two are published, and the third will be submitted for publication. These three chapters address the following objectives and that were developed to answer the research questions above.

Chapter 2: Exposure of Canadian electronic waste dismantlers to flame retardants (Addressing

RQ 1)

The goal of this study was to advance the understanding of occupational exposure to FRs in e-waste recycling industry by documenting the exposure levels of FRs among e-waste workers via non-dietary pathways. This chapter reports on measured air and dust concentrations of 13 abundant FRs in a formal e-waste dismantling facility (Ontario, Canada) and the associated estimates of worker exposure via inhalation, dermal absorption, and dust ingestion in this facility.

Results indicated Canadian e-waste workers in an Ontario facility were at risk to expose to many

FRs in respirable particles (<~3 μm). Exposure estimates indicated that dust ingestion (accounted for 63% of total FR exposure) was the main exposure route among non-dietary pathways. Further, some air and dust concentrations as well as some estimated exposures in this formal facility in a high-income country exceeded those from informal e-waste facilities located in low- and middle- income countries. Results of this chapter indicated the need to better control exposure to FRs during e-waste handling in order to minimize occupational exposure. Furthermore, results here called for more attention in chemical management to account for exposures to e-waste recyclers who mostly handle old electronics containing many banned FRs.

Reference: Nguyen, L.V., Diamond, M.L., Venier, M., Stubbings, W.A., Romanak, K.,

Bajard, L., Melymuk, L., Jantunen, L.M. and Arrandale, V.H., 2019. Exposure of Canadian electronic waste dismantlers to flame retardants. Environment International, 129: 95-104.

For this chapter, I contributed to designing the sampling campaign in consultation with

Prof.s Miriam Diamond, Victoria Arrandale, and co-authors. I conducted sampling with Prof.

Victoria Arrandale, was responsible for sample preparation, and I coordinated the distribution of samples to collaborators for analysis. Active air and dust samples were extracted and analyzed by

Dr. Marta Venier and co-workers at Indiana University, USA. MOUDI samples were extracted and analyzed by Dr. Liisa Jantunen and Sarah Bernstein at Environment and Climate Change

Canada. I was responsible for data analysis and writing the initial draft of the paper with guidance from Prof.s Victoria Arrandale and Miriam Diamond. All co-authors provided suggestions regarding interpretation of data and were also involved in reviewing the manuscript.

Chapter 3: The use of silicone passive samplers for measuring exposure of e-waste workers to flame retardants (Addressing RQ 1, 3 and 4)

This goal of this study was to evaluate the use of silicone personal passive samplers to measure occupational exposure to FRs in e-waste recycling facilities for assessing worker’s internal and external exposure. Results from silicone passive samplers, worn as brooches, wristbands and armbands, were reported and compared with the reference personal active air samplers and biomarkers (plasma and urine). Concentrations of OPEs on silicone brooches and wristbands were compared to the corresponding concentrations in active air samples and their urinary metabolites. Concentrations of PBDEs on silicone brooches, wristbands and armbands were compared to the corresponding concentrations in active air samples and concentrations of

PBDEs in plasma. The moderate and statistically significant correlation was found between BDE-

209 concentrations in brooches and wristbands with BDE-209 levels in plasma. There were weak and insignificant relationship between OPEs in brooches and wristbands versus their urinary metabolites (Spearman’s rho = 0.008 – 0.34, p-values > 0.05). Results indicated that the brooch was the most reliable alternative to active air sampler for assessing inhalation exposure of FRs since brooches compared to wristband and armbands showed stronger correlations to active air samplers for most FRs, except from Tris(2-chloroethyl) phosphate (TCEP) and TCIPP,

(Spearman’s rho = 0.46 to 0.82, p < 0.05). Based on those results, the generic sampling rate of the brooch (19 ± 11 m3day-1dm-2) was also estimated for a dusty occupational setting like e-waste recycling facilities. Further, results of this chapter suggested personal passive samplers did not appear to be promising indicators for internal exposure levels to most FRs over ~8 working hours in a dusty occupational setting.

Reference: Nguyen, L.V., Gravel, S., Labreche, F., Bakhiyi, B., Verner, M-A., Zayed, J.,

Jantunen, L.M., Arrandale, V.H. and Diamond, M.L, 2020. Can silicone passive samplers be used for measuring exposure of e-waste workers to flame retardants? Environmental Science and

Technology, 54 (23) : 15277 – 15286.

For this chapter, I designed the silicone wristbands and armbands as well as participated in the designing the sampling campaign, specifically the deployment of the person passive samplers, in consultation with Prof.s Miriam Diamond, Victoria Arrandale and co-authors. Sarah

Bernstein and I were responsible for sample preparation. Sampling was conducted by myself and collaborators at the Institut de recherche Robert-Sauvé en santé et en sécurité du travail (IRSST) in Montreal, Quebec. Personal passive samplers (brooches, wristbands and armbands) were extracted, and all sample types were analyzed for PBDEs and NFRs by myself at University of

Toronto. Extraction of the OVS samplers and OPEs analysis for all sample types was conducted by Dr. Liisa Jantunen and Sarah Bernstein at Environment and Climate Change Canada.

Additionally, Dr. Congqiao Yang analyzed OVS samplers’ extracts for PBDEs and NFRs in the

Diamond lab. I was responsible for data analysis and writing the initial draft of the paper with guidance from Prof.s Miriam Diamond and Victoria Arrandale. All co-authors provided suggestions regarding interpretation of data and were also involved in reviewing the manuscript.

Chapter 4 Occupational exposure of Canadian nail salon workers to FRs and plasticizers including phthalates and organophosphorus esters (OPEs) (Addressing RQ 2 and 3)

This goal of this study was to report the exposure to FRs and plasticizers among nail salon workers in Toronto and to evaluate the use of silicone personal passive samplers to exposure. This study afforded a comparison of the use of these personal passive samplers in a less dusty workplace compared to the very dusty e-waste facilities tested. Results from silicone passive samplers worn as brooches and wristbands were reported and compared with the reference personal active air samplers. Concentrations of phthalates and OPEs on silicone brooches and wristbands were correlated to the corresponding concentrations in active air samples. This study did not include biomonitoring samples.

A wide range of phthalates and OPEs found in both active air and passive samplers within the relatively short deployment (~8 working hours) indicate that nail salon workers exposed to those hazardous chemicals during their workday. Among those compounds, high concentrations of TCEP and TCIPP that are not known to be used as an ingredients of personal care products used in the nail salons. Additionally, the thesis found that number of services workers performed were not associated with air concentrations of phthalates and OPEs collected by active air samplers (p values > 0.05). The thesis did not test the relationships between air concentrations with other potential cofounders (e.g., air exchange rates, sources of chemicals, etc.). Future studies should investigate on those relationships to advance the understanding of exposure characteristics in nail salon environment in order to minimize the occupational exposure to hazardous chemicals among nail salon workers. Further, for targeted phthalates and OPEs, neither silicone brooches or wristbands showed the strong and statistically significant correlations to active air samplers (p- values > 0.05). The inconsistency of results suggest brooch can be useful as a screening tool for

20 qualitative studies, but it is not yet a reliable quantitative tool for measuring SVOC exposure in the occupational settings.

Reference: Nguyen, L.V., Arrandale, V.H, Kalenge S, Kirkham TL, Holness D.L., and

Diamond, M.L. Occupational exposure to phthalates and organophosphorus esters among

Canadian nail technicians. Prepared for submission to Environmental Science and Technology.

This study is part of larger study of occupational exposure in Ontario nail salons coordinated through the Occupational Cancer Research Centre at Cancer Care Ontario. I designed the passive samplers and participated in sampling design, in consultation with all collaborators. I did pilot sampling with Prof. Victoria Arrandale and Ms. Sheila Kalenge. Sarah Bernstein and I were responsible for sample preparation forth the full study. Sample collection for the full study was done by collaborators at Occupational Cancer Research Centre. Sarah Bernstein extracted and analyzed active air samplers and I extracted and analyzed silicone brooches and wristbands.

I was responsible for data analysis and writing drafts of the paper with guidance from Prof.s

Miriam Diamond and Victoria Arrandale. All co-authors will provide suggestions regarding interpretation of data and were also involved in reviewing the manuscript.

References

10983. https://doi.org/10.1021/acs.est.5b03904 Abou-Elwafa Abdallah, M., Pawar, G., Harrad, S., 2016. Human dermal absorption of chlorinated organophosphate flame retardants; implications for human exposure. Toxicol. Appl. Pharmacol. 291, 28–37. https://doi.org/10.1016/j.taap.2015.12.004 ACGIH, 2018. TLVs ® and BEIs ® : Threshold limit values for chemical substances and physical agents biological exposure indices. American Conference of Governmental Industrial Hygienists, Cincinnati, OH, OH. ACGIH, 2001. Documentation of threshold limit values for substances in work environment. American Conference of Governmental Industrial Hygienists, Cincinnati, OH, OH. Ait, Y., Araki, A., Kawai, T., Tsuboi, T., Saito, I., Yoshioka, E., Kanazawa, A., 2014. Science of the Total Environment Associations of phthalate concentrations in fl oor dust and multi- surface dust with the interior materials in Japanese dwellings. Sci. Total Environ. 468–469, 147–157. https://doi.org/10.1016/j.scitotenv.2013.07.107 Akormedi, M., Asampong, E., Fobil, J.N., 2013. Working conditions and environmental exposures among electronic waste workers in Ghana. Int. J. Occup. Environ. Health 19, 278–286. https://doi.org/10.1179/2049396713Y.0000000034 Allen, J.G., McClean, M.D., Stapleton, H.M., Nelson, J.W., Webster, T.F., 2007. Personal Exposure to Polybrominated Diphenyl Ethers (PBDEs) in Residential Indoor Air. Environ. Sci. Technol. 41, 4574–4579. https://doi.org/10.1021/es0703170 Allen, J.O., Dookeran, N.M., Smith, K.A., Sarofim, A.F., Taghizadeh, K., Lafleur, A.L., 1996. Measurement of polycyclic aromatic hydrocarbons associated with size-segregated atmospheric aerosols in Massachusetts. Environ. Sci. Technol. 30, 1023–1031. https://doi.org/10.1021/es950517o Andersen, C., Krais, A.M., Eriksson, A.C., Jakobsson, J., Löndahl, J., Nielsen, J., Lindh, C.H., Pagels, J., Gudmundsson, A., Wierzbicka, A., 2018. Inhalation and Dermal Uptake of Particle and Gas-Phase Phthalates—A Human Exposure Study. Environ. Sci. Technol. 52, 12792–12800. https://doi.org/10.1021/acs.est.8b03761 Asante, K.A., Agusa, T., Biney, C.A., Agyekum, W.A., Bello, M., Otsuka, M., Itai, T., Takahashi, S., Tanabe, S., 2012. Multi-trace element levels and arsenic speciation in urine of e-waste recycling workers from Agbogbloshie, Accra in Ghana. Sci. Total Environ. 424, 63–73. https://doi.org/10.1016/j.scitotenv.2012.02.072 ATSDR, 2012. Toxicological Profile for Phosphate Ester Flame Retardants. ATSDR, 2005. Public Health Assessment Guidance Manual (2005 Update). Atlanta, Georgia. ATSDR, 2004. Toxicological profile for polybrominated biphenyl and polybrominated diphenyl ethers 1–599. Awasthi, A.K., Wang, M., Wang, Z., Awasthi, M.K., Li, J., 2018. E-waste management in India: A mini-review. Waste Manag. Res. 36, 408–414. https://doi.org/10.1177/0734242X18767038

Bakhiyi, B., Gravel, S., Ceballos, D., Flynn, M.A., Zayed, J., 2018. Has the question of e-waste opened a Pandora’s box? An overview of unpredictable issues and challenges. Environ. Int. 110, 173–192. https://doi.org/https://doi.org/10.1016/j.envint.2017.10.021 Balde, C.P., Forti, V., Gray, V., Kuehr, R., Stegmann, P., 2017. The global e-waste monitor 2017, United Nations University. https://doi.org/10.1016/j.proci.2014.05.148 Baldé, C.P., Wang, F., Kuehr, R., Huisman, J., 2015. The Global E-waste Monitor 2014: Quantitites, flows and resources. Bonn, Germany. https://doi.org/ISBN 978-92-808-4556-3 Bartkow, M.E., Booij, K., Kennedy, K.E., Müller, J.F., Hawker, D.W., 2005. Passive air sampling theory for semivolatile organic compounds. Chemosphere 60, 170–176. https://doi.org/10.1016/j.chemosphere.2004.12.033 Basel Convention, 2011. Electrical and electronic equipment when becoming waste (e-waste) such as personal computers, printers, televisions, mobile phones, refrigerators and air- conditioning units is one of the fastest growing waste streams in the world today. [WWW Document]. URL http://www.basel.int/Implementation/Ewaste/Overview/tabid/4063/Default.aspx (accessed 3.8.20). Beaucham, C.C., Ceballos, D., Page, E.H., Mueller, C., Calafat, A.M., Sjodin, A., Ospina, M., Guardia, M. La, Glassford, E., 2018. Evaluation of Exposure to Metals , Flame Retardants , and Nanomaterials at an Electronics Recycling Company 1–80. Behl, M., Hsieh, J.H., Shafer, T.J., Mundy, W.R., Rice, J.R., Boyd, W.A., Freedman, J.H., Hunter, E.S., Jarema, K.A., Padilla, S., Tice, R.R., 2015. Use of alternative assays to identify and prioritize organophosphorus flame retardants for potential developmental and neurotoxicity. Neurotoxicol. Teratol. 52, 181–193. https://doi.org/10.1016/j.ntt.2015.09.003 Behl, M., Rice, J.R., Smith, M. V., Co, C.A., Bridge, M.F., Hsieh, J.-H., Freedman, J.H., Boyd, W.A., 2016. Editor’s Highlight: Comparative Toxicity of Organophosphate Flame Retardants and Polybrominated Diphenyl Ethers to Caenorhabditis elegans. Toxicol. Sci. 154, 241–252. https://doi.org/10.1093/toxsci/kfw162 Bergh, C., Torgrip, R., Emenius, G., Östman, C., 2011. Organophosphate and phthalate esters in air and settled dust - a multi-location indoor study. Indoor Air 21, 67–76. https://doi.org/10.1111/j.1600-0668.2010.00684.x Betts, K.S., 2002. Rapidly rising PBDE levels in North America. Environ. Sci. Technol. 36, 50A-52A. https://doi.org/10.1021/es022197w Bi, C., Liang, Y., Xu, Y., 2015. Fate and Transport of Phthalates in Indoor Environments and the Influence of Temperature: A Case Study in a Test House. Environ. Sci. Technol. 49, 9674–9681. https://doi.org/10.1021/acs.est.5b02787 Bidleman, T.F., 1988. Atmospheric processes. Environ. Sci. Technol. 22, 361–367. https://doi.org/10.1021/es00169a002 Blum, A., Behl, M., Birnbaum, L.S., Diamond, M.L., Phillips, A., Singla, V., Sipes, N.S., Stapleton, H.M., Venier, M., 2019. Organophosphate Ester Flame Retardants: Are They a Regrettable Substitution for Polybrominated Diphenyl Ethers? Environ. Sci. Technol. Lett. 23

6, 638–649. https://doi.org/10.1021/acs.estlett.9b00582 Bohlin, P., Audy, O., Škrdlíková, L., Kukučka, P., Přibylová, P., Prokeš, R., Vojta, Š., Klánová, J., 2014. Outdoor passive air monitoring of semi volatile organic compounds (SVOCs): a critical evaluation of performance and limitations of polyurethane foam (PUF) disks. Environ. Sci. Process. Impacts 16, 433–444. https://doi.org/10.1039/C3EM00644A Bohlin, Pernilla, Audy, O., Škrdlíková, L., Kukučka, P., Vojta, Š., Přibylová, P., Prokeš, R., Čupr, P., Klánová, J., 2014. Evaluation and guidelines for using polyurethane foam (PUF) passive air samplers in double-dome chambers to assess semi-volatile organic compounds (SVOCs) in non-industrial indoor environments. Environ. Sci. Process. Impacts 16, 2617– 2626. https://doi.org/10.1039/C4EM00305E Bohlin, P., Jones, K.C., Levin, J.-O., Lindahl, R., Strandberg, B., 2010a. Field evaluation of a passive personal air sampler for screening of PAH exposure in workplaces. J. Environ. Monit. 12, 1437. https://doi.org/10.1039/c0em00018c Bohlin, P., Jones, K.C., Strandberg, B., 2010b. Field evaluation of polyurethane foam passive air samplers to assess airborne PAHs in occupational environments. Environ. Sci. Technol. 44, 749–754. https://doi.org/10.1021/es902318g Bohlin, P., Jones, K.C., Strandberg, B., 2007. Occupational and indoor air exposure to persistent organic pollutants: A review of passive sampling techniques and needs. J. Environ. Monit. 9, 501. https://doi.org/10.1039/b700627f Bornehag, C.G., Nanberg, E., 2010. Phthalate exposure and asthma in children 33, 333–345. https://doi.org/10.1111/j.1365-2605.2009.01023.x Braun, J.M., Kalkbrenner, A.E., Just, A.C., Yolton, K., Calafat, A.M., Sjödin, A., Hauser, R., Webster, G.M., Chen, A., Lanphear, B.P., 2014. Gestational Exposure to Endocrine- Disrupting Chemicals and Reciprocal Social, Repetitive, and Stereotypic Behaviors in 4- and 5-Year-Old Children: The HOME Study. Environ. Health Perspect. 122, 513–520. https://doi.org/10.1289/ehp.1307261 Breul, S., Van Landuyt, K.L., Reichl, F.X., Högg, C., Hoet, P., Godderis, L., Van Meerbeek, B., Cokic, S.M., 2020. Filtration efficiency of surgical and FFP3 masks against composite dust. Eur. J. Oral Sci. 128, 233–240. https://doi.org/10.1111/eos.12697 Brown, J., Gordon, T., Price, O., Asgharian, B., 2013. Thoracic and respirable particle deinitions for human health risk assessment. Part. Fibre Toxicol. 10, 1–12. Cahill, T.M., Groskova, D., Charles, M.J., Sanborn, J.R., Denison, M.S., Baker, L., 2007. Atmospheric concentrations of polybrominated diphenyl ethers at near-source sites. Environ. Sci. Technol. 41, 6370–6377. https://doi.org/10.1021/es070844j Callesen, M., Bekö, G., Weschler, C.J., Langer, S., Brive, L., Clausen, G., Toftum, J., Sigsgaard, T., Høst, A., Kold, T., 2014. International Journal of Hygiene and Phthalate metabolites in urine and asthma , allergic rhinoconjunctivitis and atopic dermatitis in preschool children. Int. J. Hyg. Environ. Health 217, 645–652. https://doi.org/10.1016/j.ijheh.2013.12.001 Cao, Z., Xu, F., Covaci, A., Wu, M., Wang, H., Yu, G., Wang, B., Deng, S., Huang, J., Wang, X., 2014. Distribution patterns of brominated, chlorinated, and phosphorus flame retardants 24

with particle size in indoor and outdoor dust and implications for human exposure. Environ. Sci. Technol. 48, 8839–8846. https://doi.org/10.1021/es501224b Carignan, C.C., Mínguez-Alarcón, L., Butt, C.M., Williams, P.L., Meeker, J.D., Stapleton, H.M., Toth, T.L., Ford, J.B., Hauser, R., 2017. Urinary Concentrations of Organophosphate Flame Retardant Metabolites and Pregnancy Outcomes among Women Undergoing in Vitro Fertilization. Environ. Health Perspect. 125, 087018. https://doi.org/10.1289/EHP1021 Carignan, C.C., Mínguez-Alarcón, L., Williams, P.L., Meeker, J.D., Stapleton, H.M., Butt, C.M., Toth, T.L., Ford, J.B., Hauser, R., 2018. Paternal urinary concentrations of organophosphate flame retardant metabolites, fertility measures, and pregnancy outcomes among couples undergoing in vitro fertilization. Environ. Int. 111, 232–238. https://doi.org/10.1016/j.envint.2017.12.005 Castorina, R., Bradman, A., Stapleton, H.M., Butt, C., Avery, D., Harley, K.G., Gunier, R.B., Holland, N., Eskenazi, B., 2017. Current-use flame retardants: Maternal exposure and neurodevelopment in children of the CHAMACOS cohort. Chemosphere 189, 574–580. https://doi.org/10.1016/j.chemosphere.2017.09.037 Ceballos, D.M., Côté, D., Bakhiyi, B., Flynn, M.A., Zayed, J., Gravel, S., Herrick, R.F., Labrèche, F., 2020. Overlapping vulnerabilities in workers of the electronics recycling industry formal sector: A commentary. Am. J. Ind. Med. 63, 955–962. https://doi.org/10.1002/ajim.23173 Ceballos, D.M., Dong, Z., 2016. The formal electronic recycling industry: Challenges and opportunities in occupational and environmental health research. Environ. Int. 95, 157–166. https://doi.org/10.1016/j.envint.2016.07.010 CEPA, 1999. Canadian Environmental Protection Act. Cequier, E., Sakhi, A.K., Marcé, R.M., Becher, G., Thomsen, C., 2015. Human exposure pathways to organophosphate triesters — A biomonitoring study of mother–child pairs. Environ. Int. 75, 159–165. https://doi.org/10.1016/j.envint.2014.11.009 Chan, J.K.Y., Wong, M.H., 2013. A review of environmental fate, body burdens, and human health risk assessment of PCDD/Fs at two typical electronic waste recycling sites in China. Sci. Total Environ. 463–464, 1111–1123. https://doi.org/10.1016/j.scitotenv.2012.07.098 Cherrie, J.W., 2003. CommentaryThe Beginning of the Science Underpinning Occupational Hygiene. Ann. Occup. Hyg. 47, 179–185. https://doi.org/10.1093/annhyg/meg030 City of Toronto, 2019. Search for an Establishment Monitored by BodySafe [WWW Document]. URL https://www.toronto.ca/community-people/health-wellness-care/health- programs-advice/bodysafe/search-for-an-establishment-space-holder-for-map/ (accessed 7.18.19). Consumer Product Safety Commission, 2008. Consumer Product Safety Improvement Act of 2008. Craig, J.A., Ceballos, D.M., Fruh, V., Petropoulos, Z.E., Allen, J.G., Calafat, A.M., Ospina, M., 25

Stapleton, H.M., Hammel, S., Gray, R., Webster, T.F., 2019. Exposure of Nail Salon Workers to Phthalates, Di(2-ethylhexyl) Terephthalate, and Organophosphate Esters: A Pilot Study. Environ. Sci. Technol. 53, 14630–14637. https://doi.org/10.1021/acs.est.9b02474 de Winter-Sorkina, R., Bakker, M.., Wolterink, G., Zielmaker, M.J., 2006. Brominated flame retardants: occurrence, dietary intake and risk assessment [WWW Document]. URL https://www.rivm.nl/bibliotheek/rapporten/320100002.pdf (accessed 6.7.18). Delgado-Saborit, J.M., Stark, C., Harrison, R.M., 2014. Use of a versatile high efficiency multiparallel denuder for the sampling of PAHs in ambient air: Gas and particle phase concentrations, particle size distribution and artifact formation. Environ. Sci. Technol. 48, 499–507. https://doi.org/10.1021/es402937d Dixon, H.M., Scott, R.P., Holmes, D., Calero, L., Kincl, L.D., Waters, K.M., Camann, D.E., Calafat, A.M., Herbstman, J.B., Anderson, K.A., 2018. Silicone wristbands compared with traditional polycyclic aromatic hydrocarbon exposure assessment methods. Anal. Bioanal. Chem. 410, 3059–3071. https://doi.org/10.1007/s00216-018-0992-z Eakin, J.M., Champoux, D., MacEachen, E., 2017. Health and safety in small workplaces: refocusing upstream. Can. J. Public Health 101 Suppl, S29-33. EC, 2018. Waste Electrical & Electronic Equipment (WEEE) [WWW Document]. Eur. Comm. https://doi.org/10.1016/j.geb.2005.03.002 Ekelund, M., Azhdar, B., Gedde, U.W., 2010. Evaporative loss kinetics of di(2- ethylhexyl)phthalate (DEHP) from pristine DEHP and plasticized PVC. Polym. Degrad. Stab. 95, 1789–1793. https://doi.org/10.1016/j.polymdegradstab.2010.05.007 Eriksson, P., Jakobsson, E., Fredriksson, A., 2001. Brominated flame retardants: a novel class of developmental toxicants in our environment? Environ. Health Perspect. 109, 903–908. https://doi.org/10.1289/ehp.01109903 Estill, C.F., Slone, J., Mayer, A., Chen, I.-C., La Guardia, M.J., 2020. Worker exposure to flame retardants in manufacturing, construction and service industries. Environ. Int. 135, 105349. https://doi.org/10.1016/j.envint.2019.105349 European Commission, 2014. COMMUNICATION FROM THE COMMISSION on the finalisation of the restriction process on the four phthalates (DEHP, DBP, BBP and DIBP) under Regulation (EC) No 1907/2006 of the European Parliament and of the Council concerning Registration, Evaluation, Authori. Off. J. Eur. Union 73, 1–4. ExpoStats, 2015. NDExpo – Treatment of non-detects in industrial hygiene samples [WWW Document]. URL http://www.expostats.ca/site/app-local/NDExpo/ (accessed 2.20.20). Factor-Litvak, P., Insel, B., Calafat, A.M., Liu, X., Perera, F., Rauh, V.A., Whyatt, R.M., 2014. Persistent Associations between Maternal Prenatal Exposure to Phthalates on Child IQ at Age 7 Years. PLoS One 9, e114003. https://doi.org/10.1371/journal.pone.0114003 Federman, M.N., Harrington, D.E., Krynski, K.J., 2006. Vietnamese Manicurists: Are Immigrants Displacing Natives or Finding New Nails to Polish? ILR Rev. 59, 302–318. https://doi.org/10.1177/001979390605900207 26

Fisher, M., Arbuckle, T.E., MacPherson, S., Braun, J.M., Feeley, M., Gaudreau, É., 2019. Phthalate and BPA Exposure in Women and Newborns through Personal Care Product Use and Food Packaging. Environ. Sci. Technol. 53, 10813–10826. https://doi.org/10.1021/acs.est.9b02372 Flanagan, M.E., Seixas, N., Majar, M., Camp, J., Morgan, M., 2003. Silica Dust Exposures During Selected Construction Activities. AIHA J. 64, 319–328. https://doi.org/10.1080/15428110308984823 Fortia, V., Balde, C.P., Kuehr, R., Bel, G., 2020. The Global E-waste Monitor 2020: Quantitites, flows and circular economy potential [WWW Document]. URL https://collections.unu.edu/view/UNU:7737 (accessed 10.13.20). Fraser, A.J., Webster, T.F., McClean, M.D., 2009. Diet Contributes Significantly to the Body Burden of PBDEs in the General U.S. Population. Environ. Health Perspect. 117, 1520– 1525. https://doi.org/10.1289/ehp.0900817 Frazzoli, C., Orisakwe, O.E., Dragone, R., Mantovani, A., 2010. Diagnostic health risk assessment of electronic waste on the general population in developing countries’ scenarios. Environ. Impact Assess. Rev. 30, 388–399. https://doi.org/10.1016/j.eiar.2009.12.004 Frederiksen, M., Stapleton, H.M., Vorkamp, K., Webster, T.F., Jensen, N.M., Sørensen, J.A., Nielsen, F., Knudsen, L.E., Sørensen, L.S., Clausen, P.A., Nielsen, J.B., 2018. Dermal uptake and percutaneous penetration of organophosphate esters in a human skin ex vivo model. Chemosphere 197, 185–192. https://doi.org/10.1016/j.chemosphere.2018.01.032 Fromme, H., Becher, G., Hilger, B., Völkel, W., 2016. Brominated flame retardants - Exposure and risk assessment for the general population. Int. J. Hyg. Environ. Health 219, 1–23. https://doi.org/10.1016/j.ijheh.2015.08.004 Gaspar, F.W., Castorina, R., Maddalena, R.L., Nishioka, M.G., McKone, T.E., Bradman, A., 2014. Phthalate exposure and risk assessment in California child care facilities. Environ. Sci. Technol. 48, 7593–7601. https://doi.org/10.1021/es501189t Gevao, B., Al-Bahloul, M., Al-Ghadban, A.N., Ali, L., Al-Omair, A., Helaleh, M., Al-Matrouk, K., Zafar, J., 2006. Polybrominated diphenyl ethers in indoor air in Kuwait: Implications for human exposure. Atmos. Environ. 40, 1419–1426. https://doi.org/10.1016/j.atmosenv.2005.10.053 Gioia, R., Steinnes, E., Thomas, G.O., Mejier, S.N., Jones, K.C., 2006. Persistent organic pollutants in European background air: derivation of temporal and latitudinal trends. J. Environ. Monit. 8, 700. https://doi.org/10.1039/b604821h Giovanoulis, G., Bui, T., Xu, F., Papadopoulou, E., Padilla-Sanchez, J.A., Covaci, A., Haug, L.S., Cousins, A.P., Magnér, J., Cousins, I.T., de Wit, C.A., 2018. Multi-pathway human exposure assessment of phthalate esters and DINCH. Environ. Int. 112, 115–126. https://doi.org/10.1016/j.envint.2017.12.016 Glazer, L., Hawkey, A.B., Wells, C.N., Drastal, M., Odamah, K.-A., Behl, M., Levin, E.D., 2018. Developmental Exposure to Low Concentrations of Organophosphate Flame

Retardants Causes Life-Long Behavioral Alterations in Zebrafish. Toxicol. Sci. 165, 487– 498. https://doi.org/10.1093/toxsci/kfy173 Godwin, A.D., 2017. Plasticizers, in: Applied Plastics Engineering Handbook. Elsevier, pp. 533–553. Godwin, A.D., 2010. Uses of Phthalates and Other Plasticizers [WWW Document]. URL https://www.cpsc.gov/s3fs-public/godwin.pdf (accessed 10.21.20). Gong, M., Weschler, C.J., Zhang, Y., 2016. Impact of Clothing on Dermal Exposure to Phthalates: Observations and Insights from Sampling Both Skin and Clothing. Environ. Sci. Technol. 50, 4350–4357. https://doi.org/10.1021/acs.est.6b00113 Goodyer, C.G., Poon, S., Aleksa, K., Hou, L., Atehortua, V., Carnevale, A., Jednak, R., Emil, S., Bagli, D., Dave, S., Hales, B.F., Chevrier, J., 2017. A case-control study of maternal polybrominated diphenyl ether (PBDE) exposure and cryptorchidism in Canadian populations. Environ. Health Perspect. 125, 1–9. https://doi.org/10.1289/EHP522 Gouin, T., Harner, T., Blanchard, P., Mackay, D., 2005. Passive and Active Air Samplers as Complementary Methods for Investigating Persistent Organic Pollutants in the Great Lakes Basin. Environ. Sci. Technol. 39, 9115–9122. https://doi.org/10.1021/es051397f Goverment of Canada, 2017. Phthalates Regulations Règlement sur les phtalates 21–23. Government of Canada, 2019. Cosmetic Ingredient Hotlist [WWW Document]. URL https://www.canada.ca/en/health-canada/services/consumer-product- safety/cosmetics/cosmetic-ingredient-hotlist-prohibited-restricted- ingredients/hotlist.html#tbl1 (accessed 5.4.20). Government of Canada, 2016. Toxic substances list: PBDEs [WWW Document]. Government of Canada, 2012. Regulations Amending the Prohibition of Certain Toxic Substances Regulations, 2012 [WWW Document]. Canada Gaz. Part II. URL http://www.gazette.gc.ca/rp-pr/p2/2016/2016-10-05/pdf/g2-15020.pdf (accessed 2.18.21). Government of Ontario, 2018. Waste management [WWW Document]. URL https://www.ontario.ca/page/waste-management (accessed 12.9.18). Graham, P.R., 1973. Phthalate ester plasticizers—why and how they are used. Environ. Health Perspect. 3, 3–12. https://doi.org/10.1289/ehp.73033 Grant, K., Goldizen, F.C., Sly, P.D., Brune, M.-N., Neira, M., van den Berg, M., Norman, R.E., 2013. Health consequences of exposure to e-waste: a systematic review. Lancet Glob. Heal. 1, e350–e361. https://doi.org/10.1016/S2214-109X(13)70101-3 Gravel, S., Bakhiyi, B., Lavoué, J., Verner, M.-A., Zayed, J., Labreche, F., 2019a. Electronic waste recycling exposure and hormone levels in workers., in: 27th EPICOH International Symposium on Epidemiology in Occupational Health. Wellington, NewZealand. Gravel, S., Diamond, M.L., Jantunen, L.M., Verner, M.-A., Zayed, J., Labrèche, F., 2019b. Is airborne concentration of BDE209 associated with serum concentration in recycling workers?, in: 9th International Symposium on Flame Retardants BFR 2019. Montreal,

Canada. Gravel, S., Lavoué, J., Bakhiyi, B., Diamond, M.L., Jantunen, L.M., Lavoie, J., Roberge, B., Verner, M.-A., Zayed, J., Labrèche, F., 2019c. Halogenated flame retardants and organophosphate esters in the air of electronic waste recycling facilities: Evidence of high concentrations and multiple exposures. Environ. Int. 128, 244–253. https://doi.org/10.1016/j.envint.2019.04.027 Gravel, S., Lavoué, J., Bakhiyi, B., Lavoie, J., Roberge, B., Patry, L., Bouchard, M.F., Verner, M., Zayed, J., Labrèche, F., 2020. Multi-exposures to suspected endocrine disruptors in electronic waste recycling workers: Associations with thyroid and reproductive hormones. Int. J. Hyg. Environ. Health 225, 113445. https://doi.org/10.1016/j.ijheh.2019.113445 Guo, J., Lin, K., Deng, J., Fu, X., Xu, Z., 2015. Polybrominated diphenyl ethers in indoor air during waste TV recycling process. J. Hazard. Mater. 283, 439–446. https://doi.org/10.1016/j.jhazmat.2014.09.044 Guo, Y., Kannan, K., 2013. A survey of phthalates and parabens in personal care products from the United States and its implications for human exposure. Environ. Sci. Technol. 47, 14442–14449. https://doi.org/10.1021/es4042034 Guo, Y., Kannan, K., 2011. Comparative Assessment of Human Exposure to Phthalate Esters from House Dust in China and the United States. Environ. Sci. Technol. 45, 3788–3794. https://doi.org/10.1021/es2002106 Hammel, S., Hoffman, K., Webster, T.F., Anderson, K.A., Stapleton, H.M., 2016. Measuring Personal Exposure to Organophosphate Flame Retardants using Silicone Wristbands and Hand Wipes. Environ. Sci. Technol. acs.est.6b00030. https://doi.org/10.1021/acs.est.6b00030 Hammel, S.C., Phillips, A.L., Hoffman, K., Stapleton, H.M., 2018. Evaluating the Use of Silicone Wristbands To Measure Personal Exposure to Brominated Flame Retardants. Environ. Sci. Technol. 52, acs.est.8b03755. https://doi.org/10.1021/acs.est.8b03755 Harley, K.G., Marks, A.R., Chevrier, J., Bradman, A., Sjödin, A., Eskenazi, B., 2010. PBDE Concentrations in Women’s Serum and Fecundability. Environ. Health Perspect. 118, 699– 704. https://doi.org/10.1289/ehp.0901450 Harner, T., Bartkow, M., Holoubek, I., Klanova, J., Wania, F., Gioia, R., Moeckel, C., Sweetman, A.J., Jones, K.C., 2006. Passive air sampling for persistent organic pollutants: Introductory remarks to the special issue. Environ. Pollut. 144, 361–364. https://doi.org/10.1016/j.envpol.2005.12.044 Hartmann, P.C., Burgi, D., Giger, W., 2004. Organophosphate flame retardants and plasticizers in indoor air. Chemosphere 57, 781–787. https://doi.org/10.1016/j.chemosphere.2004.08.051 Hays, S.M., Kirman, C.R., 2017. Risk assessment and Biomonitoring Equivalent for 2- ethylhexyl-2,3,4,5 tetrabromobenzoate (TBB) and tetrabromobenzoic acid (TBBA). Regul. Toxicol. Pharmacol. 89, 186–192. https://doi.org/10.1016/j.yrtph.2017.07.022 Hazrati, S., Harrad, S., 2006. Causes of Variability in Concentrations of Polychlorinated 29

Biphenyls and Polybrominated Diphenyl Ethers in Indoor air. Environ. Sci. Technol. 40, 7584–7589. https://doi.org/10.1021/es0617082 Heacock, M., Kelly, C.B., Asante, K.A., Birnbaum, L.S., Bergman, Å.L., Bruné, M.-N., Buka, I., Carpenter, D.O., Chen, A., Huo, X., Kamel, M., Landrigan, P.J., Magalini, F., Diaz- Barriga, F., Neira, M., Omar, M., Pascale, A., Ruchirawat, M., Sly, L., Sly, P.D., Van den Berg, M., Suk, W.A., 2015. E-Waste and Harm to Vulnerable Populations: A Growing Global Problem. Environ. Health Perspect. 124, 550–555. https://doi.org/10.1289/ehp.1509699 Heudorf, U., Mersch-Sundermann, V., Angerer, J., 2007. Phthalates: Toxicology and exposure. Int. J. Hyg. Environ. Health 210, 623–634. https://doi.org/10.1016/j.ijheh.2007.07.011 Hill, K.L., Hamers, T., Kamstra, J.H., Willmore, W.G., Letcher, R.J., 2018. Organophosphate triesters and selected metabolites enhance binding of thyroxine to human transthyretin in vitro. Toxicol. Lett. 285, 87–93. https://doi.org/10.1016/j.toxlet.2017.12.030 Hites, R.A., 2004. Polybrominated Diphenyl Ethers in the Environment and in People: A Meta- Analysis of Concentrations. Environ. Sci. Technol. 38, 945–956. https://doi.org/10.1021/es035082g Hoffman, K., Butt, C.M., Webster, T.F., Preston, E. V., Hammel, S.C., Makey, C., Lorenzo, A.M., Cooper, E.M., Carignan, C., Meeker, J.D., Hauser, R., Soubry, A., Murphy, S.K., Price, T.M., Hoyo, C., Mendelsohn, E., Congleton, J., Daniels, J.L., Stapleton, H.M., 2017a. Temporal Trends in Exposure to Organophosphate Flame Retardants in the United States. Environ. Sci. Technol. Lett. 4, 112–118. https://doi.org/10.1021/acs.estlett.6b00475 Hoffman, K., Lorenzo, A., Butt, C.M., Hammel, S.C., Henderson, B.B., Roman, S.A., Scheri, R.P., Stapleton, H.M., Sosa, J.A., 2017b. Exposure to flame retardant chemicals and occurrence and severity of papillary thyroid cancer: A case-control study. Environ. Int. 107, 235–242. https://doi.org/10.1016/j.envint.2017.06.021 Holmes, A.K., Koller, K.R., Kieszak, S.M., Sjodin, A., Calafat, A.M., Sacco, F.D., Varner, D.W., Lanier, A.P., Rubin, C.H., 2014. Case–control study of breast cancer and exposure to synthetic environmental chemicals among Alaska Native women. Int. J. Circumpolar Health 73, 25760. https://doi.org/10.3402/ijch.v73.25760 Hou, R., Xu, Y., Wang, Z., 2016. Review of OPFRs in animals and humans: Absorption, bioaccumulation, metabolism, and internal exposure research. Chemosphere 153, 78–90. https://doi.org/10.1016/j.chemosphere.2016.03.003 Hubinger, J.C., Havery, D.C., 2006. Analysis of consumer cosmetic products for phthalate esters. J. Cosmet. Sci. 57, 127–37. Hutter, H.-P., Haluza, D., Piegler, K., Hohenblum, P., Fröhlich, M., Scharf, S., Uhl, M., Damberger, B., Tappler, P., Kundi, M., Wallner, P., Moshammer, H., 2013. Semivolatile compounds in schools and their influence on cognitive performance of children. Int. J. Occup. Med. Environ. Health 26, 628–635. https://doi.org/10.2478/s13382-013-0125-z IARC Working Group on the Evaluation of Carcinogenic Risks to Humans, 2013. Some chemicals present in industrial and consumer products, food and drinking-water. IARC

Monogr. Eval. Carcinog. Risks Hum. 101, 9–549. Igharo, O.G., Anetor, J.I., Osibanjo, O., Osadolor, H.B., Odazie, E.C., Uche, Z.C., 2018. Endocrine disrupting metals lead to alteration in the gonadal hormone levels in Nigerian e- waste workers. Universa Med. 37, 65. https://doi.org/10.18051/UnivMed.2018.v37.65-74 Iqbal, M., Syed, J.H., Breivik, K., Chaudhry, M.J.I., Li, J., Zhang, G., Malik, R.N., 2017. E- Waste Driven Pollution in Pakistan: The First Evidence of Environmental and Human Exposure to Flame Retardants (FRs) in Karachi City. Environ. Sci. Technol. 51, 13895– 13905. https://doi.org/10.1021/acs.est.7b03159 Jacobson, M.H., Barr, D.B., Marcus, M., Muir, A.B., Lyles, R.H., Howards, P.P., Pardo, L., Darrow, L.A., 2016. Serum polybrominated diphenyl ether concentrations and thyroid function in young children. Environ. Res. 149, 222–230. https://doi.org/10.1016/j.envres.2016.05.022 Jarema, K.A., Hunter, D.L., Shaffer, R.M., Behl, M., Padilla, S., 2015. Acute and developmental behavioral effects of flame retardants and related chemicals in zebrafish. Neurotoxicol. Teratol. 52, 194–209. https://doi.org/10.1016/j.ntt.2015.08.010 Julander, A., Westberg, H., Engwall, M., van Bavel, B., 2005. Distribution of brominated flame retardants in different dust fractions in air from an electronics recycling facility. Sci. Total Environ. 350, 151–160. https://doi.org/10.1016/j.scitotenv.2005.01.015 Kahhat, R., Williams, E., 2012. Materials flow analysis of e-waste: Domestic flows and exports of used computers from the United States. Resour. Conserv. Recycl. 67, 67–74. https://doi.org/10.1016/j.resconrec.2012.07.008 Kammerer, F., 2017. Safe Drinking Water and Toxic Enforcement Act of 1986. Environ. Heal. 1–22. Kile, M.L., Scott, R.P., O’Connell, S.G., Lipscomb, S., MacDonald, M., McClelland, M., Anderson, K.A., Gibson, E.A., Stapleton, H.M., Calero, L., Holmes, D., Burke, K., Martinez, R., Cortes, B., Nematollahi, A., Evans, D., Anderson, K.A., Herbstman, J.B., Fisher, M., Arbuckle, T.E., MacPherson, S., Braun, J.M., Feeley, M., Gaudreau, É., Dixon, H.M., Scott, R.P., Holmes, D., Calero, L., Kincl, L.D., Waters, K.M., Camann, D.E., Calafat, A.M., Herbstman, J.B., Anderson, K.A., Bohlin, P., Jones, K.C., Levin, J.O., Lindahl, R., Strandberg, B., 2019. Using silicone wristbands to evaluate preschool children’s exposure to flame retardants. Chemosphere 219, 567–573. https://doi.org/10.1007/s00216-018-0992-z Kim, E.-H., Jeon, B.-H., Kim, J., Kim, Y.-M., Han, Y., Ahn, K., Cheong, H.-K., 2017. Exposure to phthalates and bisphenol A are associated with atopic dermatitis symptoms in children: a time-series analysis. Environ. Heal. 16, 24. https://doi.org/10.1186/s12940-017-0225-5 Kim, Y.H., Wyrzykowska-Ceradini, B., Touati, A., Krantz, Q.T., Dye, J.A., Linak, W.P., Gullett, B., Gilmour, M.I., 2015. Characterization of Size-Fractionated Airborne Particles Inside an Electronic Waste Recycling Facility and Acute Toxicity Testing in Mice. Environ. Sci. Technol. 49, 11543–11550. https://doi.org/10.1021/acs.est.5b03263 Koniecki, D., Wang, R., Moody, R.P., Zhu, J., 2011. Phthalates in cosmetic and personal care

products: Concentrations and possible dermal exposure. Environ. Res. 111, 329–336. https://doi.org/10.1016/j.envres.2011.01.013 Kuo, L., Cade, S.E., Cullinan, V., Schultz, I.R., 2019. Polybrominated diphenyl ethers (PBDEs) in plasma from E-waste recyclers, outdoor and indoor workers in the Puget Sound, WA region. Chemosphere 219, 209–216. https://doi.org/10.1016/j.chemosphere.2018.12.006 Kuriyama, S.N., Talsness, C.E., Grote, K., Chahoud, I., 2005. Developmental exposure to low- dose PBDE-99: Effects on male fertility and neurobehavior in rat offspring. Environ. Health Perspect. 113, 149–154. https://doi.org/10.1289/ehp.7421 La Guardia, M.J., Hale, R.C., Harvey, E., 2006. Detailed Polybrominated Diphenyl Ether (PBDE) Congener Composition of the Widely Used Penta-, Octa-, and Deca-PBDE Technical Flame-retardant Mixtures. Environ. Sci. Technol. 40, 6247–6254. https://doi.org/10.1021/es060630m Labunska, I., Harrad, S., Wang, M., Santillo, D., Johnston, P., 2014. Human Dietary Exposure to PBDEs Around E-Waste Recycling Sites in Eastern China. Environ. Sci. Technol. 48, 5555–5564. https://doi.org/10.1021/es500241m Lam, J., Lanphear, B.P., Bellinger, D., Axelrad, D.A., McPartland, J., Sutton, P., Davidson, L., Daniels, N., Sen, S., Woodruff, T.J., 2017. Developmental PBDE Exposure and IQ/ADHD in Childhood: A Systematic Review and Meta-analysis. Environ. Health Perspect. 125. https://doi.org/10.1289/EHP1632 Lenters, V., Portengen, L., Rignell-Hydbom, A., Jönsson, B.A.G., Lindh, C.H., Piersma, A.H., Toft, G., Bonde, J.P., Heederik, D., Rylander, L., Vermeulen, R., 2016. Prenatal Phthalate, Perfluoroalkyl Acid, and Organochlorine Exposures and Term Birth Weight in Three Birth Cohorts: Multi-Pollutant Models Based on Elastic Net Regression. Environ. Health Perspect. 124, 365–372. https://doi.org/10.1289/ehp.1408933 Li, F., Xie, Q., Li, X., Li, N., Chi, P., Chen, J., Wang, Z., Hao, C., 2010. Hormone Activity of Hydroxylated Polybrominated Diphenyl Ethers on Human Thyroid Receptor-β: In Vitro and In Silico Investigations. Environ. Health Perspect. 118, 602–606. https://doi.org/10.1289/ehp.0901457 Lilienthal, H., Hack, A., Roth-Härer, A., Grande, S.W., Talsness, C.E., 2006. Effects of developmental exposure to 2,2′,4,4′, 5-pentabromodiphenyl ether (PBDE-99) on sex steroids, sexual development, and sexually dimorphic behavior in rats. Environ. Health Perspect. 114, 194–201. https://doi.org/10.1289/ehp.8391 Lippmann, M., 1998. The 1997 US EPA Standards for Particulate Matter and Ozone, in: Air Pollution and Health. pp. 75–100. https://doi.org/10.1039/9781847550095-00075 Little, J.C., Weschler, C.J., Nazaroff, W.W., Liu, Z., Cohen Hubal, E.A., 2012. Rapid Methods to Estimate Potential Exposure to Semivolatile Organic Compounds in the Indoor Environment. Environ. Sci. Technol. 46, 11171–11178. https://doi.org/10.1021/es301088a Liu, C., Zhang, Y., Weschler, C.J., 2017. Exposure to SVOCs from Inhaled Particles: Impact of Desorption. Environ. Sci. Technol. 51, 6220–6228. https://doi.org/10.1021/acs.est.6b05864 Lu, S.Y., Li, Y.X., Zhang, T., Cai, D., Ruan, J.J., Huang, M.Z., Wang, L., Zhang, J.Q., Qiu, 32

R.L., 2017. Effect of E-waste Recycling on Urinary Metabolites of Organophosphate Flame Retardants and Plasticizers and Their Association with Oxidative Stress. Environ. Sci. Technol. 51, 2427–2437. https://doi.org/10.1021/acs.est.6b05462 Lucas, D., Petty, S.M., Keen, O., Luedeka, B., Schlummer, M., Weber, R., Barlaz, M., Yazdani, R., Riise, B., Rhodes, J., Nightingale, D., Diamond, M.L., Vijgen, J., Lindeman, A., Blum, A., Koshland, C.P., 2017. Methods of Responsibly Managing End-of-Life Foams and Plastics Containing Flame Retardants: Part I. Environ. Eng. Sci. https://doi.org/10.1089/ees.2017.0147 Ma, J., Addink, R., Yun, S., Cheng, J., Wang, W., Kannan, K., 2009. Polybrominated Dibenzo- p -dioxins/Dibenzofurans and Polybrominated Diphenyl Ethers in Soil, Vegetation, Workshop-Floor Dust, and Electronic Shredder Residue from an Electronic Waste Recycling Facility and in Soils from a Chemical Industrial Complex in Ea. Environ. Sci. Technol. 43, 7350–7356. https://doi.org/10.1021/es901713u MacIntosh, D.L., Minegishi, T., Fragala, M.A., Allen, J.G., Coghlan, K.M., Stewart, J.H., McCarthy, J.F., 2012. Mitigation of building-related polychlorinated biphenyls in indoor air of a school. Environ. Heal. A Glob. Access Sci. Source 11, 1–10. https://doi.org/10.1186/1476-069X-11-24 Mäkinen, M.S.E., Mäkinen, M.R.A., Koistinen, J.T.B., Pasanen, A.-L., Pasanen, P.O., Kalliokoski, P.J., Korpi, A.M., 2009. Respiratory and Dermal Exposure to Organophosphorus Flame Retardants and Tetrabromobisphenol A at Five Work Environments. Environ. Sci. Technol. 43, 941–947. https://doi.org/10.1021/es802593t Marek, R.F., Thorne, P.S., Herkert, N.J., Awad, A.M., Hornbuckle, K.C., 2017. Airborne PCBs and OH-PCBs Inside and Outside Urban and Rural U.S. Schools. Environ. Sci. Technol. 51, 7853–7860. https://doi.org/10.1021/acs.est.7b01910 Meeker, J.D., Cooper, E.M., Stapleton, H.M., Hauser, R., 2013. Exploratory analysis of urinary metabolites of phosphorus-containing flame retardants in relation to markers of male reproductive health. Endocr. Disruptors 1, e26306. https://doi.org/10.4161/endo.26306 Meeker, J.D., Stapleton, H.M., 2009. House Dust Concentrations of Organophosphate Flame Retardants in Relation to Hormone Levels and Semen Quality Parameters. Environ. Health Perspect. 118, 318–323. https://doi.org/10.1289/ehp.0901332 Meironyté, D., Norén, K., Bergman, Å., 1999. Analysis of polybrominated diphenyl ethers in swedish human milk. A time-related trend study, 1972–1997. J. Toxicol. Environ. Heal. - Part A 58, 329–341. https://doi.org/10.1080/009841099157197 Melymuk, L., Robson, M., Helm, P.A., Diamond, M.L., 2011. Evaluation of passive air sampler calibrations: Selection of sampling rates and implications for the measurement of persistent organic pollutants in air. Atmos. Environ. 45, 1867–1875. https://doi.org/10.1016/j.atmosenv.2011.01.011 Mendelsohn, E., Hagopian, A., Hoffman, K., Butt, C.M., Lorenzo, A., Congleton, J., Webster, T.F., Stapleton, H.M., 2016. Nail polish as a source of exposure to triphenyl phosphate. Environ. Int. 86, 45–51. https://doi.org/10.1016/j.envint.2015.10.005

Moeckel, C., Harner, T., Nizzetto, L., Strandberg, B., Lindroth, A., Jones, K.C., 2009. Use of depuration compounds in passive air samplers: Results from active sampling-supported field deployment, potential uses, and recommendations. Environ. Sci. Technol. 43, 3227– 3232. https://doi.org/10.1021/es802897x Morrison, G.C., Weschler, C.J., Bekö, G., Koch, H.M., Salthammer, T., Schripp, T., Toftum, J., Clausen, G., 2016. Role of clothing in both accelerating and impeding dermal absorption of airborne SVOCs. J. Expo. Sci. Environ. Epidemiol. 26, 113–118. https://doi.org/10.1038/jes.2015.42 Muenhor, D., Harrad, S., Ali, N., Covaci, A., 2010. Brominated flame retardants (BFRs) in air and dust from electronic waste storage facilities in Thailand. Environ. Int. 36, 690–698. https://doi.org/10.1016/j.envint.2010.05.002 Nalli, S., Horn, O.J., Grochowalski, A.R., Cooper, D.G., Nicell, J.A., 2006. Origin of 2- ethylhexanol as a VOC. Environ. Pollut. 140, 181–185. https://doi.org/10.1016/j.envpol.2005.06.018 National Academies of Sciences Engineering and Medicine, 2017. Application of Systematic Review Methods in an Overall Strategy for Evaluating Low-Dose Toxicity from Endocrine Active Chemicals. The National Academies Press, Washington,DC. https://doi.org/10.17226/24758 Nguyen, L. V., Diamond, M.L., Venier, M., Stubbings, W.A., Romanak, K., Bajard, L., Melymuk, L., Jantunen, L.M., Arrandale, V.H., 2019. Exposure of Canadian electronic waste dismantlers to flame retardants. Environ. Int. 129, 95–104. https://doi.org/10.1016/j.envint.2019.04.056 Nguyen, L. V., Gravel, S., Labrèche, F., Bakhiyi, B., Verner, M.A., Zayed, J., Jantunen, L.M., Arrandale, V.H., Diamond, M.L., 2020. Can Silicone Passive Samplers be Used for Measuring Exposure of e-Waste Workers to Flame Retardants? Environ. Sci. Technol. 54, 15277–15286. https://doi.org/10.1021/acs.est.0c05240 North, M.L., Takaro, T.K., Diamond, M.L., Ellis, A.K., 2014. Effects of phthalates on the development and expression of allergic disease and asthma. Ann. Allergy, Asthma Immunol. 112, 496–502. https://doi.org/10.1016/j.anai.2014.03.013 NTP, 1991. Toxicology and Carcinogenesis Studies of TRIS(2- CHLOROETHYL)PHOSPHATE (CAS NO. 115-96-8) in F344 / N Rats. Natl. Toxicol. Program Tech. Rep. Ser. 409, 1–171. O’Connell, S.G., Kincl, L.D., Anderson, K.A., 2014. Silicone Wristbands as Personal Passive Samplers. Environ. Sci. Technol. 48, 3327–3335. https://doi.org/10.1021/es405022f Okeme, J.O., Nguyen, L. V., Lorenzo, M., Dhal, S., Pico, Y., Arrandale, V.H., Diamond, M.L., 2018a. Polydimethylsiloxane (silicone rubber) brooch as a personal passive air sampler for semi-volatile organic compounds. Chemosphere 208, 1002–1007. https://doi.org/10.1016/j.chemosphere.2018.05.196 Okeme, J.O., Nguyen, L. V., Lorenzo, M., Dhal, S., Pico, Y., Arrandale, V.H., Diamond, M.L., 2018b. Polydimethylsiloxane (silicone rubber) brooch as a personal passive air sampler for

semi-volatile organic compounds. Chemosphere 208, 1002–1007. https://doi.org/10.1016/j.chemosphere.2018.05.196 Okeme, J.O., Parnis, J.M., Poole, J., Diamond, M.L., Jantunen, L.M., 2016a. Polydimethylsiloxane-air partition ratios for semi-volatile organic compounds by GC-based measurement and COSMO-RS estimation: Rapid measurements and accurate modelling. Chemosphere 156, 204–211. https://doi.org/10.1016/j.chemosphere.2016.04.094 Okeme, J.O., Rodgers, T.F.M., Jantunen, L.M., Diamond, M.L., 2018c. Examining the Gas- Particle Partitioning of Organophosphate Esters: How Reliable Are Air Measurements? Environ. Sci. Technol. 52, 13834–13844. https://doi.org/10.1021/acs.est.8b04588 Okeme, J.O., Saini, A., Yang, C., Zhu, J., Smedes, F., Klánová, J., Diamond, M.L., 2016b. Calibration of polydimethylsiloxane and XAD-Pocket passive air samplers (PAS) for measuring gas- and particle-phase SVOCs. Atmos. Environ. 143, 202–208. https://doi.org/10.1016/j.atmosenv.2016.08.023 Okeme, J.O., Yang, C., Abdollahi, A., Dhal, S., Harris, S.A., Jantunen, L.M., Tsirlin, D., Diamond, M.L., 2018d. Passive air sampling of flame retardants and plasticizers in Canadian homes using PDMS, XAD-coated PDMS and PUF samplers. Environ. Pollut. 239, 109–117. https://doi.org/10.1016/j.envpol.2018.03.103 Okonski, K., Degrendele, C., Melymuk, L., Landlová, L., Kukučka, P., Vojta, Š., Kohoutek, J., Čupr, P., Klánová, J., 2014. Particle Size Distribution of Halogenated Flame Retardants and Implications for Atmospheric Deposition and Transport. Environ. Sci. Technol. 48, 14426–14434. https://doi.org/10.1021/es5044547 Ospina, M., Jayatilaka, N.K., Wong, L.-Y., Restrepo, P., Calafat, A.M., 2018. Exposure to organophosphate flame retardant chemicals in the U.S. general population: Data from the 2013–2014 National Health and Nutrition Examination Survey. Environ. Int. 110, 32–41. https://doi.org/10.1016/j.envint.2017.10.001 Park, S.A., Gwak, S., Choi, S., 2014. Assessment of occupational symptoms and chemical exposures for nail salon technicians in Daegu City, Korea. J. Prev. Med. Public Heal. 47, 169–176. https://doi.org/10.3961/jpmph.2014.47.3.169 Pawar, G., 2017. Exploring the utility of 3-D skin models to evaluate trans-dermal uptake of flame retardants from indoor dust and consumer product. University of Birmingham. Pelucchi, C., Negri, E., Gallus, S., Boffetta, P., Tramacere, I., La Vecchia, C., 2009. Long-term particulate matter exposure and mortality: a review of European epidemiological studies. BMC Public Health 9, 453. https://doi.org/10.1186/1471-2458-9-453 Percy, Z., Vuong, A.M., Ospina, M., Calafat, A.M., La Guardia, M.J., Xu, Y., Hale, R.C., Dietrich, K.N., Xie, C., Lanphear, B.P., Braun, J.M., Cecil, K.M., Yolton, K., Chen, A., 2020. Organophosphate esters in a cohort of pregnant women: Variability and predictors of exposure. Environ. Res. 184, 109255. https://doi.org/10.1016/j.envres.2020.109255 Pettersson-Julander, A., van Bavel, B., Engwall, M., Westberg, H., 2004. Personal air sampling and analysis of polybrominated diphenyl ethers and other bromine containing compounds at an electronic recycling facility in Sweden. J. Environ. Monit. 6, 874.

https://doi.org/10.1039/b408381d Philippat, C., Bennett, D., Calafat, A.M., Picciotto, I.H., Xu, F., Giovanoulis, G., Van Waes, S., Padilla-Sanchez, J.A., Papadopoulou, E., Magnér, J., Haug, L.S., Neels, H., Covaci, A., 2016. Exposure to select phthalates and phenols through use of personal care products among Californian adults and their children. Environ. Res. 50, 7752–7760. https://doi.org/10.1021/acs.est.6b00246 Pinson, A., Bourguignon, J.P., Parent, A.S., 2016. Exposure to endocrine disrupting chemicals and neurodevelopmental alterations. Andrology 4, 706–722. https://doi.org/10.1111/andr.12211 Pope III, C.A., 2002. Lung Cancer, Cardiopulmonary Mortality, and Long-term Exposure to Fine Particulate Air Pollution. JAMA 287, 1132. https://doi.org/10.1001/jama.287.9.1132 Quach, T., Gunier, R., Tran, A., Von Behren, J., Doan-Billings, P.-A., Nguyen, K.-D., Okahara, L., Lui, B.Y.-B., Nguyen, M., Huynh, J., Reynolds, P., 2011. Characterizing Workplace Exposures in Vietnamese Women Working in California Nail Salons. Am. J. Public Health 101, S271–S276. https://doi.org/10.2105/AJPH.2010.300099 Radke, E.G., Braun, J.M., Meeker, J.D., Cooper, G.S., Agency, U.S.E.P., States, U., 2018. Phthalate exposure and male reproductive outcomes : A systematic review of the human epidemiological evidence. Environ. Int. 121, 764–793. https://doi.org/10.1016/j.envint.2018.07.029 Rakkestad, K.E., Dye, C.J., Yttri, K.E., Holme, J.A., Hongslo, J.K., Schwarze, P.E., Becher, R., 2007. Phthalate levels in Norwegian indoor air related to particle size fraction. J. Environ. Monit. 9, 1419. https://doi.org/10.1039/b709947a Rengasamy, S., Eimer, B., Shaffer, R.E., 2010. Simple respiratory protection - Evaluation of the filtration performance of cloth masks and common fabric materials against 20-1000 nm size particles. Ann. Occup. Hyg. 54, 789–798. https://doi.org/10.1093/annhyg/meq044 Richman, K.E., Butt, C.M., Young, C.J., 2018. Size-resolved particle measurements of polybrominated diphenyl ethers indoors: Implications for sources and human exposure. Environ. Toxicol. Chem. 37, 481–490. https://doi.org/10.1002/etc.3981 Robinson, B.H., 2009. E-waste: An assessment of global production and environmental impacts. Sci. Total Environ. 408, 183–191. https://doi.org/10.1016/j.scitotenv.2009.09.044 Rodes, C.E., Kamens, R.M., Wiener, R.W., 1991. The Significance and Characteristics of the Personal Activity Cloud on Exposure Assessment Measurements for Indoor Contaminants. Indoor Air 1, 123–145. https://doi.org/10.1111/j.1600-0668.1991.03-12.x Romanak, K.A., Wang, S., Stubbings, W.A., Hendryx, M., Venier, M., Salamova, A., 2019. Analysis of brominated and chlorinated flame retardants, organophosphate esters, and polycyclic aromatic hydrocarbons in silicone wristbands used as personal passive samplers. J. Chromatogr. A 1588, 41–47. https://doi.org/10.1016/j.chroma.2018.12.041 Romero-Franco, M., Hernández-Ramírez, R.U., Calafat, A.M., Cebrián, M.E., Needham, L.L., Teitelbaum, S., Wolff, M.S., López-Carrillo, L., 2011. Personal care product use and urinary levels of phthalate metabolites in Mexican women. Environ. Int. 37, 867–871. 36

https://doi.org/10.1016/j.envint.2011.02.014 Rosenberg, C., Hämeilä, M., Tornaeus, J., Säkkinen, K., Puttonen, K., Korpi, A., Kiilunen, M., Linnainmaa, M., Hesso, A., 2011. Exposure to Flame Retardants in Electronics Recycling Sites. Ann. Occup. Hyg. 55, 658–665. https://doi.org/10.1093/annhyg/mer033 Saini, A., Okeme, J.O., Goosey, E., Diamond, M.L., 2015. Calibration of two passive air samplers for monitoring phthalates and brominated flame-retardants in indoor air. Chemosphere 137, 166–173. https://doi.org/10.1016/j.chemosphere.2015.06.099 Saini, A., Okeme, J.O., Mark Parnis, J., McQueen, R.H., Diamond, M.L., 2016. From air to clothing: characterizing the accumulation of semi-volatile organic compounds to fabrics in indoor environments. Indoor Air. https://doi.org/10.1111/ina.12328 SCHETTLER, T., 2006. Human exposure to phthalates via consumer products. Int. J. Androl. 29, 134–139. https://doi.org/10.1111/j.1365-2605.2005.00567.x Schreder, E.D., Uding, N., La Guardia, M.J., 2016. Inhalation a significant exposure route for chlorinated organophosphate flame retardants. Chemosphere 150, 499–504. https://doi.org/10.1016/j.chemosphere.2015.11.084 Schwartz, J., Neas, L.M., 2000. Fine particles are more strongly associated than coarse particleswithacute respiratoryhealtheffectsinschoolchildren. Epidemiology 11, 6–10. Shi, T., Chen, S.-J., Luo, X.-J., Zhang, X.-L., Tang, C.-M., Luo, Y., Ma, Y.-J., Wu, J.-P., Peng, X.-Z., Mai, B.-X., 2009. Occurrence of brominated flame retardants other than polybrominated diphenyl ethers in environmental and biota samples from southern China. Chemosphere 74, 910–916. https://doi.org/10.1016/j.chemosphere.2008.10.047 Shoeib, M., Harner, T., 2002. Characterization and Comparison of Three Passive Air Samplers for Persistent Organic Pollutants. Environ. Sci. Technol. 36, 4142–4151. https://doi.org/10.1021/es020635t Sindiku, O., Babayemi, J., Osibanjo, O., Schlummer, M., Schluep, M., Watson, A., Weber, R., 2015. Polybrominated diphenyl ethers listed as Stockholm Convention POPs, other brominated flame retardants and heavy metals in e-waste polymers in Nigeria. Environ. Sci. Pollut. Res. 22, 14489–14501. https://doi.org/10.1007/s11356-014-3266-0 Singh, M., Thind, P.S., John, S., 2018. Health risk assessment of the workers exposed to the heavy metals in e-waste recycling sites of Chandigarh and Ludhiana, Punjab, India. Chemosphere 203, 426–433. https://doi.org/10.1016/j.chemosphere.2018.03.138 Sjödin, A., Carlsson, H., Thuresson, K., Sjölin, S., Bergman, Å., Östman, C., 2001. Flame Retardants in Indoor Air at an Electronics Recycling Plant and at Other Work Environments. Environ. Sci. Technol. 35, 448–454. https://doi.org/10.1021/es000077n Slotkin, T.A., Skavicus, S., Stapleton, H.M., Seidler, F.J., 2017. Brominated and organophosphate flame retardants target different neurodevelopmental stages, characterized with embryonic neural stem cells and neuronotypic PC12 cells. Toxicology 390, 32–42. https://doi.org/10.1016/j.tox.2017.08.009 Smil, V., 2017. PLANET OF THE COWS. IEEE Spectr. 54, 24.

Snedeker, S.M., 2014. Toxicants in Food Packaging and Household Plastics, Molecular and Integrative Toxicology. Springer London, London. https://doi.org/10.1007/978-1-4471- 6500-2 Staaf, T., Ostman, C., 2005. Organophosphate triesters in indoor environments. J. Environ. Monit. 7, 883–887. https://doi.org/10.1039/b506631j Stapleton, H.M., Allen, J.G., Kelly, S.M., Konstantinov, A., Klosterhaus, S., Watkins, D., McClean, M.D., Webster, T.F., 2008a. Alternate and New Brominated Flame Retardants Detected in U.S. House Dust. Environ. Sci. Technol. 42, 6910–6916. https://doi.org/10.1021/es801070p Stapleton, H.M., Kelly, S.M., Allen, J.G., McClean, M.D., Webster, T.F., Stapleton, M.H., Kelly, S.M., Allen, J.G., McClean, M.D., Webster, T.F., Stapleton, H.M., Kelly, S.M., Allen, J.G., McClean, M.D., Webster, T.F., 2008b. Measurement of Polybrominated Diphenyl Ethers on Hand Wipes: Estimating Exposure from Hand-to-Mouth Contact. Environ. Sci. Technol. 42, 3329–3334. https://doi.org/10.1021/es7029625 Statistics Canada, 2016. EnviroStats Trash talking: Dealing with Canadian household e-waste. [WWW Document]. URL http://www.statcan.gc.ca/pub/16-002-x/2016001/article/14570- eng.htm (accessed 7.15.18). Stubbings, W.A., Nguyen, L. V., Romanak, K., Jantunen, L., Melymuk, L., Arrandale, V., Diamond, M.L., Venier, M., 2019a. Flame retardants and plasticizers in a Canadian waste electrical and electronic equipment (WEEE) dismantling facility. Sci. Total Environ. 675, 594–603. https://doi.org/10.1016/j.scitotenv.2019.04.265 Stubbings, W.A., Nguyen, L. V., Romanak, K., Jantunen, L., Melymuk, L., Arrandale, V., Diamond, M.L., Venier, M., 2019b. Flame retardants and plasticizers in a Canadian waste electrical and electronic equipment (WEEE)dismantling facility. Sci. Total Environ. 675, 594–603. https://doi.org/10.1016/j.scitotenv.2019.04.265 Suzuki, G., Tue, N.M., Malarvannan, G., Sudaryanto, A., Takahashi, S., Tanabe, S., Sakai, S., Brouwer, A., Uramaru, N., Kitamura, S., Takigami, H., 2013. Similarities in the Endocrine- Disrupting Potencies of Indoor Dust and Flame Retardants by Using Human Osteosarcoma (U2OS) Cell-Based Reporter Gene Assays. Environ. Sci. Technol. 47, 2898–2908. https://doi.org/10.1021/es304691a Swedish Chemicals Inspectorate, 2003. Brominated flame retardants – Prospects of a national ban. KemI Report 4/03. Takigami, H., Suzuki, G., Hirai, Y., Sakai, S., 2008. Transfer of brominated flame retardants from components into dust inside television cabinets. Chemosphere 73, 161–169. https://doi.org/10.1016/j.chemosphere.2008.06.032 Tansel, B., 2017. From electronic consumer products to e-wastes: Global outlook, waste quantities, recycling challenges. Environ. Int. 98, 35–45. https://doi.org/10.1016/j.envint.2016.10.002 Thuresson, K., Höglund, P., Hagmar, L., Sjödin, A., Bergman, Å., Jakobsson, K., 2006. Apparent Half-Lives of Hepta- to Decabrominated Diphenyl Ethers in Human Serum as

Determined in Occupationally Exposed Workers. Environ. Health Perspect. 114, 176–181. https://doi.org/10.1289/ehp.8350 Tran, T.M., Kannan, K., 2015. Occurrence of Phthalate Diesters in Particulate and Vapor Phases in Indoor Air and Implications for Human Exposure in Albany, New York, USA. Arch. Environ. Contam. Toxicol. 68, 489–499. https://doi.org/10.1007/s00244-015-0140-0 Tran, T.M., Le, H.T., Minh, T.B., Kannan, K., 2017. Occurrence of phthalate diesters in indoor air from several Northern cities in Vietnam, and its implication for human exposure. Sci. Total Environ. 601–602, 1695–1701. https://doi.org/10.1016/j.scitotenv.2017.06.016 Traore, I.T., Gravel, S., Diamond, M.L., Jantunen, L., Nguyen, L.V., Yang, C., Bernstein, S., Zayed, J., Labrèche, F., Verner, M.-A., 2018. Urinary Metabolites of Organophosphate Esters (OPEs) in Electronic Waste Recycling Workers from the Province of Quebec, Canada. ISEE Conf. Abstr. 2018, isesisee.2018.P01.3100. https://doi.org/10.1289/isesisee.2018.P01.3100 Tromp, P.C., Beeltje, H., Okeme, J.O., Vermeulen, R., Pronk, A., Diamond, M.L., 2019. Calibration of polydimethylsiloxane and polyurethane foam passive air samplers for measuring semi volatile organic compounds using a novel exposure chamber design. Chemosphere 227, 435–443. https://doi.org/10.1016/j.chemosphere.2019.04.043 Tue, N.M., Takahashi, S., Suzuki, G., Isobe, T., Viet, P.H., Kobara, Y., Seike, N., Zhang, G., Sudaryanto, A., Tanabe, S., 2013. Contamination of indoor dust and air by polychlorinated biphenyls and brominated flame retardants and relevance of non-dietary exposure in Vietnamese informal e-waste recycling sites. Environ. Int. 51, 160–167. https://doi.org/10.1016/j.envint.2012.11.006 U.S.Bureau of Labor, 2020. Occupational Outlook Handbook [WWW Document]. UCLA Labor Center, 2018. Nail Files: A study of nail salon workers and industry in United States. UNEP, 2019. A New Circular Vision for Electronics Time for a Global Reboot 24. UNEP, 2016. GEO-6 North America Regional Assessment [WWW Document]. URL http://wedocs.unep.org/bitstream/handle/20.500.11822/7611/GEO_North_America_201611 .pdf?sequence=1&isAllowed=y (accessed 6.27.18). UNEP, 2010. Technical review of the implications of recycling commercial pentabromodiphenyl ether and commercial octabromodi- phenyl ether. UNEP, 2008. Report of the Persistent Organic Pollutants Review Committee on the work of its fourth meeting. United States Department of Labor, 2017. Occupational Employment and Wages, May 2017 [WWW Document]. URL https://www.bls.gov/oes/current/oes395092.htm#st US EPA, 2018a. IRIS Assessments [WWW Document]. URL https://cfpub.epa.gov/ncea/iris2/atoz.cfm (accessed 6.27.18). US EPA, 2018b. Chemistry Dashboard [WWW Document]. URL

https://comptox.epa.gov/dashboard (accessed 6.27.18). US EPA, 2018c. 2,2’,4,4’,5-Pentabromodiphenyl ether (BDE-99) [WWW Document]. URL https://cfpub.epa.gov/ncea/iris2/chemicalLanding.cfm?substance_nmbr=1008 (accessed 6.27.18). US EPA, 2011. September 2011 EXPOSURE FACTORS HANDBOOK : 2011 EDITION National Center for Environmental Assessment Office of Research and Development U . S . Environmental Protection Agency Washington , DC 20460 Exposure Factors Handbook. Exposure. USEPA, 2020. CHEMICALS KNOWN TO THE STATE TO CAUSE CANCER OR REPRODUCTIVE TOXICITY January 3, 2020. Veen, I. Van Der, Boer, J. De, 2012. Chemosphere Phosphorus flame retardants : Properties , production , environmental occurrence , toxicity and analysis. Chemosphere 88, 1119– 1153. https://doi.org/10.1016/j.chemosphere.2012.03.067 Venier, M., Ma, Y., Hites, R.A., 2012. Brominated flame retardants in the Great Lakes atmosphere. Environ. Sci. Technol. 46, 8653–8660. https://doi.org/dx.doi.org/10.1021/es3015919 Viberg, H., Fredriksson, A., Eriksson, P., 2004. Investigations of strain and/or gender differences in developmental neurotoxic effects of polybrominated diphenyl ethers in mice. Toxicol. Sci. 81, 344–353. https://doi.org/10.1093/toxsci/kfh215 Viberg, H., Fredriksson, A., Jakobsson, E., Orn, U., Erikson, P., 2003. Neurobehavioral derangements in adult mice receiving decabrominated diphenyl ether (PBDE 209) during a defined period of neonatal brain development. Toxicol. Sci. 76, 112–120. https://doi.org/10.1093/toxsci/kfg210 Vojta, Š., Bečanová, J., Melymuk, L., Komprdová, K., Kohoutek, J., Kukučka, P., Klánová, J., 2017. Screening for halogenated flame retardants in European consumer products, building materials and wastes. Chemosphere 168, 457–466. https://doi.org/10.1016/j.chemosphere.2016.11.032 Vuong, A.M., Braun, J.M., Webster, G.M., Thomas Zoeller, R., Hoofnagle, A.N., Sjödin, A., Yolton, K., Lanphear, B.P., Chen, A., 2018. Polybrominated diphenyl ether (PBDE) exposures and thyroid hormones in children at age 3 years. Environ. Int. 117, 339–347. https://doi.org/10.1016/j.envint.2018.05.019 Vuong, A.M., Yolton, K., Xie, C., Webster, G.M., Sjödin, A., Braun, J.M., Dietrich, K.N., Lanphear, B.P., Chen, A., 2017. Childhood polybrominated diphenyl ether (PBDE) exposure and neurobehavior in children at 8 years. Environ. Res. 158, 677–684. https://doi.org/10.1016/j.envres.2017.07.028 Vykoukalová, M., Venier, M., Vojta, Š., Melymuk, L., Bečanová, J., Romanak, K., Prokeš, R., Okeme, J.O., Saini, A., Diamond, M.L., Klánová, J., 2017. Organophosphate esters flame retardants in the indoor environment. Environ. Int. 106, 97–104. https://doi.org/10.1016/j.envint.2017.05.020 Wallace, L., 2000. Correlations of personal exposure to particles with outdoor air measurements: 40

A review of recent studies. Aerosol Sci. Technol. 32, 15–25. https://doi.org/10.1080/027868200303894 Wallner, P., Kundi, M., Hohenblum, P., Scharf, S., Hutter, H., 2016. Phthalate Metabolites, Consumer Habits and Health Effects. Int. J. Environ. Res. Public Health 13, 717. https://doi.org/10.3390/ijerph13070717 Wan, Y., Diamond, M.L., Siegel, J.A., 2020. Elevated Concentrations of Semivolatile Organic Compounds in Social Housing Multiunit Residential Building Apartments. Environ. Sci. Technol. Lett. 7, 191–197. https://doi.org/10.1021/acs.estlett.0c00068 Wang, D.G., Alaee, M., Byer, J.D., Brimble, S., Pacepavicius, G., 2013. Human health risk assessment of occupational and residential exposures to dechlorane plus in the manufacturing facility area in China and comparison with e-waste recycling site. Sci. Total Environ. 445–446, 329–336. https://doi.org/10.1016/j.scitotenv.2012.12.059 Wang, S., Romanak, K.A., Stubbings, W.A., Arrandale, V.H., Hendryx, M., Diamond, M.L., Salamova, A., Venier, M., 2019. Silicone wristbands integrate dermal and inhalation exposures to semi-volatile organic compounds (SVOCs). Environ. Int. 132, 105104. https://doi.org/10.1016/j.envint.2019.105104 Wang, Y., Peris, A., Rifat, M.R., Ahmed, S.I., Aich, N., Nguyen, L. V., Urík, J., Eljarrat, E., Vrana, B., Jantunen, L.M., Diamond, M.L., 2020. Measuring exposure of e-waste dismantlers in Dhaka Bangladesh to organophosphate esters and halogenated flame retardants using silicone wristbands and T-shirts. Sci. Total Environ. 720, 137480. https://doi.org/10.1016/j.scitotenv.2020.137480 Wei, G.-L., Li, D.-Q., Zhuo, M.-N., Liao, Y.-S., Xie, Z.-Y., Guo, T.-L., Li, J.-J., Zhang, S.-Y., Liang, Z.-Q., 2015. Organophosphorus flame retardants and plasticizers: Sources, occurrence, toxicity and human exposure. Environ. Pollut. 196, 29–46. https://doi.org/10.1016/j.envpol.2014.09.012 Wei, W., Bonvallot, N., Gustafsson, Å., Raffy, G., Glorennec, P., Krais, A., Ramalho, O., Le Bot, B., Mandin, C., 2018. Bioaccessibility and bioavailability of environmental semi- volatile organic compounds via inhalation: A review of methods and models. Environ. Int. 113, 202–213. https://doi.org/10.1016/j.envint.2018.01.024 Wei, W., Mandin, C., Ramalho, O., 2017. Reactivity of Semivolatile Organic Compounds with Hydroxyl Radicals, Nitrate Radicals, and Ozone in Indoor Air. Int. J. Chem. Kinet. 49, 506–521. https://doi.org/10.1002/kin.21093 Weschler, C.J., Nazaroff, W.W., 2014. Dermal Uptake of Organic Vapors Commonly Found in Indoor Air. Environ. Sci. Technol. 48, 1230–1237. https://doi.org/10.1021/es405490a Weschler, C.J., Nazaroff, W.W., 2012. SVOC exposure indoors: Fresh look at dermal pathways. Indoor Air. https://doi.org/10.1111/j.1600-0668.2012.00772.x Weschler, C.J., Nazaroff, W.W., 2010. SVOC partitioning between the gas phase and settled dust indoors. Atmos. Environ. 44, 3609–3620. https://doi.org/10.1016/j.atmosenv.2010.06.029 Weschler, C.J., Nazaroff, W.W., 2008. Semivolatile organic compounds in indoor environments. 41

Atmos. Environ. 42, 9018–9040. https://doi.org/10.1016/j.atmosenv.2008.09.052 Whitman, W.G., 1962. The two film theory of gas absorption. Int. J. Heat Mass Transf. 5, 429– 433. https://doi.org/10.1016/0017-9310(62)90032-7 Wielsøe, M., Kern, P., Bonefeld-Jørgensen, E.C., 2017. Serum levels of environmental pollutants is a risk factor for breast cancer in Inuit: a case control study. Environ. Heal. 16, 56. https://doi.org/10.1186/s12940-017-0269-6 Wong, C.S.C., Duzgoren-Aydin, N.S., Aydin, A., Wong, M.H., 2007. Evidence of excessive releases of metals from primitive e-waste processing in Guiyu, China. Environ. Pollut. 148, 62–72. https://doi.org/10.1016/j.envpol.2006.11.006 Wu, C.-C., Bao, L.-J., Tao, S., Zeng, E.Y., 2016. Dermal Uptake from Airborne Organics as an Important Route of Human Exposure to E-Waste Combustion Fumes. Environ. Sci. Technol. 50, 6599–6605. https://doi.org/10.1021/acs.est.5b05952 Xu, F., Zhang, G., Wang, J., Zhang, W., Liu, L., Lin, K., 2015. Polybrominated diphenyl ethers in air and fallouts from an e-waste polluted region in southeast China: insight into levels, compositional profiles, and seasonal variation. Environ. Sci. Pollut. Res. 22, 19676–19686. https://doi.org/10.1007/s11356-015-5168-1 Xu, Y., Cohen Hubal, E.A., Clausen, P.A., Little, J.C., 2009. Predicting Residential Exposure to Phthalate Plasticizer Emitted from Vinyl Flooring: A Mechanistic Analysis. Environ. Sci. Technol. 43, 2374–2380. https://doi.org/10.1021/es801354f Xu, Y., Cohen Hubal, E.A., Little, J.C., 2010. Predicting residential exposure to phthalate plasticizer emitted from vinyl flooring: Sensitivity, uncertainty, and implications for biomonitoring. Environ. Health Perspect. 118, 253–258. https://doi.org/10.1289/ehp.0900559 Yang, C., Harris, S.A., Jantunen, L.M., Kvasnicka, J., Nguyen, L. V., Diamond, M.L., 2020a. Phthalates: Relationships between Air, Dust, Electronic Devices, and Hands with Implications for Exposure. Environ. Sci. Technol. 54, acs.est.0c00229. https://doi.org/10.1021/acs.est.0c00229 Yang, C., Harris, S.A., Jantunen, L.M., Siddique, S., Kubwabo, C., Tsirlin, D., Latifovic, L., Fraser, B., St-Jean, M., De La Campa, R., You, H., Kulka, R., Diamond, M.L., 2018. Are cell phones an indicator of personal exposure to organophosphate flame retardants and plasticizers? Environ. Int. in press, 1–13. https://doi.org/10.1016/j.envint.2018.10.021 Yang, C., Jílková, S.R., Melymuk, L., Harris, S.A., Jantunen, L.M., Pertili, J., Winn, L., Diamond, M.L., 2020b. Are We Exposed to Halogenated Flame Retardants from both Primary and Secondary Sources? Environ. Sci. Technol. Lett. 7, 585–593. https://doi.org/10.1021/acs.estlett.0c00268 Young, A.S., Allen, J.G., Kim, U.-J.J., Seller, S., Webster, T.F., Kannan, K., Ceballos, D.M., 2018. Phthalate and Organophosphate Plasticizers in Nail Polish: Evaluation of Labels and Ingredients. Environ. Sci. Technol. 52, acs.est.8b04495. https://doi.org/10.1021/acs.est.8b04495 Zabiegała, B., Zygmunt, B., Przyk, E., Namieśnik, J., 2000. Applicability of silicone membrane 42

passive samplers for monitoring of indoor air quality. Anal. Lett. 33, 1361–1372. https://doi.org/10.1080/00032710008543127 Zeng, X., Yang, C., Chiang, J.F., Li, J., 2017. Innovating e-waste management: From macroscopic to microscopic scales. Sci. Total Environ. 575, 1–5. https://doi.org/10.1016/j.scitotenv.2016.09.078 Zhang, H., Yolton, K., Webster, G.M., Sjödin, A., Calafat, A.M., Dietrich, K.N., Xu, Y., Xie, C., Braun, J.M., Lanphear, B.P., Chen, A., 2016. Prenatal PBDE and PCB Exposures and Reading, Cognition, and Externalizing Behavior in Children. Environ. Health Perspect. 125, 7–16. https://doi.org/10.1289/EHP478 Zhang, X., Diamond, M.L., Robson, M., Harrad, S., 2011. Sources, emissions, and fate of polybrominated diphenyl ethers and polychlorinated biphenyls indoors in Toronto, Canada. Environ. Sci. Technol. 45, 3268–3274. https://doi.org/10.1021/es102767g Zhang, Z., Sun, Z.-Z., Xiao, X., Zhou, S., Wang, X.X.-C., Gu, J., Qiu, L.-L., Zhang, X.-H., Xu, Q., Zhen, B., Wang, X.X.-C., Wang, S.-L., 2013a. Mechanism of BDE209-induced impaired glucose homeostasis based on gene microarray analysis of adult rat liver. Arch. Toxicol. 87, 1557–1567. https://doi.org/10.1007/s00204-013-1059-8 Zhang, Z., Zhang, X., Sun, Z., Dong, H., Qiu, L., Gu, J., Zhou, J., Wang, X., Wang, S.L., 2013b. Cytochrome P450 3A1 Mediates 2,2′,4,4′-Tetrabromodiphenyl Ether-Induced Reduction of Spermatogenesis in Adult Rats. PLoS One 8. https://doi.org/10.1371/journal.pone.0066301 Zheng, X., Xu, F., Chen, K., Zeng, Y., Luo, X., Chen, S., Mai, B., Covaci, A., 2015. Flame retardants and organochlorines in indoor dust from several e-waste recycling sites in South China: Composition variations and implications for human exposure. Environ. Int. 78, 1–7. https://doi.org/10.1016/j.envint.2015.02.006 Zota, A.R., Rudel, R.A., Morello-Frosch, R.A., Brody, J.G., 2008. Elevated House Dust and Serum Concentrations of PBDEs in California: Unintended Consequences of Furniture Flammability Standards? Environ. Sci. Technol. 42, 8158–8164. https://doi.org/10.1021/es801792z

Chapter 2 - Exposure of Canadian Electronic Waste Dismantlers to Flame Retardants

Abstract

Exposure of e-waste workers to eight halogenated and five organophosphate ester flame retardant chemicals (FRs) was studied at a Canadian e-waste dismantling facility. FR concentrations were measured in air and dust samples collected at a central location and at four work benches over five 24-hour periods spanning two weeks. The highest concentrations in air from workbenches were of BDE-209 (median 156 ng m-3), followed by Tris(2-chloroethyl) phosphate (TCEP, median 59 ng m-3). Dust concentrations at the workbenches were higher than those measured at the central location, consistent with the release of contaminated dust during dismantling. Dust concentrations from the workbenches were also dominated by BDE-209

(median 96,300 ng g-1), followed by Triphenyl phosphate (TPhP, median 47,000 ng g-1). Most

FRs were in coarse particles 5.6 - 18 µm diameter and ~30 % were in respirable particles (<~3

µm). Exposure estimates indicated that dust ingestion accounted for 63 % of total FR exposure; inhalation and dermal absorption contributed 35 and 2 %, respectively. Some air and dust concentrations as well as some estimated exposures in this formal facility in a high-income country exceeded those from informal e-waste facilities located in low- and middle-income countries. Although there is demonstrated toxicity of some FRs, FR exposure in the e-waste industry has received minimal attention and occupational limits do not exist for most FRs.

2.1 Introduction

The significant increase in electronic and electrical waste (e-waste) is of considerable concern for global environmental and human health. In 2014, approximately 41.8 million tonnes of e-waste was generated, which is expected to increase to 50 million tonnes annually by 2018

(Baldé et al., 2015). For comparison, the mass of e-waste generated annually is nearly 10% of the human biomass on Earth, which was approximately 370 million tonnes in 2014 (Smil, 2017).

Though estimates of e-waste generation are highly uncertain, it is clear that globally we are confronted with large masses of e-waste and that the rate of e-waste generation is increasing

(Bakhiyi et al., 2018; Kahhat and Williams, 2012; Robinson, 2009).

Nearly 20 years ago, Sjödin et al. (2001) reported elevated exposures of e-waste workers in Sweden to Polybrominated diphenyl ethers (PBDEs). Since then, studies from several countries have shown that e-waste recycling workers can be exposed to a wide variety of hazardous substances including heavy metals (Asante et al., 2012; Singh et al., 2018; Wong et al., 2007) and flame retardants (FRs) (Mäkinen et al., 2009; Rosenberg et al., 2011; Sjödin et al., 2001). The latter include halogenated FRs (HFRs) such as PBDEs, novel brominated FRs (NBFRs), and organophosphate esters (OPEs). Penta- (consisting mainly of BDE-47 and BDE-99), Octa-

(consisting mainly of BDE-183), and Deca-BDE (almost exclusively BDE-209) were PBDE commercial formulations (La Guardia et al., 2006) that were added to upholstery textiles and foams, polymers used in the plastic casings of electrical and electronic products, motherboards, transistors, capacitors and battery casings to comply with flammability standards (Abbasi et al.,

2015; UNEP, 2010; Vojta et al., 2017).

A large body of evidence shows that human exposure to FRs can be associated with adverse health effects. Fetal and early life exposure to PBDEs at ambient levels has been linked

45 to neurodevelopmental outcomes, notably reduced IQ and externalizing behavior problems (Lam et al., 2017; Vuong et al., 2017; Zhang et al., 2016), abnormal migration of testes (Goodyer et al.,

2017), and alterations in timing to puberty, as well as breast cancer among Alaskan women

(Holmes et al., 2014) (but not women in Greenland (Wielsøe et al., 2017)). PBDEs came under national and international controls in the 2000s and early 2010s (UNEP, 2008) in response to evidence showing increasing human exposure and their widespread global environmental distribution (Betts, 2002; Hites, 2004; Meironyté et al., 1999).

In response to controls placed on PBDEs, the marketplace has shifted to other compounds, notably OPEs which function both as FRs and plasticizers. Studies conducted a decade ago reported relatively high indoor concentrations of OPEs, some of which were traced to electronic products (Hartmann et al., 2004; Staaf and Ostman, 2005). Widespread human exposure to OPEs is now apparent (Cequier et al., 2015; Hoffman et al., 2017a; Ospina et al., 2018; Yang et al.,

2018) and evidence mounts of adverse health effects related to some OPE exposures at ambient levels. Among the adverse effects related to exposure to several OPEs are poor in vitro fertilization outcomes and reduced semen quality (Carignan et al., 2018; Carignan et al., 2017; Meeker et al.,

2013; Meeker and Stapleton, 2009), as well as increased risk of papillary thyroid cancer in adults

(Hoffman et al., 2017b). Fetal exposure to some OPEs has been found to decrease Full-Scale IQ and working memory at age 7 (Castorina et al., 2017), and exposure in children aged 6-8 years has also been associated with reduced cognitive performance (Hutter et al., 2013). In vitro and embryo studies have provided evidence that OPEs can cause neurotoxicity, endocrine modulation, and steroidogenesis (Behl et al., 2016; Glazer et al., 2018; Slotkin et al., 2017).

In an occupational setting of e-waste recycling, opportunities for exposure to FR- containing dust can occur during two main processes. First, dust that has accumulated inside

46 products over the course of the product’s life is released during dismantling. This “aged” dust can directly sorb FRs from the interior electronic components leading to 2-3 orders-of-magnitude higher concentrations than in typical indoor dust (Takigami et al., 2008). Second, dust containing

FRs is generated when e-waste undergoes grinding, shredding, compaction and further processing.

With a few exceptions (Beaucham et al., 2018; Kuo et al., 2019; Sjödin et al., 2001), many studies of FR exposure in e-waste have come from low- and middle-income countries (LMICs) where e-waste dismantling is, or has been, conducted in informal settings with minimal controls on the disposal of final wastes (e.g, Labunska et al., 2014). In LMICs, the work typically occurs in the community, such as the backyard of the houses within 20 m of the living area (Tue et al.,

2013), leading to high levels of exposure both to workers as well as to their families by direct exposure and exposure through eating contaminated foods (Akormedi et al., 2013; Chan and

Wong, 2013; Frazzoli et al., 2010; Grant et al., 2013; Heacock et al., 2015; Labunska et al., 2014).

High income countries (HICs), such as Canada and countries in the European Union, have legislation promoting the safe handling of e-waste domestically (EC, 2018; Government of

Ontario, 2018). In contrast to LMICs, e-waste recycling in HICs generally occurs in more formal industrial settings where dismantling occurs in an enclosed building and the components from dismantling are removed for processing elsewhere, e.g., high temperature recovery of metals from wiring. We note that dismantling is often done manually in both formal and informal settings. As discussed by Bakhiyi et al. (2018), the “formality” of dismantling activities in HICs comes from government licensing and the need to comply with environmental laws and regulations (e.g.,

Ceballos and Dong, 2016), which may or may not be adequate.

Elevated exposures of e-waste dismantlers in formal settings has been documented.

Contrary to the presumption of safe handling, Sjödin et al. (2001) found that FR exposures in

47 personal air samples collected in Sweden about 20 years ago were at least an order of magnitude higher in an electronics recycling facility as compared to the other workplaces including a circuit board factory and a computer repair business. In another Swedish e-waste recycling facility,

Pettersson-Julander et al. (2004) reported that dismantlers consistently had the highest mean levels of personal exposure to PBDEs, 1,2-bis(2,4,6-tribromophenyoxy)ethane (BTBPE) and

Decabromodiphenyl ethane (DBDPE) when compared with other workers. Recently, Beaucham et al. (2018) reported worker exposure to PBDEs and other FRs in an US e-waste facility. They also found that dismantlers, and especially those working in the shredder/sorter area, were exposed to higher levels of FRs than workers in other areas of the facility. In addition, Rosenberg et al.

(2011), who measured airborne FR concentrations at four e-waste handling facilities in Finland in

2008 - 2009, found that exposures were partly explained by the type of material being processed and the volume processed on the sampling day.

Outside of occupational regulations, a challenge for e-waste workers is that regulatory

(e.g., US Toxic Substances Control Act or TSCA, Canadian Environmental Protection Act or

CEPA, European Commission’s Registration, Evaluation, Authorisation and Restriction of

Chemicals or REACH) and non-regulatory (e.g., Stockholm Convention) controls on toxic chemicals pertain to prohibiting the production and uses of FRs in new products such as electrical and electronic equipment. However, e-waste workers are handling old electrical and electronic equipment some (if not much) of which contains controlled substances, notably PBDEs, as it takes decades for these controlled substances to leave the use phase (Abbasi et al., 2015; Lucas et al.,

2017). Surprisingly, there are few occupational exposure limits in Canada to protect e-waste handlers from FRs. In addition, legislative frameworks for chemical management in Canada do not consider occupational exposure or impacts that could occur as a prohibited chemical in a

48 product reaches its End-of-Life (CEPA, 1999). Both chemical management and occupational health and safety legislative frameworks consider exposure on an individual chemical-by- chemical basis, potentially overlooking the effects of exposure to complex mixtures of FRs and other toxic compounds such as metals.

The focus of this study was to document occupational exposure of Canadian workers to

HFRs and OPEs. This study reports on measured air and dust concentrations of 13 common FRs in a formal e-waste dismantling facility in Ontario, Canada, and the associated estimates of workers’ exposure in this facility. Our aim is to shed light on occupational exposures in this industry in Canada.

2.2 Materials and Methods

2.2.1 Study Location

The sampling was conducted at an e-waste recycling facility located in a multi-unit industrial building in Ontario, Canada. The facility processed approximately 4000 tonnes of mixed e-waste annually, based on reported amounts processed during the study period. Products sorted and/or dismantled included televisions, monitors, computers, as well as small electronics (e.g., telephones, toasters, curling irons) and medical equipment. Plastics from cases, wiring and electrical components were bundled separately and physically compacted in the facility using a crusher to reduce volume. Compaction took place in the facility without exterior venting. A shredder was not operated in the facility. Employment numbers varied seasonally ranging from approximately 20 to 30 people. At the time of study, the facility operated 16 hours per day, with two 8-hour shifts. Workers dismantled each product by hand at dismantling benches using power

49 tools as necessary. Workers did not appear to specialize in the type of e-waste that he/she dismantled. Inconsistent use of protective clothing, gloves and surgical/dust masks was observed in the facility; no workers were observed to wear respirators (N95 or otherwise).

2.2.2 Sampling Strategy

The sampling was conducted at two types of locations: a central workplace where no dismantling activities were performed and at four workbenches where dismantling took place. We had limited access to the facility. As such we sampled, in total, five 24-hour periods over two weeks in February 2017. No sampling was conducted over weekends. A schematic of the facility and the locations sampled is depicted in Figure A2.1 in Appendix 1. We were allowed access once per 24-hour period and were not allowed to have contact with any workers. All samples collected were stationary samples.

Indoor air samplers were deployed for 24 hours at two locations in the plant, a central location (n = 10) and at the workbenches (n = 20) where workers manually dismantled e-waste

(displayed in Figure A2.2 in Appendix 1). At the central location, two stationary active air samplers were deployed side-by-side. The sampling train consisted of a glass fiber filter (GFF-

AA) (Whatman, UK, diameter 47 mm, pore size 0.1µm) followed by an ORBO 1500 (PUF/XAD-

2/PUF, 22 mm x 100 mm) sorbent cartridge (Supelco, Sigma Aldrich, Canada) connected to an active air pump (BGI 400S, PacWill Environmental, Canada) set at a flow rate of 10 L min-1.

Stationary air samples taken at the dismantling workbenches were collected using OSHA

Versatile Samplers (OVS) (ORBO 49P (OVS), Supelco, Sigma Aldrich, Canada) that is typically worn as a personal active air sampler. The OVS tube (13 mm x 75 mm) consisted of a glass fiber filter (GFF-OVS, diameter 13 mm, pore size 0.1 µm) and PUF/XAD-2/PUF sandwich, connected

50 to an AirCheck XR500 pump (SKC Inc., Pennsylvania, USA) set at a flow rate of 2 L min-1. The

OVS was hung on the front of the work bench near the breathing zone (within 1-2 m) of the workers (see Figure A2.2 in Appendix 1). Pumps were calibrated pre- and post-deployment each day to assess the drift in the flow rate. Three samples (all from the central location) had a flow rate drift > 5% (in occupational hygiene acceptable drift is considered to be <5%). One of the three samples was discarded because of problems encountered with analysis. Chemical concentrations of the remaining two samples were statistically indistinguishable from all others and thus were included in the final statistical analysis. Here we report on 9 and 20 samples in total at the central area and workbenches, respectively.

A Micro-Orifice Uniform Deposition Impactor (MOUDI) (MOUDI, MSP, Shoreview N,

USA, model 110NR) was deployed twice at the central location to obtain size segregated air particle samples. The MOUDI operated at a flow rate of 16 L min-1 and collected particles over

10 size fractions (0.056, 0.1, 0.18, 0.32, 0.56, 1.0, 1.8, 3.2, 5.6, 10 and 18 µm) using GFFs (GFF-

MOUDI) (Whatman, UK, diameter 47 mm, pore size 0.1µm) and a Gast diaphragm pump (MFG.

Corp., Michigan, USA). A total of two samples, each with 10 size fractions, were collected with the MOUDI.

Dust samples were collected using a vacuum cleaner (Sanitare Professional, Canada) fitted with a nylon vacuum sock using the method of Yang et al. (2018). Dust samples were collected from the floor (n = 7) and the top of the work benches (n = 8). The sampling area (ca. 1.5 m2) was vacuumed for one minute per sample.

After sampling, each type of air sample, including GFF-AAs, GFF-MOUDIs, ORBO cartridges and OVS tubes, was wrapped separately in pre-cleaned aluminum foil and stored in air-

51 tight glass jars at -20 0C until extraction. All dust samples were wrapped in pre-cleaned aluminum foil and stored in Ziploc bags at -20 0C until extraction.

2.2.3 Pre-cleaning, Extraction and Analysis

Prior to sampling, all media (GFF-AAs, GFF-MOUDIs, ORBO cartridges, OVS tubes and nylons socks) were pre-cleaned. Detailed pre-cleaning methods can be found in section A2.1 in

Appendix 1.

The GFF-AAs and ORBO cartridges used in the active air samplers at the central location were extracted separately and results were combined to provide the bulk air concentrations. The

GFF-OVS and a PUF/XAD-2/PUF sandwich of the OVS sampler were extracted together to report the bulk air concentrations. The ORBO cartridges and OVS (filters and sorbent) samples were extracted in acetone, dichloromethane and n-hexane (1:1:1 v:v:v) via accelerated solvent extraction (ASE) (Dionex, Sunnyvale, CA, USA). GFF-AAs, GFF-MOUDIs and dust samples were extracted in acetone and n-hexane (1:1 v:v) by sonication followed by vortexing. Individual dust samples were sieved to <500 µm from which 50 mg was subsampled. All samples and blanks

(in section 2.2 and 2.4) were analyzed for 8 HFRs and 5 OPEs (Table A2.1 in Appendix 1 lists full names and CAS numbers) using gas chromatography mass spectrometry (GC-MS) in electron capture negative ionization (ECNI) mode (HFRs) or electron impact (EI) mode (OPEs). Full details of sample extraction and instrumental analysis with monitored ions are given in sections

A2.2, Tables A2.2 and A2.3 in Appendix 1.

2.2.4 Quality Assurance and Quality Control (QA/QC)

Field blanks were collected each day and analyzed along with laboratory blanks for all sample types. All blanks and samples were spiked with surrogate standards to evaluate recoveries of the sample preparation methods. Averages of field blank levels of each sample type were used for blank correction (and discarding samples) according to the criteria described by Saini et al.

(2015). Blanks levels were low and thus no blank correction was necessary. BDE-77, BDE-166

13 and C12-BDE-209 (Wellington Laboratories Inc., Ontario, Canada) were used as surrogate

13 standards for HFRs; d12-TCEP and C18-TPhP (Wellington Laboratories Inc., Ontario, Canada) were used as surrogate standards for OPEs. For air and dust samples, the recoveries of individual compounds were determined using a set of pre-cleaned sampling media (n = 3 for dust, 1 for

ORBO, 2 for OVS, and 3 for GFF) for each batch of samples spiked with the native analytes prior to extraction. The recoveries of matrix spikes varied between 79 % to 120 %. Average recoveries for surrogates were 98 – 145 % (HFRs) and 104 – 128 % (OPEs). Results were not recovery corrected based on the criteria described by Vykoukalová et al. (2017). Full details of the QA/QC are provided in section A2.3 in Appendix 1.

2.2.5 Exposure Estimates

Exposure though inhalation, dust ingestion and dermal absorption was calculated from the measured concentrations of workbench dust and air using the equations from Agency for Toxic

Substances and Disease Registry (ATSDR, 2005) with exposure factors obtained from the U.S.

Environmental Protection Agency (US EPA, 2011) (Table A2.4 in Appendix 1). Inhalation and dust ingestion of FRs were assumed to occur at the workbench only during 8 working hours, thus ignoring the exposure of workers in other environments during the remaining 16 hours each day. 53

The inhalation rate for male and female workers was 18 and 14 m3 day-1, respectively (US

EPA, 2011). Here, we assumed 100 % absorption of air intake when estimating inhalation exposure because most workers did not wear any respiratory protective equipment and none were observed to use N95 respirators. We observed that some workers wore surgical/dust masks.

However, previous studies have found that surgical or face masks, with penetration levels for nano-size particles of more than 50 %, are inadequate to prevent inhalation of air particles

(Flanagan et al., 2003; Rengasamy et al., 2010).

Dermal absorption was assumed to occur only through exposed skin on the head and hands of workers because workers were observed to wear long sleeves and pants, but not protective gloves. We adopted estimates of the fraction of chemical absorbed by skin reported by Abdallah et al. (2015b, 2015a), Abdallah et al. (2016) and Pawar (2017) (Table A2.5 in Appendix 1).

Since this facility was an environment with a high particle load, we used the dust ingestion rate at 95th percentile that US EPA recommended for adults, namely 0.06 g day-1 (US EPA, 2011).

2.2.6 Data Analysis

Statistical analysis was performed with R version 3.4.1 (R Foundation for Statistical

Computing, Vienna, Austria). All air and dust samples reported here were greater than method detection limits, hence we did not have any censored data. Averages, medians, minimum and maximum values were reported in order to compare with exposure levels of FRs found in previous studies. Non-parametric tests were used for comparisons since dust and air concentrations were not normally distributed. Differences in concentrations were investigated using the Mann Whitney

U and Kruskal-Wallis tests. Spearman’s analysis was used to assess correlations. Differences were considered significant at p < 0.05.

2.3 Results and Discussion

Here we report on the concentration of 13 FRs in 29 air samples (n = 9 at a central location and n = 20 at the work benches), two MOUDI samples (each with 10 size fractions), and 15 dust samples (n = 7 from the floor beside the work benches; n = 8 from the work bench tops where the dismantling work was performed). A summary of the concentrations is presented in Table 2.1.

2.3.1 Air Concentrations

The HFR and OPE levels in air at the workbenches were consistently higher compared to the central workplace; most comparisons were statistically significant (p < 0.05) with the exceptions of BDE-209, 2-Ethylhexyl-tetrabromobenzoate (EHTBB), syn-Dechlorane plus (s-

DP) and anti-DP (a-DP) (Table 2.1). Air concentrations of FRs were not significantly different among workbenches collected on the same day and from the same workbenches collected on different days, although trends suggested that Bench 1 tended to have higher levels, and that Day

2 may have had higher concentrations relative to other sampling days (Table A2.6 in Appendix

1). A moderate correlation was observed between both BDE-209 and Tris(2-chloroisopropyl) phosphate (TCIPP) in the workbench air and the amount of waste reportedly processed each day

(Spearman’s rho = 0.5, p < 0.05) (Table A2.7 in Appendix 1).

BDE-209 was the most abundant compound in air samples collected at both the central workplace and the workbenches, accounting for more than 30 % of ∑13 FRs in air. At the workbenches, the median concentration of BDE-209 in air was 156 ng m-3. The next most abundant HFR in air at the workbenches was Bis(2-ethlyhexyl) tetrabromophthalate (BEHTBP), with a median concentration of 5.4 ng m-3. BEHTBP and EHTBB have been used as replacements for the withdrawn penta-BDE commercial mixture, at least for upholstered furniture (Stapleton et

55 al., 2008a), and have been reported to be found in electronic and electrical devices (e.g., personal computers, CRT TV and flat screen televisions) (Abbasi et al., 2016; Hazrati and Harrad, 2006;

Vojta et al., 2017). Tris(2-chloroethyl) phosphate (TCEP) was the most abundant OPE in workbench air samples, with a median concentration of 59 ng m-3, followed by TCIPP with a median of 50 ng m-3.

The higher concentrations at work the benches than at the central location is consistent with the hypothesis of Takigami et al. (2008) that higher FR concentrations are released from dust that accumulates in the interior of electronic devices during dismantling than in ambient house dust. Our results suggest that workers performing dismantling tasks have higher levels of personal exposure than workers in the central area of the facility.

Table 2.2 shows that FR air concentrations in the Ontario facility were similar for BDE-

47 and -99, 8 times lower for BDE-183, and 5 times higher for BDE-209, TCEP and TCIPP compared to those measured indoors in Sweden some 20 years ago (Sjödin et al., 2001). TCIPP and Tris(1,3-dichloro-2-propyl) phosphate (TDCIPP) concentrations were ~1.5 times higher while

TCEP was lower compared to a Finnish study of an e-waste dismantling hall conducted about 10 years ago (Mäkinen et al., 2009). Levels of BDE-47, -99 and -209 measured here were up to 650 times higher than those measured in Vietnamese informal dismantling houses in 2008 (Tue et al.,

2013).

The comparison with the Swedish study of Sjödin et al. (2001) is interesting because those concentrations were measured before new uses of Penta- and Octa-BDE were banned in 2003

(Swedish Chemicals Inspectorate, 2003) while our measurements were taken nearly 10 years after

Canadian controls were implemented (Government of Canada, 2016). However, caution must be used in this comparison because samples reported here represent 24-hour integrated

56 concentrations that include 8-hours when no dismantling was being done. As such, we have likely underestimated the air concentrations during active work periods and hence worker exposure during working hours. In contrast, Sjödin et al. (2001) and Mäkinen et al. (2009) measured air concentrations using active samplers during the working day for shorter periods (range 2 - 11 hours), which more accurately approximates average concentrations during the work period.

Compounds Locations Statistical BDE BDE BDE BDE EHTBB BEHTBP s-DP a-DP TCEP TCIPP TDCIPP TPhP EHDPP (units) parameters 47 99 183 209 Air (ng m-3) Central area, Average 0.46 1.0 1.5 108 0.84 2.8 1.9 4.0 19 25 17 26 15 n = 9 Median 0.46 1.0 1.5 101 0.69 2.6 1.8 4.0 19 24 17 26 16 Minimum 0.13 0.35 0.26 16 0.6 1.5 0.51 2.2 14 19 11 16 11 Maximum 0.73 1.6 2.3 165 1.3 4.6 3.3 6.4 24 33 20 35 20 SD 0.17 0.36 0.59 45 0.29 1.1 0.78 1.3 3.6 4.9 3.1 6.2 3.0 Workbench, Average 1.1 2.1 2.4 175 2.2 12 2.2 4.3 61 59 142 66 31 n = 20 Median 0.83 1.5 2.1 156 1.2 5.4 2.0 3.8 59 50 48 46 21 Minimum 0.55 0.94 1.5 65 0.31 2.1 1.5 2.3 30 34 17 29 12 Maximum 3.1 6.4 4.5 469 12 55 3.1 8.5 118 119 790 226 110 SD 0.66 1.5 0.8 94 3.0 16 0.54 1.5 24 22 222 50 27 Central area versus workbench <0.05 <0.05 <0.05 0.10 0.18 <0.05 0.47 0.66 <0.05 <0.05 <0.05 <0.05 <0.05 p-value Dust (ng g-1) Floor, Average 432 813 1,300 96,700 1,340 1,990 6,840 13,840 7,860 11,090 33,600 39,500 7,860 n = 7 Median 402 618 1,380 89,200 693 1,940 2,090 4,520 7,440 10,900 21,500 36,700 8,190 Minimum 304 570 832 78,800 196 41 609 1,540 5,350 9,410 13,400 25,400 4,240 Maximum 611 1,170 1,570 119,000 5,170 3,680 19,400 40,680 12,400 12,600 114,000 62,800 10,840 SD 116 289 256 18,000 1,720 1,260 8,040 15,160 2,250 1,210 35,900 13,500 2,450 Workbench, Average 446 616 2,730 112,000 861 3,420 1,620 3,730 9,110 11,700 18,000 45,300 7,480 n = 8 Median 403 534 1,910 96,300 738 2,710 614 1,650 9,260 11,800 16,300 47,000 6,080 Minimum 304 262 774 29,600 546 1,260 366 1,170 6,890 9,770 12,600 26,700 3,700 Maximum 739 1,190 7,160 244,000 1,610 6,660 5,170 10,800 11,500 13,400 27,700 57,900 14,800 SD 156 279 2,140 72,500 352 2,120 2,030 4,170 1,660 1,290 5,080 11,700 3,570 Floor versus workbench 0.96 0.15 0.07 0.96 0.10 0.34 0.05 0.05 0.15 0.53 0.23 0.40 0.69 p-value Mann-Whitney U test was used to determine the significant association of FRs concentrations between workbenches and central area. Null hypothesis was that the FR concentrations collected from workbenches and floor were from identical populations.

SD: standard deviation

Table 2.2 Comparison of concentrations of 13 halogenated and organophosphorus flame retardants measured in air and dust reported for indoor e-waste handling facilities in a Canadian facility and in various countries.

Compounds Statistical BDE BDE BDE BDE EH- BEH- Location (reference) s-DP a-DP TCEP TCIPP TDCIPP TPhP EHDPP parameter 47 99 183 209 TBB TBP Air (ng m-3) Average 1.1 2.1 2.4 175 2.2 12 2.2 4.3 61 59 142 66 31 Canada, this study, four Median 0.83 1.5 2.1 156 1.2 5.4 2.0 3.8 59 50 48 46 21 workbenches, n = 20 Minimum 0.55 0.94 1.5 65 0.31 2.1 1.5 2.3 30 34 17 29 12 Maximum 3.1 6.4 4.5 469 12 55 3.1 8.5 118 119 790 226 110 Sweden, dismantling hall, Average 1.2 2.6 19 36 - - - - 25 21 - - - n =12 Minimum 0.40 0.5 6.3 12 - - - - 15 14 - - - (Sjӧdin et al., 2001) Maximum 2.1 5.5 44 70 - - - - 36 28 - - - Finland, dismantling Median ------78 17 ND 70 - facility*, n = 6 Minimum ------< 3.0 < 9.0 <36 <5.0 - (Mäkinen et al., 2009) Maximum ------203 26 44 657 - Vietnam, informal e- waste houses┼, n = 4 Average 0.11 0.07 - 0.27 ------(Tue et al., 2013) Dust (ng g-1) Average 432 813 1,300 96,700 1,340 1,990 6,840 13,840 7,860 11,090 33,600 39,500 7,860 Canada, this study, Median 402 618 1,370 89,200 693 1,940 2,086 4,520 7,440 10,890 21,500 36,700 8,190 workshop floor, n = 7 Minimum 304 570 832 78,810 196 41 609 1,540 5,350 9,406 13,400 25,400 4,240 Maximum 611 1,170 1,570 119,000 5,170 3,680 19,400 40,700 12,400 12,600 114,000 63,000 10,800 Taizhou, China, Average 310 270 - 30,000 ------workshop floor, n =5 (Ma Minimum 70 24 - 5,600 ------et al., 2009) Maximum 530 510 - 81,000 ------Average 410 870 1,800 33,000 ------Thailand, workshop Median 160 380 1,700 20,000 ------floor, n = 25 (Muenhor et al., 2010) Minimum 6.9 10 11 250 ------Maximum 1,800 4,600 6,700 250,000 ------Vietnam, informal e- Median 160 150 18 860 ------waste houses, n = 4 Minimum 7.6 7.1 2.8 69 ------(Tue et al., 2013) Maximum 670 770 100 7,900 ------Guiyu, China, furniture, Median 984 1,370 2,030 55,100 60 49 1,050 2,378 633 3,760 1,500 9,810 2,180 windowsills and Minimum 26 48 60 1,770 <1.0 <5.0 49 196 149 854 228 371 222 workshop floor, n = 14 (Zheng et al., 2015) Maximum 3,440 7,720 24,500 232,000 178 779 4,530 9,940 6,920 10,000 14,100 332,000 6,900 “-“: No information; ND: non-detects; * Calculated from air concentrations in e-waste dismantling facilities collected by stationary IOM samplers reported in TableS4 and S5 of Mäkinen et al (2009) ; ┼ Average concentration was calculated from air concentration reported for TM-EW and BD-EW location in Table 2 of Tue et al (2013)

150

) ∑8 HFRs ∑5 OPEs

3 - 100

Concentration (ng (ng m Concentration 1* 2* 3* 4* 5* 6* 7* 8 9 10 Stages

* Respirable particles

Particle sizes of: stage 1 = 0.056 – 0.1 µm; stage 2 = 0.1 – 0.18 µm; stage 3 = 0.18 – 0.32 µm; stage 4 = 0.32 – 0.56 µm; stage 5 = 0.56 – 1 µm; stage 6 = 1 – 1.8 µm; stage 7 = 1.8 – 3.2 µm; stage 8 = 3.2 – 5.6 µm; stage 9 = 5.6 – 10 µm and stage 10 = 10 – 18 µm.

Concentrations of Ʃ8 HFRs and Ʃ5 OPEs on size-fractionated air particles (0.05 to 18 µm diameter) collected by the MOUDI are shown in Figure 2.1 with details in Table A2.8 (Appendix

1). More than 70 % of total airborne FR mass was found in coarse particles ranging from 3.2 to

18 µm diameter and conversely, 30 % were in respirable particles (< ~3µm diameter). The most abundant size fraction in terms of total airborne FR concentrations was on inhalable particles 3.2

- 5.6 µm diameter. The abundance of FRs in the larger size fractions is consistent with the dusty environment caused by the dismantling and compacting e-waste components. Surgical masks have been observed to filter 92% of coarse particles (>4-10μm) and could be effective in preventing inhalation of these particles (Breul et al., 2020); however, we observed that many workers working in the facility did not wear a mask of any kind.

-3 -3 Concentrations of 191 ng m for Ʃ8 HFRs and 215 ng m for Ʃ5 OPEs when all size ranges were summed were comparable to measured bulk air concentrations. Brown et al. (2013) found

-3 that the concentrations of Ʃ5 OPEs and Ʃ8 HFRs in respirable particles were 62 and 55 ng m , respectively. The concentrations of Ʃ5 OPE and Ʃ8 HFR in respirable particles constituted 14 and

18 % of total FR concentrations collected across all the entire particle size range. The most abundant compounds measured in the respirable particles range were BDE-209 among PBDEs and Triphenyl phosphate (TPhP) among OPEs, accounting for 13 and 11 % of Ʃ13 FRs, respectively. These respirable particles can reach the gas exchange region of the lung and are of concern for worker health.

Similarly to our findings, BDE-209 was the most abundant PBDE in respirable particles in a Swedish e-waste facility sampled in 2002 (Julander et al., 2005). The BDE-209 average concentration in respirable particles of 53 ng m-3 we measured here was 18 times higher than the value of 3.1 ng m-3 reported by Julander et al. (2005). However, concentrations of other PBDEs reported here were at similar or lower concentrations than those in the Swedish study of Julander et al. (2005): 0.93 (Sweden) vs. 0.33 ng m-3 for BDE-183; 0.26 (Sweden) vs. 0.10 ng m-3 for BDE-

47; and 0.52 (Sweden) vs. 0.21 ng m-3 for BDE-99. As noted above, these differences are consistent with the timing of the sampling by Julander et al. (2005) versus our study, the implementation of restrictions on PBDEs in Sweden versus Canada, as well as geographic differences in usage of PBDEs.

Results from the MOUDI are similar to those reported by Kim et al. (2015) for a US e- waste recycling plant where particulate matter of 2.5 - 10 µm was 3 - 4 times more abundant than the <2.5 µm fraction. Other studies showed that smaller size fractions contain a greater concentration of OPEs and HFRs but they refer to outdoor air particles at background sites

(Okonski et al., 2014) and an indoor home setting (Richman et al., 2018), which are not comparable to an indoor e-waste dismantling facility.

2.3.2 Dust Concentrations

The most abundant compound found in dust samples was BDE-209, which accounted for more than 40% of all FRs (Table 2.1). The median concentration of BDE-209 in dust at the workbenches was 96,300 ng g-1, followed by BEHTBP and then a-DP and s-DP, with median values of 2,710, 1,650 and 614 ng g-1, respectively. Among OPEs, the highest dust concentration at workbenches was of TPhP with a median concentration of 47,000 ng g-1, followed by TDCIPP with a median concentration of 16,300 ng g-1. No significant differences (p-values ≥ 0.05) were found when comparing each FR in floor and workbench dust, suggesting that they had similar sources. A moderate correlation was observed between BDE-47 (Spearman’s rho = 0.5), BDE-

183 (Spearman’s rho = 0.6) and 2-Ethylhexyl diphenyl phosphate (EHDPP) (Spearman’s rho =

0.4) in workbench dust and the amount of waste processed each day, but these did not reach statistical significance (Table A2.7 in Appendix 1).

Similarly to our finding, BDE-209 was the most abundant PBDE in dust collected at e- waste dismantling sites in the US (Kuo et al., 2019), China (Ma et al., 2009; Zheng et al., 2015),

Thailand (Muenhor et al., 2010), and Vietnam (Tue et al., 2013). These findings are consistent with Deca-BDE being, by far, the dominant commercial mixture found in waste electrical and electronic equipment (Abbasi et al., 2015).

Indoor dust levels of HFRs and OPEs in this study were generally higher than those reported in the most recent indoor e-waste studies conducted in low and middle income countries

(LMICs) such as China (Ma et al., 2009; Zheng et al., 2015) and Vietnam (Tue et al., 2013). Levels

62 of PBDEs found in indoor Thai e-waste dust (Muenhor et al., 2010) were comparable to those reported here. One exception to this trend was the levels of Penta- and Octa-BDEs in the current study that were half of the levels found in indoor dust from a site at Guiyu, China e-waste, where the type of facility was not specified (Zheng et al., 2015).

It is noteworthy that in some cases, the dust concentrations, air concentrations and estimated exposures estimated here exceeded those from informal recycling situations in LMICs.

For air concentrations, one explanation is that the recycling facility in Ontario was contained in a large, but enclosed indoor facility while the informal e-waste facilities in Vietnam (Tue et al.,

2013) were small and likely had more natural ventilation. For dust concentrations, two explanations may pertain. First, the dust in informal e-waste facilities could be diluted by outdoor dust entering via natural ventilation. Second, the higher FR concentrations per mass of dust could be due to the compactor used in this Ontario facility that was not vented. We were not aware of any operating emission abatement equipment.

2.3.3 Occupational Exposure to Flame Retardants

The estimated exposure of workers in the e-waste facility to FRs via inhalation, dermal absorption and dust ingestion during work hours is summarized in Table 2.3. Median total FR exposure for men through the three pathways was 80,900 pg kg-bw-1 day-1 with 42,400 (52 %)

-1 -1 and 38,500 pg kg-bw day (48%) for Ʃ8 HFRs and Ʃ5 OPEs, respectively. Dust ingestion accounted for 63% of total estimated FR exposure while dermal absorption contributed the least

(2% of total exposure). Among PBDEs, BDE-209 had the highest exposure levels through both inhalation and dust ingestion pathways.

Table 2.3 Estimated occupational exposure of male and female workers in a Canadian e-waste recycling facility via air inhalation, dermal absorption and dust ingestion. Details of exposure factors and calculations are provided in section 2.5, and Tables S4 and S5.

Compounds (pg kg-bw-1 day-1) Statistical BDE BDE BDE BDE EH- BEH- Exposure pathway s-DP a-DP TCEP TCIPP TDCIPP TPhP EHDPP ∑ FRs parameters 47 99 183 209 TBB TBP 13 Median 59 107 150 11,030 84 385 143 270 4,130 3,540 3,380 3,220 1,500 28,000 Air inhalation 5th percentile 39 66 109 5,430 30 178 105 198 2,280 2,430 1,280 2,320 920 15,400 (male) 95th percentile 160 426 258 19,420 611 3,740 211 512 7,880 7,280 52,070 12,070 7,670 112,000 Median 0.95 0.94 0.1 - 0.55 - - - 243 274 201 795 61 1,600 Dermal absorption 5th percentile 0.83 0.60 0.04 - 0.41 - - - 187 231 163 474 39 1,096 (male) 95th percentile 1.9 2.0 0.30 - 0.96 - - - 305 312 314 971 129 2,036 Median 82 118 414 28,000 193 810 138 393 2,120 2,730 3,900 10,900 1,490 51,300 Dust ingestion 5th percentile 72 75 212 8,030 144 304 90 276 1,630 2,310 3,160 6,500 957 23,800 (male) 95th percentile 164 247 1,510 52,500 340 1,500 1,180 2,490 2,670 3,120 6,100 13,300 3,140 88,000 Median 141 227 564 39,000 277 1,200 280 663 6,500 6,550 7,480 14,900 3,050 80,900 Total exposure 5th percentile 112 142 321 13,500 175 482 195 474 4,090 4,970 4,600 9,290 1,920 40,200 (male) 95th percentile 326 676 1,760 71,900 952 5,200 1,400 3,000 10,900 10,700 58,500 26,400 10,940 203,000 Median 53 97 136 9,990 76 348 129 244 3,740 3,210 3,060 2,920 1,350 25,400 Air inhalation 5th percentile 35 60 98 4,910 27 161 95 180 2,060 2,200 1,160 2,100 833 13,900 (female) 95th percentile 144 386 233 17,600 554 3,390 191 463 7,140 6,590 47,200 10,900 6,940 101,700 Median 0.92 0.91 0.08 - 0.53 - - - 237 266 195 773 60 1,530 Dermal absorption 5th percentile 0.81 0.58 0.04 - 0.40 - - - 182 225 158 461 38 1,066 (female) 95th percentile 1.8 1.9 0.30 - 0.94 - - - 297 303 305 944 126 1,980 Median 95 138 482 32,600 225 943 160 458 2,470 3,180 4,540 12,700 1,730 59,700 Dust ingestion 5th percentile 84 88 247 9,350 168 355 105 321 1,900 2,700 3,700 7,570 1,120 27,700 (female) 95th percentile 192 288 1,750 61,100 396 1,750 1,370 2,900 3,100 3,627 7,100 15,500 3,660 102,800 Median 149 236 618 42,600 301 1,290 289 702 6,450 6,660 7,800 16,400 149 86,600 Total exposure 5th percentile 120 148 345 14,300 196 516 200 501 4,140 5,120 5,000 10,130 120 42,700 (female) 95th percentile 338 676 1,990 78,700 951 5,140 1,560 3,360 10,540 10,520 54,600 27,400 338 206,500 “-“: No information

For the inhalation pathway, the median of BDE-209 exposure levels among male and female dismantlers were 11,030 and 9,990 pg kg-bw-1 day-1, respectively. Among OPEs, the highest inhalation exposure levels were for TCEP, with median values of 4,130 and 3,740 pg kg- bw-1 day-1 for male and female dismantlers, respectively. The second highest exposure level through inhalation was for TDCIPP with median exposures of 3,380 and 3,060 pg kg-bw-1 day-1 for male and female workers respectively.

Exposure to FRs via air inhalation among e-waste dismantlers in this study was generally higher than those among indoor e-waste workers in other countries (Table A2.9 in Appendix 1).

Exposure to BDE-99 via air inhalation (estimated with a similar equation and exposure factors except for body weight) was 10 times greater than that reported in Thai e-waste storage facilities

(Muenhor et al., 2010) and comparable to those reported in an US e-waste recycling site with shredding activities sampled in 2004 (Cahill et al., 2007). Inhalation exposure to other PBDE congeners (BDE-47, -183 and -209) reported here were at least 2-3 times lower than those estimated among US e-waste workers (Cahill et al., 2007). However, as mentioned above, the latter measurements were taken in 2004 when levels of Penta- and Octa-BDEs were likely at their highest, since controls on their production were negotiated in late 2004 in the US. Estimated inhalation exposure for BDE-47 and -99 among Canadian dismantlers here was 3-4 times lower than those reported recently for Chinese e-waste workers (without facemasks) (Guo et al., 2015).

The difference in exposure estimates is attributable to the choice of inhalation rate. The higher exposure estimated by Guo et al. (2015) is likely due to their assumed inhalation rate of 72 m3 day-1 (for adults working at high intensity activity for short-term exposure) over an 8-hour exposure period. We assumed a lower inhalation rate of 16 m3 day-1 (for adults for long-term exposure) (US EPA, 2011), also over an 8-hour exposure period. We believe that the inhalation

rate we used was appropriate since workers who dismantled computers and small appliances worked continuously, but not at high intensity.

Dermal exposure contributed minimally to overall exposure, particularly for PBDEs. For

OPEs, dermal absorption was highest for TPhP with median levels of 795 and 773 pg kg-bw-1 day-1 for male and female workers, respectively. Only a Chinese study (Wu et al., 2016) has reported exposure to FRs via dermal absorption among e-waste handling workers studied in 2005.

Wu et al. (2016a) reported that dermal absorption of BDE-47 and -99 among Chinese e-waste workers in Guiyu, China that was 200 and 50 times higher than levels found in our study. Wu et al. (2016a) calculated dermal exposure based on whole body surface area, which was approximately 10 times higher than our assumption of the surface area of head and hands only.

For dust ingestion, the median BDE-209 exposure was 28,000 and 32,600 pg kg-bw-1 day-

1 for male and female workers, respectively. Dust ingestion levels for EHTBB plus BEHTBP were approximately 2 times higher than the levels of the sum of a-DP and s-DP, which we expected to be relatively high since the latter are alternatives to Deca-BDE. TPhP was the OPE for which dust ingestion was highest with median levels of 10,900 and 12,700 pg kg-bw-1 day-1, respectively.

The second highest exposure level through dust ingestion was that of TDCIPP with median exposure of 3,900 and 4,540 pg kg-bw-1 day-1 for male and female workers, respectively.

Our results of estimated dust ingestion levels showed that Canadian e-waste dismantlers had a higher exposure to most FRs (except for BDE-99, s-DP and TCIPP) compared to other current e-waste workers in China (Zheng et al., 2015) and Thailand (Muenhor et al., 2010) (Table

A2.9 in Appendix 1). Exposures to BDE-209 via dust ingestion among Canadian e-waste dismantlers were 4-6 times higher than levels estimated for Thai (Muenhor et al., 2010) and

Chinese (Zheng et al., 2015) e-waste workers. Dust ingestion levels of TCEP, TCIPP and TPhP

in this study were ~10 times higher than levels reported in an e-waste recycling facility in Guiyu,

China (Zheng et al., 2015). This difference reflects higher concentrations of these FRs in the

Ontario facility.

2.3.4 Comparison of exposure with recommended doses

We found reference values (Reference dose or RfD), Minimal Risk Levels (MRL) or maximal allowed daily intake (ADI) values for BDE-47, -99 and -209, TCEP, TCIPP and TDCIPP in the Integrated Risk Information System (IRIS) (US EPA, 2018a), the Agency for Toxic

Substances and Disease Registry (ATSDR) (ATSDR, 2012), the National Institute for Public

Health and the Environment from Netherlands (RIVM) (de Winter-Sorkina et al., 2006), and/or the US EPA Chemistry Dashboard (US EPA, 2018b) (Table A2.10 in Appendix 1). These reference values provide an estimate of a daily (24 hour) exposure to humans that is likely to be without risk of adverse effects during a lifetime.

For PBDEs and OPEs, estimated occupational exposure via dust ingestion was several orders of magnitude lower than the reference values, even for BDE-209, which was the most abundant compound. However, the reference values must be interpreted critically; most are outdated and overestimate the “safe” level. For example, toxicological studies have suggested a much lower RfD for BDE-99 (260 pg kg-bw-1 day-1) (de Winter-Sorkina et al., 2006) compared to the current RfD (100,000 pg kg-bw-1 day-1) (US EPA, 2018c). The exposure to BDE-99 among male and female e-waste dismantlers estimated from the Canadian dust would exceed this proposed RfD of 260 pg kg-bw-1 day-1 at the 95th percentile concentration.

Additionally, several of these reference values are based on data up to 2004 and thus do not account for the large body of recent evidence from in vitro, in vivo and epidemiological studies

that have documented adverse effects. For OPEs, toxicological data remains incomplete, but available studies indicate that some OPEs may result in human health effects. Associations have been reported between TDCIPP and reproductive outcomes, as well as neurobehavioral outcomes

(Carignan et al., 2018; Hutter et al., 2013; Meeker et al., 2013). A recent study also showed a statistical correlation between exposure to OPEs in an e-waste dismantling area and the level of oxidative stress of workers, an indicator of potential health risk (Lu et al., 2017). Additionally, reference values for BDE-47 and -99 are up to 2 orders of magnitude lower than those for TCEP,

TCIPP or TDCIPP despite evidence from in vitro, in vivo and human studies that have analyzed

PBDEs and OPEs toxicity in parallel, and concluded that they have comparable levels of toxicity

(Behl et al., 2016, 2015; Hoffman et al., 2017b; Jarema et al., 2015; Suzuki et al., 2013).

Furthermore, reference values are typically calculated for non-carcinogenic systemic toxicity, although there are some indications that TCEP, TDCIPP and TPhP may be carcinogenic.

TDCIPP is included in California Proposition 65 list of chemicals known to cause cancer

(Kammerer, 2017) and TCEP and TPhP have been associated with papillary thyroid cancer

(Hoffman et al., 2017b). No reference values exist for many FRs (e.g., EHTBB, BEHTBP, DPs,

BDE-183, TPhP, EHDPP). Reference values also consider hazard on a chemical-by-chemical basis and do not consider exposure to the complex mixture of FRs and metals to which e-waste workers are very likely exposed.

In Ontario, e-waste facilities must comply with occupational exposure limits for various exposures, notably metals (e.g., lead, mercury, copper, cadmium) and other hazardous chemicals that may be present in the e-waste environment (Ontario Occupational Health and Safety Act,

1990). Under this Act, the employer must maintain exposure limits below the listed occupational exposure limit without use of personal protective equipment, with few exceptions (Ontario

Regulation 833, 1990). There is only one occupational exposure limit for a FR, TPhP, which is set at 3 mg m-3 based on cholinesterase inhibition (ACGIH, 2018). This value was first proposed in 1961, well before current studies indicating other toxicological modes-of-actions of TPhP

(ACGIH, 2001).

Where personal protective equipment is used, the Ontario Occupational Health and Safety

Act (1990) requires the employer to provide, and maintain in good condition, protective devices that are provided as prescribed. Despite the presence of detailed occupational health and safety legislation in Ontario (Canada), the enforcement of these regulations, particularly in small and medium sized enterprises (SMEs) is thought to be scarce. Further, the awareness of occupational health and safety regulations and best practices among SMEs has been shown previously to be low (Eakin et al., 2017).

2.3.5 Strengths and Limitations

Our study is one of the first studies to report levels of OPEs in e-waste indoor dust in a high-income country, that can help estimate the non-dietary ingestion of e-waste workers. This study also provides both air and dust levels of TPhP, which is of increasing concern due to its negative reproductive effects (Carignan et al., 2018; Carignan et al., 2017).

A limitation of this study was that collected samples from only one facility. As such, our results do not reflect the e-waste recycling industry as a whole. Another limitation of this study was the inability to collect personal (mobile) exposure samples in the facility. However, the bench samples (located at breathing zone height, approximately 1-2 m away from the worker) were positioned in order to best approximate worker exposure under the circumstances. Workers stood at the bench for the vast majority of the day, leaving only for short breaks and lunch. Results

showed that the bench air concentrations were consistently higher than at the central location samples, suggesting that personal exposure levels may be even higher than those measured here.

In addition, air concentrations in this study were estimated over 24 hours although dismantling activities occurred over only 16 hours per day. Sampling took place over two weeks and thus did not fully capture the variability that is expected over time as a result of cyclical e-waste volumes and seasonal variability due to changes in general (non-mechanical) ventilation. Furthermore, the use of GFFs as an impactor substrate in MOUDI can reduce particle bounce since GFFs have a rougher surface compared to aluminum foil and plastic film and thus have better capture efficiency. However, the use of GFFs could lead to artifacts if gas-phase polar SVOCs (e.g TCEP,

TCIPP) dissolve in the thin aqueous layer that can develop on GFFs (Delgado-Saborit et al., 2014;

Okeme et al., 2018c), thereby artificially increasing the measured concentrations. Conversely, the pressure drop at smaller size fraction stages can lead to stripping of more volatile SVOCs from particles through evaporative loss, as the chemical seeks to restore gas-particle equilibrium in smaller size fraction stages (Delgado-Saborit et al., 2014). As a result, we may have overestimated some OPEs and underestimated the more volatile SVOCs in the smaller size-fraction stages.

2.4 Implications

The results presented here suggest e-waste workers in a formal e-waste dismantling facility in Ontario, Canada had higher exposure to FRs than reported in several previous e-wastes studies of formal and informal facilities in other countries. The health implications of these exposures are unclear because there is incomplete knowledge of FR toxicity. However, intentions to reduce population-wide exposure to FRs through chemical management regulations for new uses of several FRs does not affect the exposure circumstance of e-waste workers, who are handing old

electronics. As such, chemical management needs to account for exposures to e-waste handlers long after controls have been implemented. Further, exposures to a mixture of known and potentially toxic compounds should also be considered. Finally, our analysis points to the need to improve exposure prevention for a wide range of toxic compounds in the growing industry of e- waste recycling.

Results from our study and those from previous studies in formal and informal recycling facilities indicate the need to better control exposure to FRs during e-waste handling in order to reduce occupational exposures (Awasthi et al., 2018; Bakhiyi et al., 2018; Zeng et al., 2017).

Finally, the growth of e-waste is expected to continue unabated. Indeed, “smart” appliances,

“smart” vehicles, and “smart” cities are being promoted for their potential to reduce environmental impacts, such as climate-related emissions (UNEP, 2016). The consequences of e-waste handling should be added to these discussions.

Acknowledgments

Funding was provided by Ontario Ministry of Labour Research Opportunities Program and Natural Sciences and Engineering Research Council of Canada (NSERC, RGPAS 429679-

12 and RGPIN-2017-06654) and the Czech Ministry of Education, Youth and Sports (LO2014).

We thank Elizabeth Galarneau of Environment and Climate Change Canada (ECCC) for lending us the MOUDI sampler and Sarah Bernstein for laboratory support.

References

Abbasi, G., Saini, A., Goosey, E., Diamond, M.L., 2016. Product screening for sources of halogenated flame retardants in Canadian house and office dust. Sci. Total Environ. 545– 546, 299–307. https://doi.org/10.1016/j.scitotenv.2015.12.028 Abdallah, M.A.-E., Pawar, G., Harrad, S., 2015a. Evaluation of 3D-human skin equivalents for assessment of human dermal absorption of some brominated flame retardants. Environ. Int. 84, 64–70. https://doi.org/10.1016/j.envint.2015.07.015 Abdallah, M.A.-E., Pawar, G., Harrad, S., 2015b. Effect of Bromine Substitution on Human Dermal Absorption of Polybrominated Diphenyl Ethers. Environ. Sci. Technol. 49, 10976– 10983. https://doi.org/10.1021/acs.est.5b03904 Abou-Elwafa Abdallah, M., Pawar, G., Harrad, S., 2016. Human dermal absorption of chlorinated organophosphate flame retardants; implications for human exposure. Toxicol. Appl. Pharmacol. 291, 28–37. https://doi.org/10.1016/j.taap.2015.12.004 ACGIH, 2018. TLVs ® and BEIs ® : Threshold limit values for chemical substances and physical agents biological exposure indices. American Conference of Governmental Industrial Hygienists, Cincinnati, OH, OH. ACGIH, 2001. Documentation of threshold limit values for substances in work environment. American Conference of Governmental Industrial Hygienists, Cincinnati, OH, OH. Ait, Y., Araki, A., Kawai, T., Tsuboi, T., Saito, I., Yoshioka, E., Kanazawa, A., 2014. Science of the Total Environment Associations of phthalate concentrations in fl oor dust and multi- surface dust with the interior materials in Japanese dwellings. Sci. Total Environ. 468–469, 147–157. https://doi.org/10.1016/j.scitotenv.2013.07.107 Akormedi, M., Asampong, E., Fobil, J.N., 2013. Working conditions and environmental exposures among electronic waste workers in Ghana. Int. J. Occup. Environ. Health 19, 278–286. https://doi.org/10.1179/2049396713Y.0000000034 Allen, J.G., McClean, M.D., Stapleton, H.M., Nelson, J.W., Webster, T.F., 2007. Personal Exposure to Polybrominated Diphenyl Ethers (PBDEs) in Residential Indoor Air. Environ. Sci. Technol. 41, 4574–4579. https://doi.org/10.1021/es0703170 Allen, J.O., Dookeran, N.M., Smith, K.A., Sarofim, A.F., Taghizadeh, K., Lafleur, A.L., 1996. Measurement of polycyclic aromatic hydrocarbons associated with size-segregated atmospheric aerosols in Massachusetts. Environ. Sci. Technol. 30, 1023–1031. https://doi.org/10.1021/es950517o Andersen, C., Krais, A.M., Eriksson, A.C., Jakobsson, J., Löndahl, J., Nielsen, J., Lindh, C.H., Pagels, J., Gudmundsson, A., Wierzbicka, A., 2018. Inhalation and Dermal Uptake of Particle and Gas-Phase Phthalates—A Human Exposure Study. Environ. Sci. Technol. 52, 12792–12800. https://doi.org/10.1021/acs.est.8b03761 Asante, K.A., Agusa, T., Biney, C.A., Agyekum, W.A., Bello, M., Otsuka, M., Itai, T., Takahashi, S., Tanabe, S., 2012. Multi-trace element levels and arsenic speciation in urine of e-waste recycling workers from Agbogbloshie, Accra in Ghana. Sci. Total Environ. 424, 63–73. https://doi.org/10.1016/j.scitotenv.2012.02.072 ATSDR, 2012. Toxicological Profile for Phosphate Ester Flame Retardants. ATSDR, 2005. Public Health Assessment Guidance Manual (2005 Update). Atlanta, Georgia. ATSDR, 2004. Toxicological profile for polybrominated biphenyl and polybrominated diphenyl ethers 1–599. Awasthi, A.K., Wang, M., Wang, Z., Awasthi, M.K., Li, J., 2018. E-waste management in India: A mini-review. Waste Manag. Res. 36, 408–414. https://doi.org/10.1177/0734242X18767038

Čupr, P., Klánová, J., 2014. Evaluation and guidelines for using polyurethane foam (PUF) passive air samplers in double-dome chambers to assess semi-volatile organic compounds (SVOCs) in non-industrial indoor environments. Environ. Sci. Process. Impacts 16, 2617– 2626. https://doi.org/10.1039/C4EM00305E Bohlin, P., Jones, K.C., Levin, J.-O., Lindahl, R., Strandberg, B., 2010a. Field evaluation of a passive personal air sampler for screening of PAH exposure in workplaces. J. Environ. Monit. 12, 1437. https://doi.org/10.1039/c0em00018c Bohlin, P., Jones, K.C., Strandberg, B., 2010b. Field evaluation of polyurethane foam passive air samplers to assess airborne PAHs in occupational environments. Environ. Sci. Technol. 44, 749–754. https://doi.org/10.1021/es902318g Bohlin, P., Jones, K.C., Strandberg, B., 2007. Occupational and indoor air exposure to persistent organic pollutants: A review of passive sampling techniques and needs. J. Environ. Monit. 9, 501. https://doi.org/10.1039/b700627f Bornehag, C.G., Nanberg, E., 2010. Phthalate exposure and asthma in children 33, 333–345. https://doi.org/10.1111/j.1365-2605.2009.01023.x Braun, J.M., Kalkbrenner, A.E., Just, A.C., Yolton, K., Calafat, A.M., Sjödin, A., Hauser, R., Webster, G.M., Chen, A., Lanphear, B.P., 2014. Gestational Exposure to Endocrine- Disrupting Chemicals and Reciprocal Social, Repetitive, and Stereotypic Behaviors in 4- and 5-Year-Old Children: The HOME Study. Environ. Health Perspect. 122, 513–520. https://doi.org/10.1289/ehp.1307261 Breul, S., Van Landuyt, K.L., Reichl, F.X., Högg, C., Hoet, P., Godderis, L., Van Meerbeek, B., Cokic, S.M., 2020. Filtration efficiency of surgical and FFP3 masks against composite dust. Eur. J. Oral Sci. 128, 233–240. https://doi.org/10.1111/eos.12697 Brown, J., Gordon, T., Price, O., Asgharian, B., 2013. Thoracic and respirable particle deinitions for human health risk assessment. Part. Fibre Toxicol. 10, 1–12. Cahill, T.M., Groskova, D., Charles, M.J., Sanborn, J.R., Denison, M.S., Baker, L., 2007. Atmospheric concentrations of polybrominated diphenyl ethers at near-source sites. Environ. Sci. Technol. 41, 6370–6377. https://doi.org/10.1021/es070844j Callesen, M., Bekö, G., Weschler, C.J., Langer, S., Brive, L., Clausen, G., Toftum, J., Sigsgaard, T., Høst, A., Kold, T., 2014. International Journal of Hygiene and Phthalate metabolites in urine and asthma , allergic rhinoconjunctivitis and atopic dermatitis in preschool children. Int. J. Hyg. Environ. Health 217, 645–652. https://doi.org/10.1016/j.ijheh.2013.12.001 Cao, Z., Xu, F., Covaci, A., Wu, M., Wang, H., Yu, G., Wang, B., Deng, S., Huang, J., Wang, X., 2014. Distribution patterns of brominated, chlorinated, and phosphorus flame retardants with particle size in indoor and outdoor dust and implications for human exposure. Environ. Sci. Technol. 48, 8839–8846. https://doi.org/10.1021/es501224b Carignan, C.C., Mínguez-Alarcón, L., Butt, C.M., Williams, P.L., Meeker, J.D., Stapleton, H.M., Toth, T.L., Ford, J.B., Hauser, R., 2017. Urinary Concentrations of Organophosphate Flame Retardant Metabolites and Pregnancy Outcomes among Women Undergoing in Vitro Fertilization. Environ. Health Perspect. 125, 087018. https://doi.org/10.1289/EHP1021 Carignan, C.C., Mínguez-Alarcón, L., Williams, P.L., Meeker, J.D., Stapleton, H.M., Butt, C.M., Toth, T.L., Ford, J.B., Hauser, R., 2018. Paternal urinary concentrations of organophosphate flame retardant metabolites, fertility measures, and pregnancy outcomes among couples undergoing in vitro fertilization. Environ. Int. 111, 232–238. https://doi.org/10.1016/j.envint.2017.12.005

Castorina, R., Bradman, A., Stapleton, H.M., Butt, C., Avery, D., Harley, K.G., Gunier, R.B., Holland, N., Eskenazi, B., 2017. Current-use flame retardants: Maternal exposure and neurodevelopment in children of the CHAMACOS cohort. Chemosphere 189, 574–580. https://doi.org/10.1016/j.chemosphere.2017.09.037 Ceballos, D.M., Côté, D., Bakhiyi, B., Flynn, M.A., Zayed, J., Gravel, S., Herrick, R.F., Labrèche, F., 2020. Overlapping vulnerabilities in workers of the electronics recycling industry formal sector: A commentary. Am. J. Ind. Med. 63, 955–962. https://doi.org/10.1002/ajim.23173 Ceballos, D.M., Dong, Z., 2016. The formal electronic recycling industry: Challenges and opportunities in occupational and environmental health research. Environ. Int. 95, 157–166. https://doi.org/10.1016/j.envint.2016.07.010 CEPA, 1999. Canadian Environmental Protection Act. Cequier, E., Sakhi, A.K., Marcé, R.M., Becher, G., Thomsen, C., 2015. Human exposure pathways to organophosphate triesters — A biomonitoring study of mother–child pairs. Environ. Int. 75, 159–165. https://doi.org/10.1016/j.envint.2014.11.009 Chan, J.K.Y., Wong, M.H., 2013. A review of environmental fate, body burdens, and human health risk assessment of PCDD/Fs at two typical electronic waste recycling sites in China. Sci. Total Environ. 463–464, 1111–1123. https://doi.org/10.1016/j.scitotenv.2012.07.098 Cherrie, J.W., 2003. CommentaryThe Beginning of the Science Underpinning Occupational Hygiene. Ann. Occup. Hyg. 47, 179–185. https://doi.org/10.1093/annhyg/meg030 City of Toronto, 2019. Search for an Establishment Monitored by BodySafe [WWW Document]. URL https://www.toronto.ca/community-people/health-wellness-care/health- programs-advice/bodysafe/search-for-an-establishment-space-holder-for-map/ (accessed 7.18.19). Consumer Product Safety Commission, 2008. Consumer Product Safety Improvement Act of 2008. Craig, J.A., Ceballos, D.M., Fruh, V., Petropoulos, Z.E., Allen, J.G., Calafat, A.M., Ospina, M., Stapleton, H.M., Hammel, S., Gray, R., Webster, T.F., 2019. Exposure of Nail Salon Workers to Phthalates, Di(2-ethylhexyl) Terephthalate, and Organophosphate Esters: A Pilot Study. Environ. Sci. Technol. 53, 14630–14637. https://doi.org/10.1021/acs.est.9b02474 de Winter-Sorkina, R., Bakker, M.., Wolterink, G., Zielmaker, M.J., 2006. Brominated flame retardants: occurrence, dietary intake and risk assessment [WWW Document]. URL https://www.rivm.nl/bibliotheek/rapporten/320100002.pdf (accessed 6.7.18). Delgado-Saborit, J.M., Stark, C., Harrison, R.M., 2014. Use of a versatile high efficiency multiparallel denuder for the sampling of PAHs in ambient air: Gas and particle phase concentrations, particle size distribution and artifact formation. Environ. Sci. Technol. 48, 499–507. https://doi.org/10.1021/es402937d Dixon, H.M., Scott, R.P., Holmes, D., Calero, L., Kincl, L.D., Waters, K.M., Camann, D.E., Calafat, A.M., Herbstman, J.B., Anderson, K.A., 2018. Silicone wristbands compared with traditional polycyclic aromatic hydrocarbon exposure assessment methods. Anal. Bioanal. Chem. 410, 3059–3071. https://doi.org/10.1007/s00216-018-0992-z Eakin, J.M., Champoux, D., MacEachen, E., 2017. Health and safety in small workplaces: refocusing upstream. Can. J. Public Health 101 Suppl, S29-33. EC, 2018. Waste Electrical & Electronic Equipment (WEEE) [WWW Document]. Eur. Comm.

https://doi.org/10.1016/j.geb.2005.03.002 Ekelund, M., Azhdar, B., Gedde, U.W., 2010. Evaporative loss kinetics of di(2- ethylhexyl)phthalate (DEHP) from pristine DEHP and plasticized PVC. Polym. Degrad. Stab. 95, 1789–1793. https://doi.org/10.1016/j.polymdegradstab.2010.05.007 Eriksson, P., Jakobsson, E., Fredriksson, A., 2001. Brominated flame retardants: a novel class of developmental toxicants in our environment? Environ. Health Perspect. 109, 903–908. https://doi.org/10.1289/ehp.01109903 Estill, C.F., Slone, J., Mayer, A., Chen, I.-C., La Guardia, M.J., 2020. Worker exposure to flame retardants in manufacturing, construction and service industries. Environ. Int. 135, 105349. https://doi.org/10.1016/j.envint.2019.105349 European Commission, 2014. COMMUNICATION FROM THE COMMISSION on the finalisation of the restriction process on the four phthalates (DEHP, DBP, BBP and DIBP) under Regulation (EC) No 1907/2006 of the European Parliament and of the Council concerning Registration, Evaluation, Authori. Off. J. Eur. Union 73, 1–4. ExpoStats, 2015. NDExpo – Treatment of non-detects in industrial hygiene samples [WWW Document]. URL http://www.expostats.ca/site/app-local/NDExpo/ (accessed 2.20.20). Factor-Litvak, P., Insel, B., Calafat, A.M., Liu, X., Perera, F., Rauh, V.A., Whyatt, R.M., 2014. Persistent Associations between Maternal Prenatal Exposure to Phthalates on Child IQ at Age 7 Years. PLoS One 9, e114003. https://doi.org/10.1371/journal.pone.0114003 Federman, M.N., Harrington, D.E., Krynski, K.J., 2006. Vietnamese Manicurists: Are Immigrants Displacing Natives or Finding New Nails to Polish? ILR Rev. 59, 302–318. https://doi.org/10.1177/001979390605900207 Fisher, M., Arbuckle, T.E., MacPherson, S., Braun, J.M., Feeley, M., Gaudreau, É., 2019. Phthalate and BPA Exposure in Women and Newborns through Personal Care Product Use and Food Packaging. Environ. Sci. Technol. 53, 10813–10826. https://doi.org/10.1021/acs.est.9b02372 Flanagan, M.E., Seixas, N., Majar, M., Camp, J., Morgan, M., 2003. Silica Dust Exposures During Selected Construction Activities. AIHA J. 64, 319–328. https://doi.org/10.1080/15428110308984823 Fortia, V., Balde, C.P., Kuehr, R., Bel, G., 2020. The Global E-waste Monitor 2020: Quantitites, flows and circular economy potential [WWW Document]. URL https://collections.unu.edu/view/UNU:7737 (accessed 10.13.20). Fraser, A.J., Webster, T.F., McClean, M.D., 2009. Diet Contributes Significantly to the Body Burden of PBDEs in the General U.S. Population. Environ. Health Perspect. 117, 1520– 1525. https://doi.org/10.1289/ehp.0900817 Frazzoli, C., Orisakwe, O.E., Dragone, R., Mantovani, A., 2010. Diagnostic health risk assessment of electronic waste on the general population in developing countries’ scenarios. Environ. Impact Assess. Rev. 30, 388–399. https://doi.org/10.1016/j.eiar.2009.12.004 Frederiksen, M., Stapleton, H.M., Vorkamp, K., Webster, T.F., Jensen, N.M., Sørensen, J.A., Nielsen, F., Knudsen, L.E., Sørensen, L.S., Clausen, P.A., Nielsen, J.B., 2018. Dermal uptake and percutaneous penetration of organophosphate esters in a human skin ex vivo model. Chemosphere 197, 185–192. https://doi.org/10.1016/j.chemosphere.2018.01.032 Fromme, H., Becher, G., Hilger, B., Völkel, W., 2016. Brominated flame retardants - Exposure and risk assessment for the general population. Int. J. Hyg. Environ. Health 219, 1–23. https://doi.org/10.1016/j.ijheh.2015.08.004

Gaspar, F.W., Castorina, R., Maddalena, R.L., Nishioka, M.G., McKone, T.E., Bradman, A., 2014. Phthalate exposure and risk assessment in California child care facilities. Environ. Sci. Technol. 48, 7593–7601. https://doi.org/10.1021/es501189t Gevao, B., Al-Bahloul, M., Al-Ghadban, A.N., Ali, L., Al-Omair, A., Helaleh, M., Al-Matrouk, K., Zafar, J., 2006. Polybrominated diphenyl ethers in indoor air in Kuwait: Implications for human exposure. Atmos. Environ. 40, 1419–1426. https://doi.org/10.1016/j.atmosenv.2005.10.053 Gioia, R., Steinnes, E., Thomas, G.O., Mejier, S.N., Jones, K.C., 2006. Persistent organic pollutants in European background air: derivation of temporal and latitudinal trends. J. Environ. Monit. 8, 700. https://doi.org/10.1039/b604821h Giovanoulis, G., Bui, T., Xu, F., Papadopoulou, E., Padilla-Sanchez, J.A., Covaci, A., Haug, L.S., Cousins, A.P., Magnér, J., Cousins, I.T., de Wit, C.A., 2018. Multi-pathway human exposure assessment of phthalate esters and DINCH. Environ. Int. 112, 115–126. https://doi.org/10.1016/j.envint.2017.12.016 Glazer, L., Hawkey, A.B., Wells, C.N., Drastal, M., Odamah, K.-A., Behl, M., Levin, E.D., 2018. Developmental Exposure to Low Concentrations of Organophosphate Flame Retardants Causes Life-Long Behavioral Alterations in Zebrafish. Toxicol. Sci. 165, 487– 498. https://doi.org/10.1093/toxsci/kfy173 Godwin, A.D., 2017. Plasticizers, in: Applied Plastics Engineering Handbook. Elsevier, pp. 533–553. Godwin, A.D., 2010. Uses of Phthalates and Other Plasticizers [WWW Document]. URL https://www.cpsc.gov/s3fs-public/godwin.pdf (accessed 10.21.20). Gong, M., Weschler, C.J., Zhang, Y., 2016. Impact of Clothing on Dermal Exposure to Phthalates: Observations and Insights from Sampling Both Skin and Clothing. Environ. Sci. Technol. 50, 4350–4357. https://doi.org/10.1021/acs.est.6b00113 Goodyer, C.G., Poon, S., Aleksa, K., Hou, L., Atehortua, V., Carnevale, A., Jednak, R., Emil, S., Bagli, D., Dave, S., Hales, B.F., Chevrier, J., 2017. A case-control study of maternal polybrominated diphenyl ether (PBDE) exposure and cryptorchidism in Canadian populations. Environ. Health Perspect. 125, 1–9. https://doi.org/10.1289/EHP522 Gouin, T., Harner, T., Blanchard, P., Mackay, D., 2005. Passive and Active Air Samplers as Complementary Methods for Investigating Persistent Organic Pollutants in the Great Lakes Basin. Environ. Sci. Technol. 39, 9115–9122. https://doi.org/10.1021/es051397f Goverment of Canada, 2017. Phthalates Regulations Règlement sur les phtalates 21–23. Government of Canada, 2019. Cosmetic Ingredient Hotlist [WWW Document]. URL https://www.canada.ca/en/health-canada/services/consumer-product- safety/cosmetics/cosmetic-ingredient-hotlist-prohibited-restricted- ingredients/hotlist.html#tbl1 (accessed 5.4.20). Government of Canada, 2016. Toxic substances list: PBDEs [WWW Document]. Government of Canada, 2012. Regulations Amending the Prohibition of Certain Toxic Substances Regulations, 2012 [WWW Document]. Canada Gaz. Part II. URL http://www.gazette.gc.ca/rp-pr/p2/2016/2016-10-05/pdf/g2-15020.pdf (accessed 2.18.21). Government of Ontario, 2018. Waste management [WWW Document]. URL https://www.ontario.ca/page/waste-management (accessed 12.9.18). Graham, P.R., 1973. Phthalate ester plasticizers—why and how they are used. Environ. Health Perspect. 3, 3–12. https://doi.org/10.1289/ehp.73033 Grant, K., Goldizen, F.C., Sly, P.D., Brune, M.-N., Neira, M., van den Berg, M., Norman, R.E.,

2013. Health consequences of exposure to e-waste: a systematic review. Lancet Glob. Heal. 1, e350–e361. https://doi.org/10.1016/S2214-109X(13)70101-3 Gravel, S., Bakhiyi, B., Lavoué, J., Verner, M.-A., Zayed, J., Labreche, F., 2019a. Electronic waste recycling exposure and hormone levels in workers., in: 27th EPICOH International Symposium on Epidemiology in Occupational Health. Wellington, NewZealand. Gravel, S., Diamond, M.L., Jantunen, L.M., Verner, M.-A., Zayed, J., Labrèche, F., 2019b. Is airborne concentration of BDE209 associated with serum concentration in recycling workers?, in: 9th International Symposium on Flame Retardants BFR 2019. Montreal, Canada. Gravel, S., Lavoué, J., Bakhiyi, B., Diamond, M.L., Jantunen, L.M., Lavoie, J., Roberge, B., Verner, M.-A., Zayed, J., Labrèche, F., 2019c. Halogenated flame retardants and organophosphate esters in the air of electronic waste recycling facilities: Evidence of high concentrations and multiple exposures. Environ. Int. 128, 244–253. https://doi.org/10.1016/j.envint.2019.04.027 Gravel, S., Lavoué, J., Bakhiyi, B., Lavoie, J., Roberge, B., Patry, L., Bouchard, M.F., Verner, M., Zayed, J., Labrèche, F., 2020. Multi-exposures to suspected endocrine disruptors in electronic waste recycling workers: Associations with thyroid and reproductive hormones. Int. J. Hyg. Environ. Health 225, 113445. https://doi.org/10.1016/j.ijheh.2019.113445 Guo, J., Lin, K., Deng, J., Fu, X., Xu, Z., 2015. Polybrominated diphenyl ethers in indoor air during waste TV recycling process. J. Hazard. Mater. 283, 439–446. https://doi.org/10.1016/j.jhazmat.2014.09.044 Guo, Y., Kannan, K., 2013. A survey of phthalates and parabens in personal care products from the United States and its implications for human exposure. Environ. Sci. Technol. 47, 14442–14449. https://doi.org/10.1021/es4042034 Guo, Y., Kannan, K., 2011. Comparative Assessment of Human Exposure to Phthalate Esters from House Dust in China and the United States. Environ. Sci. Technol. 45, 3788–3794. https://doi.org/10.1021/es2002106 Hammel, S., Hoffman, K., Webster, T.F., Anderson, K.A., Stapleton, H.M., 2016. Measuring Personal Exposure to Organophosphate Flame Retardants using Silicone Wristbands and Hand Wipes. Environ. Sci. Technol. acs.est.6b00030. https://doi.org/10.1021/acs.est.6b00030 Hammel, S.C., Phillips, A.L., Hoffman, K., Stapleton, H.M., 2018. Evaluating the Use of Silicone Wristbands To Measure Personal Exposure to Brominated Flame Retardants. Environ. Sci. Technol. 52, acs.est.8b03755. https://doi.org/10.1021/acs.est.8b03755 Harley, K.G., Marks, A.R., Chevrier, J., Bradman, A., Sjödin, A., Eskenazi, B., 2010. PBDE Concentrations in Women’s Serum and Fecundability. Environ. Health Perspect. 118, 699– 704. https://doi.org/10.1289/ehp.0901450 Harner, T., Bartkow, M., Holoubek, I., Klanova, J., Wania, F., Gioia, R., Moeckel, C., Sweetman, A.J., Jones, K.C., 2006. Passive air sampling for persistent organic pollutants: Introductory remarks to the special issue. Environ. Pollut. 144, 361–364. https://doi.org/10.1016/j.envpol.2005.12.044 Hartmann, P.C., Burgi, D., Giger, W., 2004. Organophosphate flame retardants and plasticizers in indoor air. Chemosphere 57, 781–787. https://doi.org/10.1016/j.chemosphere.2004.08.051 Hays, S.M., Kirman, C.R., 2017. Risk assessment and Biomonitoring Equivalent for 2- ethylhexyl-2,3,4,5 tetrabromobenzoate (TBB) and tetrabromobenzoic acid (TBBA). Regul.

Toxicol. Pharmacol. 89, 186–192. https://doi.org/10.1016/j.yrtph.2017.07.022 Hazrati, S., Harrad, S., 2006. Causes of Variability in Concentrations of Polychlorinated Biphenyls and Polybrominated Diphenyl Ethers in Indoor air. Environ. Sci. Technol. 40, 7584–7589. https://doi.org/10.1021/es0617082 Heacock, M., Kelly, C.B., Asante, K.A., Birnbaum, L.S., Bergman, Å.L., Bruné, M.-N., Buka, I., Carpenter, D.O., Chen, A., Huo, X., Kamel, M., Landrigan, P.J., Magalini, F., Diaz- Barriga, F., Neira, M., Omar, M., Pascale, A., Ruchirawat, M., Sly, L., Sly, P.D., Van den Berg, M., Suk, W.A., 2015. E-Waste and Harm to Vulnerable Populations: A Growing Global Problem. Environ. Health Perspect. 124, 550–555. https://doi.org/10.1289/ehp.1509699 Heudorf, U., Mersch-Sundermann, V., Angerer, J., 2007. Phthalates: Toxicology and exposure. Int. J. Hyg. Environ. Health 210, 623–634. https://doi.org/10.1016/j.ijheh.2007.07.011 Hill, K.L., Hamers, T., Kamstra, J.H., Willmore, W.G., Letcher, R.J., 2018. Organophosphate triesters and selected metabolites enhance binding of thyroxine to human transthyretin in vitro. Toxicol. Lett. 285, 87–93. https://doi.org/10.1016/j.toxlet.2017.12.030 Hites, R.A., 2004. Polybrominated Diphenyl Ethers in the Environment and in People: A Meta- Analysis of Concentrations. Environ. Sci. Technol. 38, 945–956. https://doi.org/10.1021/es035082g Hoffman, K., Butt, C.M., Webster, T.F., Preston, E. V., Hammel, S.C., Makey, C., Lorenzo, A.M., Cooper, E.M., Carignan, C., Meeker, J.D., Hauser, R., Soubry, A., Murphy, S.K., Price, T.M., Hoyo, C., Mendelsohn, E., Congleton, J., Daniels, J.L., Stapleton, H.M., 2017a. Temporal Trends in Exposure to Organophosphate Flame Retardants in the United States. Environ. Sci. Technol. Lett. 4, 112–118. https://doi.org/10.1021/acs.estlett.6b00475 Hoffman, K., Lorenzo, A., Butt, C.M., Hammel, S.C., Henderson, B.B., Roman, S.A., Scheri, R.P., Stapleton, H.M., Sosa, J.A., 2017b. Exposure to flame retardant chemicals and occurrence and severity of papillary thyroid cancer: A case-control study. Environ. Int. 107, 235–242. https://doi.org/10.1016/j.envint.2017.06.021 Holmes, A.K., Koller, K.R., Kieszak, S.M., Sjodin, A., Calafat, A.M., Sacco, F.D., Varner, D.W., Lanier, A.P., Rubin, C.H., 2014. Case–control study of breast cancer and exposure to synthetic environmental chemicals among Alaska Native women. Int. J. Circumpolar Health 73, 25760. https://doi.org/10.3402/ijch.v73.25760 Hou, R., Xu, Y., Wang, Z., 2016. Review of OPFRs in animals and humans: Absorption, bioaccumulation, metabolism, and internal exposure research. Chemosphere 153, 78–90. https://doi.org/10.1016/j.chemosphere.2016.03.003 Hubinger, J.C., Havery, D.C., 2006. Analysis of consumer cosmetic products for phthalate esters. J. Cosmet. Sci. 57, 127–37. Hutter, H.-P., Haluza, D., Piegler, K., Hohenblum, P., Fröhlich, M., Scharf, S., Uhl, M., Damberger, B., Tappler, P., Kundi, M., Wallner, P., Moshammer, H., 2013. Semivolatile compounds in schools and their influence on cognitive performance of children. Int. J. Occup. Med. Environ. Health 26, 628–635. https://doi.org/10.2478/s13382-013-0125-z IARC Working Group on the Evaluation of Carcinogenic Risks to Humans, 2013. Some chemicals present in industrial and consumer products, food and drinking-water. IARC Monogr. Eval. Carcinog. Risks Hum. 101, 9–549. Igharo, O.G., Anetor, J.I., Osibanjo, O., Osadolor, H.B., Odazie, E.C., Uche, Z.C., 2018. Endocrine disrupting metals lead to alteration in the gonadal hormone levels in Nigerian e- waste workers. Universa Med. 37, 65. https://doi.org/10.18051/UnivMed.2018.v37.65-74

Iqbal, M., Syed, J.H., Breivik, K., Chaudhry, M.J.I., Li, J., Zhang, G., Malik, R.N., 2017. E- Waste Driven Pollution in Pakistan: The First Evidence of Environmental and Human Exposure to Flame Retardants (FRs) in Karachi City. Environ. Sci. Technol. 51, 13895– 13905. https://doi.org/10.1021/acs.est.7b03159 Jacobson, M.H., Barr, D.B., Marcus, M., Muir, A.B., Lyles, R.H., Howards, P.P., Pardo, L., Darrow, L.A., 2016. Serum polybrominated diphenyl ether concentrations and thyroid function in young children. Environ. Res. 149, 222–230. https://doi.org/10.1016/j.envres.2016.05.022 Jarema, K.A., Hunter, D.L., Shaffer, R.M., Behl, M., Padilla, S., 2015. Acute and developmental behavioral effects of flame retardants and related chemicals in zebrafish. Neurotoxicol. Teratol. 52, 194–209. https://doi.org/10.1016/j.ntt.2015.08.010 Julander, A., Westberg, H., Engwall, M., van Bavel, B., 2005. Distribution of brominated flame retardants in different dust fractions in air from an electronics recycling facility. Sci. Total Environ. 350, 151–160. https://doi.org/10.1016/j.scitotenv.2005.01.015 Kahhat, R., Williams, E., 2012. Materials flow analysis of e-waste: Domestic flows and exports of used computers from the United States. Resour. Conserv. Recycl. 67, 67–74. https://doi.org/10.1016/j.resconrec.2012.07.008 Kammerer, F., 2017. Safe Drinking Water and Toxic Enforcement Act of 1986. Environ. Heal. 1–22. Kile, M.L., Scott, R.P., O’Connell, S.G., Lipscomb, S., MacDonald, M., McClelland, M., Anderson, K.A., Gibson, E.A., Stapleton, H.M., Calero, L., Holmes, D., Burke, K., Martinez, R., Cortes, B., Nematollahi, A., Evans, D., Anderson, K.A., Herbstman, J.B., Fisher, M., Arbuckle, T.E., MacPherson, S., Braun, J.M., Feeley, M., Gaudreau, É., Dixon, H.M., Scott, R.P., Holmes, D., Calero, L., Kincl, L.D., Waters, K.M., Camann, D.E., Calafat, A.M., Herbstman, J.B., Anderson, K.A., Bohlin, P., Jones, K.C., Levin, J.O., Lindahl, R., Strandberg, B., 2019. Using silicone wristbands to evaluate preschool children’s exposure to flame retardants. Chemosphere 219, 567–573. https://doi.org/10.1007/s00216-018-0992-z Kim, E.-H., Jeon, B.-H., Kim, J., Kim, Y.-M., Han, Y., Ahn, K., Cheong, H.-K., 2017. Exposure to phthalates and bisphenol A are associated with atopic dermatitis symptoms in children: a time-series analysis. Environ. Heal. 16, 24. https://doi.org/10.1186/s12940-017-0225-5 Kim, Y.H., Wyrzykowska-Ceradini, B., Touati, A., Krantz, Q.T., Dye, J.A., Linak, W.P., Gullett, B., Gilmour, M.I., 2015. Characterization of Size-Fractionated Airborne Particles Inside an Electronic Waste Recycling Facility and Acute Toxicity Testing in Mice. Environ. Sci. Technol. 49, 11543–11550. https://doi.org/10.1021/acs.est.5b03263 Koniecki, D., Wang, R., Moody, R.P., Zhu, J., 2011. Phthalates in cosmetic and personal care products: Concentrations and possible dermal exposure. Environ. Res. 111, 329–336. https://doi.org/10.1016/j.envres.2011.01.013 Kuo, L., Cade, S.E., Cullinan, V., Schultz, I.R., 2019. Polybrominated diphenyl ethers (PBDEs) in plasma from E-waste recyclers, outdoor and indoor workers in the Puget Sound, WA region. Chemosphere 219, 209–216. https://doi.org/10.1016/j.chemosphere.2018.12.006 Kuriyama, S.N., Talsness, C.E., Grote, K., Chahoud, I., 2005. Developmental exposure to low- dose PBDE-99: Effects on male fertility and neurobehavior in rat offspring. Environ. Health Perspect. 113, 149–154. https://doi.org/10.1289/ehp.7421 La Guardia, M.J., Hale, R.C., Harvey, E., 2006. Detailed Polybrominated Diphenyl Ether (PBDE) Congener Composition of the Widely Used Penta-, Octa-, and Deca-PBDE

Technical Flame-retardant Mixtures. Environ. Sci. Technol. 40, 6247–6254. https://doi.org/10.1021/es060630m Labunska, I., Harrad, S., Wang, M., Santillo, D., Johnston, P., 2014. Human Dietary Exposure to PBDEs Around E-Waste Recycling Sites in Eastern China. Environ. Sci. Technol. 48, 5555–5564. https://doi.org/10.1021/es500241m Lam, J., Lanphear, B.P., Bellinger, D., Axelrad, D.A., McPartland, J., Sutton, P., Davidson, L., Daniels, N., Sen, S., Woodruff, T.J., 2017. Developmental PBDE Exposure and IQ/ADHD in Childhood: A Systematic Review and Meta-analysis. Environ. Health Perspect. 125. https://doi.org/10.1289/EHP1632 Lenters, V., Portengen, L., Rignell-Hydbom, A., Jönsson, B.A.G., Lindh, C.H., Piersma, A.H., Toft, G., Bonde, J.P., Heederik, D., Rylander, L., Vermeulen, R., 2016. Prenatal Phthalate, Perfluoroalkyl Acid, and Organochlorine Exposures and Term Birth Weight in Three Birth Cohorts: Multi-Pollutant Models Based on Elastic Net Regression. Environ. Health Perspect. 124, 365–372. https://doi.org/10.1289/ehp.1408933 Li, F., Xie, Q., Li, X., Li, N., Chi, P., Chen, J., Wang, Z., Hao, C., 2010. Hormone Activity of Hydroxylated Polybrominated Diphenyl Ethers on Human Thyroid Receptor-β: In Vitro and In Silico Investigations. Environ. Health Perspect. 118, 602–606. https://doi.org/10.1289/ehp.0901457 Lilienthal, H., Hack, A., Roth-Härer, A., Grande, S.W., Talsness, C.E., 2006. Effects of developmental exposure to 2,2′,4,4′, 5-pentabromodiphenyl ether (PBDE-99) on sex steroids, sexual development, and sexually dimorphic behavior in rats. Environ. Health Perspect. 114, 194–201. https://doi.org/10.1289/ehp.8391 Lippmann, M., 1998. The 1997 US EPA Standards for Particulate Matter and Ozone, in: Air Pollution and Health. pp. 75–100. https://doi.org/10.1039/9781847550095-00075 Little, J.C., Weschler, C.J., Nazaroff, W.W., Liu, Z., Cohen Hubal, E.A., 2012. Rapid Methods to Estimate Potential Exposure to Semivolatile Organic Compounds in the Indoor Environment. Environ. Sci. Technol. 46, 11171–11178. https://doi.org/10.1021/es301088a Liu, C., Zhang, Y., Weschler, C.J., 2017. Exposure to SVOCs from Inhaled Particles: Impact of Desorption. Environ. Sci. Technol. 51, 6220–6228. https://doi.org/10.1021/acs.est.6b05864 Lu, S.Y., Li, Y.X., Zhang, T., Cai, D., Ruan, J.J., Huang, M.Z., Wang, L., Zhang, J.Q., Qiu, R.L., 2017. Effect of E-waste Recycling on Urinary Metabolites of Organophosphate Flame Retardants and Plasticizers and Their Association with Oxidative Stress. Environ. Sci. Technol. 51, 2427–2437. https://doi.org/10.1021/acs.est.6b05462 Lucas, D., Petty, S.M., Keen, O., Luedeka, B., Schlummer, M., Weber, R., Barlaz, M., Yazdani, R., Riise, B., Rhodes, J., Nightingale, D., Diamond, M.L., Vijgen, J., Lindeman, A., Blum, A., Koshland, C.P., 2017. Methods of Responsibly Managing End-of-Life Foams and Plastics Containing Flame Retardants: Part I. Environ. Eng. Sci. https://doi.org/10.1089/ees.2017.0147 Ma, J., Addink, R., Yun, S., Cheng, J., Wang, W., Kannan, K., 2009. Polybrominated Dibenzo- p -dioxins/Dibenzofurans and Polybrominated Diphenyl Ethers in Soil, Vegetation, Workshop-Floor Dust, and Electronic Shredder Residue from an Electronic Waste Recycling Facility and in Soils from a Chemical Industrial Complex in Ea. Environ. Sci. Technol. 43, 7350–7356. https://doi.org/10.1021/es901713u MacIntosh, D.L., Minegishi, T., Fragala, M.A., Allen, J.G., Coghlan, K.M., Stewart, J.H., McCarthy, J.F., 2012. Mitigation of building-related polychlorinated biphenyls in indoor air of a school. Environ. Heal. A Glob. Access Sci. Source 11, 1–10.

https://doi.org/10.1186/1476-069X-11-24 Mäkinen, M.S.E., Mäkinen, M.R.A., Koistinen, J.T.B., Pasanen, A.-L., Pasanen, P.O., Kalliokoski, P.J., Korpi, A.M., 2009. Respiratory and Dermal Exposure to Organophosphorus Flame Retardants and Tetrabromobisphenol A at Five Work Environments. Environ. Sci. Technol. 43, 941–947. https://doi.org/10.1021/es802593t Marek, R.F., Thorne, P.S., Herkert, N.J., Awad, A.M., Hornbuckle, K.C., 2017. Airborne PCBs and OH-PCBs Inside and Outside Urban and Rural U.S. Schools. Environ. Sci. Technol. 51, 7853–7860. https://doi.org/10.1021/acs.est.7b01910 Meeker, J.D., Cooper, E.M., Stapleton, H.M., Hauser, R., 2013. Exploratory analysis of urinary metabolites of phosphorus-containing flame retardants in relation to markers of male reproductive health. Endocr. Disruptors 1, e26306. https://doi.org/10.4161/endo.26306 Meeker, J.D., Stapleton, H.M., 2009. House Dust Concentrations of Organophosphate Flame Retardants in Relation to Hormone Levels and Semen Quality Parameters. Environ. Health Perspect. 118, 318–323. https://doi.org/10.1289/ehp.0901332 Meironyté, D., Norén, K., Bergman, Å., 1999. Analysis of polybrominated diphenyl ethers in swedish human milk. A time-related trend study, 1972–1997. J. Toxicol. Environ. Heal. - Part A 58, 329–341. https://doi.org/10.1080/009841099157197 Melymuk, L., Robson, M., Helm, P.A., Diamond, M.L., 2011. Evaluation of passive air sampler calibrations: Selection of sampling rates and implications for the measurement of persistent organic pollutants in air. Atmos. Environ. 45, 1867–1875. https://doi.org/10.1016/j.atmosenv.2011.01.011 Mendelsohn, E., Hagopian, A., Hoffman, K., Butt, C.M., Lorenzo, A., Congleton, J., Webster, T.F., Stapleton, H.M., 2016. Nail polish as a source of exposure to triphenyl phosphate. Environ. Int. 86, 45–51. https://doi.org/10.1016/j.envint.2015.10.005 Moeckel, C., Harner, T., Nizzetto, L., Strandberg, B., Lindroth, A., Jones, K.C., 2009. Use of depuration compounds in passive air samplers: Results from active sampling-supported field deployment, potential uses, and recommendations. Environ. Sci. Technol. 43, 3227– 3232. https://doi.org/10.1021/es802897x Morrison, G.C., Weschler, C.J., Bekö, G., Koch, H.M., Salthammer, T., Schripp, T., Toftum, J., Clausen, G., 2016. Role of clothing in both accelerating and impeding dermal absorption of airborne SVOCs. J. Expo. Sci. Environ. Epidemiol. 26, 113–118. https://doi.org/10.1038/jes.2015.42 Muenhor, D., Harrad, S., Ali, N., Covaci, A., 2010. Brominated flame retardants (BFRs) in air and dust from electronic waste storage facilities in Thailand. Environ. Int. 36, 690–698. https://doi.org/10.1016/j.envint.2010.05.002 Nalli, S., Horn, O.J., Grochowalski, A.R., Cooper, D.G., Nicell, J.A., 2006. Origin of 2- ethylhexanol as a VOC. Environ. Pollut. 140, 181–185. https://doi.org/10.1016/j.envpol.2005.06.018 National Academies of Sciences Engineering and Medicine, 2017. Application of Systematic Review Methods in an Overall Strategy for Evaluating Low-Dose Toxicity from Endocrine Active Chemicals. The National Academies Press, Washington,DC. https://doi.org/10.17226/24758 Nguyen, L. V., Diamond, M.L., Venier, M., Stubbings, W.A., Romanak, K., Bajard, L., Melymuk, L., Jantunen, L.M., Arrandale, V.H., 2019. Exposure of Canadian electronic waste dismantlers to flame retardants. Environ. Int. 129, 95–104. https://doi.org/10.1016/j.envint.2019.04.056

Nguyen, L. V., Gravel, S., Labrèche, F., Bakhiyi, B., Verner, M.A., Zayed, J., Jantunen, L.M., Arrandale, V.H., Diamond, M.L., 2020. Can Silicone Passive Samplers be Used for Measuring Exposure of e-Waste Workers to Flame Retardants? Environ. Sci. Technol. 54, 15277–15286. https://doi.org/10.1021/acs.est.0c05240 North, M.L., Takaro, T.K., Diamond, M.L., Ellis, A.K., 2014. Effects of phthalates on the development and expression of allergic disease and asthma. Ann. Allergy, Asthma Immunol. 112, 496–502. https://doi.org/10.1016/j.anai.2014.03.013 NTP, 1991. Toxicology and Carcinogenesis Studies of TRIS(2- CHLOROETHYL)PHOSPHATE (CAS NO. 115-96-8) in F344 / N Rats. Natl. Toxicol. Program Tech. Rep. Ser. 409, 1–171. O’Connell, S.G., Kincl, L.D., Anderson, K.A., 2014. Silicone Wristbands as Personal Passive Samplers. Environ. Sci. Technol. 48, 3327–3335. https://doi.org/10.1021/es405022f Okeme, J.O., Nguyen, L. V., Lorenzo, M., Dhal, S., Pico, Y., Arrandale, V.H., Diamond, M.L., 2018a. Polydimethylsiloxane (silicone rubber) brooch as a personal passive air sampler for semi-volatile organic compounds. Chemosphere 208, 1002–1007. https://doi.org/10.1016/j.chemosphere.2018.05.196 Okeme, J.O., Nguyen, L. V., Lorenzo, M., Dhal, S., Pico, Y., Arrandale, V.H., Diamond, M.L., 2018b. Polydimethylsiloxane (silicone rubber) brooch as a personal passive air sampler for semi-volatile organic compounds. Chemosphere 208, 1002–1007. https://doi.org/10.1016/j.chemosphere.2018.05.196 Okeme, J.O., Parnis, J.M., Poole, J., Diamond, M.L., Jantunen, L.M., 2016a. Polydimethylsiloxane-air partition ratios for semi-volatile organic compounds by GC-based measurement and COSMO-RS estimation: Rapid measurements and accurate modelling. Chemosphere 156, 204–211. https://doi.org/10.1016/j.chemosphere.2016.04.094 Okeme, J.O., Rodgers, T.F.M., Jantunen, L.M., Diamond, M.L., 2018c. Examining the Gas- Particle Partitioning of Organophosphate Esters: How Reliable Are Air Measurements? Environ. Sci. Technol. 52, 13834–13844. https://doi.org/10.1021/acs.est.8b04588 Okeme, J.O., Saini, A., Yang, C., Zhu, J., Smedes, F., Klánová, J., Diamond, M.L., 2016b. Calibration of polydimethylsiloxane and XAD-Pocket passive air samplers (PAS) for measuring gas- and particle-phase SVOCs. Atmos. Environ. 143, 202–208. https://doi.org/10.1016/j.atmosenv.2016.08.023 Okeme, J.O., Yang, C., Abdollahi, A., Dhal, S., Harris, S.A., Jantunen, L.M., Tsirlin, D., Diamond, M.L., 2018d. Passive air sampling of flame retardants and plasticizers in Canadian homes using PDMS, XAD-coated PDMS and PUF samplers. Environ. Pollut. 239, 109–117. https://doi.org/10.1016/j.envpol.2018.03.103 Okonski, K., Degrendele, C., Melymuk, L., Landlová, L., Kukučka, P., Vojta, Š., Kohoutek, J., Čupr, P., Klánová, J., 2014. Particle Size Distribution of Halogenated Flame Retardants and Implications for Atmospheric Deposition and Transport. Environ. Sci. Technol. 48, 14426–14434. https://doi.org/10.1021/es5044547 Ospina, M., Jayatilaka, N.K., Wong, L.-Y., Restrepo, P., Calafat, A.M., 2018. Exposure to organophosphate flame retardant chemicals in the U.S. general population: Data from the 2013–2014 National Health and Nutrition Examination Survey. Environ. Int. 110, 32–41. https://doi.org/10.1016/j.envint.2017.10.001 Park, S.A., Gwak, S., Choi, S., 2014. Assessment of occupational symptoms and chemical exposures for nail salon technicians in Daegu City, Korea. J. Prev. Med. Public Heal. 47, 169–176. https://doi.org/10.3961/jpmph.2014.47.3.169

Pawar, G., 2017. Exploring the utility of 3-D skin models to evaluate trans-dermal uptake of flame retardants from indoor dust and consumer product. University of Birmingham. Pelucchi, C., Negri, E., Gallus, S., Boffetta, P., Tramacere, I., La Vecchia, C., 2009. Long-term particulate matter exposure and mortality: a review of European epidemiological studies. BMC Public Health 9, 453. https://doi.org/10.1186/1471-2458-9-453 Percy, Z., Vuong, A.M., Ospina, M., Calafat, A.M., La Guardia, M.J., Xu, Y., Hale, R.C., Dietrich, K.N., Xie, C., Lanphear, B.P., Braun, J.M., Cecil, K.M., Yolton, K., Chen, A., 2020. Organophosphate esters in a cohort of pregnant women: Variability and predictors of exposure. Environ. Res. 184, 109255. https://doi.org/10.1016/j.envres.2020.109255 Pettersson-Julander, A., van Bavel, B., Engwall, M., Westberg, H., 2004. Personal air sampling and analysis of polybrominated diphenyl ethers and other bromine containing compounds at an electronic recycling facility in Sweden. J. Environ. Monit. 6, 874. https://doi.org/10.1039/b408381d Philippat, C., Bennett, D., Calafat, A.M., Picciotto, I.H., Xu, F., Giovanoulis, G., Van Waes, S., Padilla-Sanchez, J.A., Papadopoulou, E., Magnér, J., Haug, L.S., Neels, H., Covaci, A., 2016. Exposure to select phthalates and phenols through use of personal care products among Californian adults and their children. Environ. Res. 50, 7752–7760. https://doi.org/10.1021/acs.est.6b00246 Pinson, A., Bourguignon, J.P., Parent, A.S., 2016. Exposure to endocrine disrupting chemicals and neurodevelopmental alterations. Andrology 4, 706–722. https://doi.org/10.1111/andr.12211 Pope III, C.A., 2002. Lung Cancer, Cardiopulmonary Mortality, and Long-term Exposure to Fine Particulate Air Pollution. JAMA 287, 1132. https://doi.org/10.1001/jama.287.9.1132 Quach, T., Gunier, R., Tran, A., Von Behren, J., Doan-Billings, P.-A., Nguyen, K.-D., Okahara, L., Lui, B.Y.-B., Nguyen, M., Huynh, J., Reynolds, P., 2011. Characterizing Workplace Exposures in Vietnamese Women Working in California Nail Salons. Am. J. Public Health 101, S271–S276. https://doi.org/10.2105/AJPH.2010.300099 Radke, E.G., Braun, J.M., Meeker, J.D., Cooper, G.S., Agency, U.S.E.P., States, U., 2018. Phthalate exposure and male reproductive outcomes : A systematic review of the human epidemiological evidence. Environ. Int. 121, 764–793. https://doi.org/10.1016/j.envint.2018.07.029 Rakkestad, K.E., Dye, C.J., Yttri, K.E., Holme, J.A., Hongslo, J.K., Schwarze, P.E., Becher, R., 2007. Phthalate levels in Norwegian indoor air related to particle size fraction. J. Environ. Monit. 9, 1419. https://doi.org/10.1039/b709947a Rengasamy, S., Eimer, B., Shaffer, R.E., 2010. Simple respiratory protection - Evaluation of the filtration performance of cloth masks and common fabric materials against 20-1000 nm size particles. Ann. Occup. Hyg. 54, 789–798. https://doi.org/10.1093/annhyg/meq044 Richman, K.E., Butt, C.M., Young, C.J., 2018. Size-resolved particle measurements of polybrominated diphenyl ethers indoors: Implications for sources and human exposure. Environ. Toxicol. Chem. 37, 481–490. https://doi.org/10.1002/etc.3981 Robinson, B.H., 2009. E-waste: An assessment of global production and environmental impacts. Sci. Total Environ. 408, 183–191. https://doi.org/10.1016/j.scitotenv.2009.09.044 Rodes, C.E., Kamens, R.M., Wiener, R.W., 1991. The Significance and Characteristics of the Personal Activity Cloud on Exposure Assessment Measurements for Indoor Contaminants. Indoor Air 1, 123–145. https://doi.org/10.1111/j.1600-0668.1991.03-12.x Romanak, K.A., Wang, S., Stubbings, W.A., Hendryx, M., Venier, M., Salamova, A., 2019.

Analysis of brominated and chlorinated flame retardants, organophosphate esters, and polycyclic aromatic hydrocarbons in silicone wristbands used as personal passive samplers. J. Chromatogr. A 1588, 41–47. https://doi.org/10.1016/j.chroma.2018.12.041 Romero-Franco, M., Hernández-Ramírez, R.U., Calafat, A.M., Cebrián, M.E., Needham, L.L., Teitelbaum, S., Wolff, M.S., López-Carrillo, L., 2011. Personal care product use and urinary levels of phthalate metabolites in Mexican women. Environ. Int. 37, 867–871. https://doi.org/10.1016/j.envint.2011.02.014 Rosenberg, C., Hämeilä, M., Tornaeus, J., Säkkinen, K., Puttonen, K., Korpi, A., Kiilunen, M., Linnainmaa, M., Hesso, A., 2011. Exposure to Flame Retardants in Electronics Recycling Sites. Ann. Occup. Hyg. 55, 658–665. https://doi.org/10.1093/annhyg/mer033 Saini, A., Okeme, J.O., Goosey, E., Diamond, M.L., 2015. Calibration of two passive air samplers for monitoring phthalates and brominated flame-retardants in indoor air. Chemosphere 137, 166–173. https://doi.org/10.1016/j.chemosphere.2015.06.099 Saini, A., Okeme, J.O., Mark Parnis, J., McQueen, R.H., Diamond, M.L., 2016. From air to clothing: characterizing the accumulation of semi-volatile organic compounds to fabrics in indoor environments. Indoor Air. https://doi.org/10.1111/ina.12328 SCHETTLER, T., 2006. Human exposure to phthalates via consumer products. Int. J. Androl. 29, 134–139. https://doi.org/10.1111/j.1365-2605.2005.00567.x Schreder, E.D., Uding, N., La Guardia, M.J., 2016. Inhalation a significant exposure route for chlorinated organophosphate flame retardants. Chemosphere 150, 499–504. https://doi.org/10.1016/j.chemosphere.2015.11.084 Schwartz, J., Neas, L.M., 2000. Fine particles are more strongly associated than coarse particleswithacute respiratoryhealtheffectsinschoolchildren. Epidemiology 11, 6–10. Shi, T., Chen, S.-J., Luo, X.-J., Zhang, X.-L., Tang, C.-M., Luo, Y., Ma, Y.-J., Wu, J.-P., Peng, X.-Z., Mai, B.-X., 2009. Occurrence of brominated flame retardants other than polybrominated diphenyl ethers in environmental and biota samples from southern China. Chemosphere 74, 910–916. https://doi.org/10.1016/j.chemosphere.2008.10.047 Shoeib, M., Harner, T., 2002. Characterization and Comparison of Three Passive Air Samplers for Persistent Organic Pollutants. Environ. Sci. Technol. 36, 4142–4151. https://doi.org/10.1021/es020635t Sindiku, O., Babayemi, J., Osibanjo, O., Schlummer, M., Schluep, M., Watson, A., Weber, R., 2015. Polybrominated diphenyl ethers listed as Stockholm Convention POPs, other brominated flame retardants and heavy metals in e-waste polymers in Nigeria. Environ. Sci. Pollut. Res. 22, 14489–14501. https://doi.org/10.1007/s11356-014-3266-0 Singh, M., Thind, P.S., John, S., 2018. Health risk assessment of the workers exposed to the heavy metals in e-waste recycling sites of Chandigarh and Ludhiana, Punjab, India. Chemosphere 203, 426–433. https://doi.org/10.1016/j.chemosphere.2018.03.138 Sjödin, A., Carlsson, H., Thuresson, K., Sjölin, S., Bergman, Å., Östman, C., 2001. Flame Retardants in Indoor Air at an Electronics Recycling Plant and at Other Work Environments. Environ. Sci. Technol. 35, 448–454. https://doi.org/10.1021/es000077n Slotkin, T.A., Skavicus, S., Stapleton, H.M., Seidler, F.J., 2017. Brominated and organophosphate flame retardants target different neurodevelopmental stages, characterized with embryonic neural stem cells and neuronotypic PC12 cells. Toxicology 390, 32–42. https://doi.org/10.1016/j.tox.2017.08.009 Smil, V., 2017. PLANET OF THE COWS. IEEE Spectr. 54, 24. Snedeker, S.M., 2014. Toxicants in Food Packaging and Household Plastics, Molecular and

Integrative Toxicology. Springer London, London. https://doi.org/10.1007/978-1-4471- 6500-2 Staaf, T., Ostman, C., 2005. Organophosphate triesters in indoor environments. J. Environ. Monit. 7, 883–887. https://doi.org/10.1039/b506631j Stapleton, H.M., Allen, J.G., Kelly, S.M., Konstantinov, A., Klosterhaus, S., Watkins, D., McClean, M.D., Webster, T.F., 2008a. Alternate and New Brominated Flame Retardants Detected in U.S. House Dust. Environ. Sci. Technol. 42, 6910–6916. https://doi.org/10.1021/es801070p Stapleton, H.M., Kelly, S.M., Allen, J.G., McClean, M.D., Webster, T.F., Stapleton, M.H., Kelly, S.M., Allen, J.G., McClean, M.D., Webster, T.F., Stapleton, H.M., Kelly, S.M., Allen, J.G., McClean, M.D., Webster, T.F., 2008b. Measurement of Polybrominated Diphenyl Ethers on Hand Wipes: Estimating Exposure from Hand-to-Mouth Contact. Environ. Sci. Technol. 42, 3329–3334. https://doi.org/10.1021/es7029625 Statistics Canada, 2016. EnviroStats Trash talking: Dealing with Canadian household e-waste. [WWW Document]. URL http://www.statcan.gc.ca/pub/16-002-x/2016001/article/14570- eng.htm (accessed 7.15.18). Stubbings, W.A., Nguyen, L. V., Romanak, K., Jantunen, L., Melymuk, L., Arrandale, V., Diamond, M.L., Venier, M., 2019a. Flame retardants and plasticizers in a Canadian waste electrical and electronic equipment (WEEE) dismantling facility. Sci. Total Environ. 675, 594–603. https://doi.org/10.1016/j.scitotenv.2019.04.265 Stubbings, W.A., Nguyen, L. V., Romanak, K., Jantunen, L., Melymuk, L., Arrandale, V., Diamond, M.L., Venier, M., 2019b. Flame retardants and plasticizers in a Canadian waste electrical and electronic equipment (WEEE)dismantling facility. Sci. Total Environ. 675, 594–603. https://doi.org/10.1016/j.scitotenv.2019.04.265 Suzuki, G., Tue, N.M., Malarvannan, G., Sudaryanto, A., Takahashi, S., Tanabe, S., Sakai, S., Brouwer, A., Uramaru, N., Kitamura, S., Takigami, H., 2013. Similarities in the Endocrine- Disrupting Potencies of Indoor Dust and Flame Retardants by Using Human Osteosarcoma (U2OS) Cell-Based Reporter Gene Assays. Environ. Sci. Technol. 47, 2898–2908. https://doi.org/10.1021/es304691a Swedish Chemicals Inspectorate, 2003. Brominated flame retardants – Prospects of a national ban. KemI Report 4/03. Takigami, H., Suzuki, G., Hirai, Y., Sakai, S., 2008. Transfer of brominated flame retardants from components into dust inside television cabinets. Chemosphere 73, 161–169. https://doi.org/10.1016/j.chemosphere.2008.06.032 Tansel, B., 2017. From electronic consumer products to e-wastes: Global outlook, waste quantities, recycling challenges. Environ. Int. 98, 35–45. https://doi.org/10.1016/j.envint.2016.10.002 Thuresson, K., Höglund, P., Hagmar, L., Sjödin, A., Bergman, Å., Jakobsson, K., 2006. Apparent Half-Lives of Hepta- to Decabrominated Diphenyl Ethers in Human Serum as Determined in Occupationally Exposed Workers. Environ. Health Perspect. 114, 176–181. https://doi.org/10.1289/ehp.8350 Tran, T.M., Kannan, K., 2015. Occurrence of Phthalate Diesters in Particulate and Vapor Phases in Indoor Air and Implications for Human Exposure in Albany, New York, USA. Arch. Environ. Contam. Toxicol. 68, 489–499. https://doi.org/10.1007/s00244-015-0140-0 Tran, T.M., Le, H.T., Minh, T.B., Kannan, K., 2017. Occurrence of phthalate diesters in indoor air from several Northern cities in Vietnam, and its implication for human exposure. Sci.

Total Environ. 601–602, 1695–1701. https://doi.org/10.1016/j.scitotenv.2017.06.016 Traore, I.T., Gravel, S., Diamond, M.L., Jantunen, L., Nguyen, L.V., Yang, C., Bernstein, S., Zayed, J., Labrèche, F., Verner, M.-A., 2018. Urinary Metabolites of Organophosphate Esters (OPEs) in Electronic Waste Recycling Workers from the Province of Quebec, Canada. ISEE Conf. Abstr. 2018, isesisee.2018.P01.3100. https://doi.org/10.1289/isesisee.2018.P01.3100 Tromp, P.C., Beeltje, H., Okeme, J.O., Vermeulen, R., Pronk, A., Diamond, M.L., 2019. Calibration of polydimethylsiloxane and polyurethane foam passive air samplers for measuring semi volatile organic compounds using a novel exposure chamber design. Chemosphere 227, 435–443. https://doi.org/10.1016/j.chemosphere.2019.04.043 Tue, N.M., Takahashi, S., Suzuki, G., Isobe, T., Viet, P.H., Kobara, Y., Seike, N., Zhang, G., Sudaryanto, A., Tanabe, S., 2013. Contamination of indoor dust and air by polychlorinated biphenyls and brominated flame retardants and relevance of non-dietary exposure in Vietnamese informal e-waste recycling sites. Environ. Int. 51, 160–167. https://doi.org/10.1016/j.envint.2012.11.006 U.S.Bureau of Labor, 2020. Occupational Outlook Handbook [WWW Document]. UCLA Labor Center, 2018. Nail Files: A study of nail salon workers and industry in United States. UNEP, 2019. A New Circular Vision for Electronics Time for a Global Reboot 24. UNEP, 2016. GEO-6 North America Regional Assessment [WWW Document]. URL http://wedocs.unep.org/bitstream/handle/20.500.11822/7611/GEO_North_America_201611 .pdf?sequence=1&isAllowed=y (accessed 6.27.18). UNEP, 2010. Technical review of the implications of recycling commercial pentabromodiphenyl ether and commercial octabromodi- phenyl ether. UNEP, 2008. Report of the Persistent Organic Pollutants Review Committee on the work of its fourth meeting. United States Department of Labor, 2017. Occupational Employment and Wages, May 2017 [WWW Document]. URL https://www.bls.gov/oes/current/oes395092.htm#st US EPA, 2018a. IRIS Assessments [WWW Document]. URL https://cfpub.epa.gov/ncea/iris2/atoz.cfm (accessed 6.27.18). US EPA, 2018b. Chemistry Dashboard [WWW Document]. URL https://comptox.epa.gov/dashboard (accessed 6.27.18). US EPA, 2018c. 2,2’,4,4’,5-Pentabromodiphenyl ether (BDE-99) [WWW Document]. URL https://cfpub.epa.gov/ncea/iris2/chemicalLanding.cfm?substance_nmbr=1008 (accessed 6.27.18). US EPA, 2011. September 2011 EXPOSURE FACTORS HANDBOOK : 2011 EDITION National Center for Environmental Assessment Office of Research and Development U . S . Environmental Protection Agency Washington , DC 20460 Exposure Factors Handbook. Exposure. USEPA, 2020. CHEMICALS KNOWN TO THE STATE TO CAUSE CANCER OR REPRODUCTIVE TOXICITY January 3, 2020. Veen, I. Van Der, Boer, J. De, 2012. Chemosphere Phosphorus flame retardants : Properties , production , environmental occurrence , toxicity and analysis. Chemosphere 88, 1119– 1153. https://doi.org/10.1016/j.chemosphere.2012.03.067 Venier, M., Ma, Y., Hites, R.A., 2012. Brominated flame retardants in the Great Lakes atmosphere. Environ. Sci. Technol. 46, 8653–8660.

https://doi.org/dx.doi.org/10.1021/es3015919 Viberg, H., Fredriksson, A., Eriksson, P., 2004. Investigations of strain and/or gender differences in developmental neurotoxic effects of polybrominated diphenyl ethers in mice. Toxicol. Sci. 81, 344–353. https://doi.org/10.1093/toxsci/kfh215 Viberg, H., Fredriksson, A., Jakobsson, E., Orn, U., Erikson, P., 2003. Neurobehavioral derangements in adult mice receiving decabrominated diphenyl ether (PBDE 209) during a defined period of neonatal brain development. Toxicol. Sci. 76, 112–120. https://doi.org/10.1093/toxsci/kfg210 Vojta, Š., Bečanová, J., Melymuk, L., Komprdová, K., Kohoutek, J., Kukučka, P., Klánová, J., 2017. Screening for halogenated flame retardants in European consumer products, building materials and wastes. Chemosphere 168, 457–466. https://doi.org/10.1016/j.chemosphere.2016.11.032 Vuong, A.M., Braun, J.M., Webster, G.M., Thomas Zoeller, R., Hoofnagle, A.N., Sjödin, A., Yolton, K., Lanphear, B.P., Chen, A., 2018. Polybrominated diphenyl ether (PBDE) exposures and thyroid hormones in children at age 3 years. Environ. Int. 117, 339–347. https://doi.org/10.1016/j.envint.2018.05.019 Vuong, A.M., Yolton, K., Xie, C., Webster, G.M., Sjödin, A., Braun, J.M., Dietrich, K.N., Lanphear, B.P., Chen, A., 2017. Childhood polybrominated diphenyl ether (PBDE) exposure and neurobehavior in children at 8 years. Environ. Res. 158, 677–684. https://doi.org/10.1016/j.envres.2017.07.028 Vykoukalová, M., Venier, M., Vojta, Š., Melymuk, L., Bečanová, J., Romanak, K., Prokeš, R., Okeme, J.O., Saini, A., Diamond, M.L., Klánová, J., 2017. Organophosphate esters flame retardants in the indoor environment. Environ. Int. 106, 97–104. https://doi.org/10.1016/j.envint.2017.05.020 Wallace, L., 2000. Correlations of personal exposure to particles with outdoor air measurements: A review of recent studies. Aerosol Sci. Technol. 32, 15–25. https://doi.org/10.1080/027868200303894 Wallner, P., Kundi, M., Hohenblum, P., Scharf, S., Hutter, H., 2016. Phthalate Metabolites, Consumer Habits and Health Effects. Int. J. Environ. Res. Public Health 13, 717. https://doi.org/10.3390/ijerph13070717 Wan, Y., Diamond, M.L., Siegel, J.A., 2020. Elevated Concentrations of Semivolatile Organic Compounds in Social Housing Multiunit Residential Building Apartments. Environ. Sci. Technol. Lett. 7, 191–197. https://doi.org/10.1021/acs.estlett.0c00068 Wang, D.G., Alaee, M., Byer, J.D., Brimble, S., Pacepavicius, G., 2013. Human health risk assessment of occupational and residential exposures to dechlorane plus in the manufacturing facility area in China and comparison with e-waste recycling site. Sci. Total Environ. 445–446, 329–336. https://doi.org/10.1016/j.scitotenv.2012.12.059 Wang, S., Romanak, K.A., Stubbings, W.A., Arrandale, V.H., Hendryx, M., Diamond, M.L., Salamova, A., Venier, M., 2019. Silicone wristbands integrate dermal and inhalation exposures to semi-volatile organic compounds (SVOCs). Environ. Int. 132, 105104. https://doi.org/10.1016/j.envint.2019.105104 Wang, Y., Peris, A., Rifat, M.R., Ahmed, S.I., Aich, N., Nguyen, L. V., Urík, J., Eljarrat, E., Vrana, B., Jantunen, L.M., Diamond, M.L., 2020. Measuring exposure of e-waste dismantlers in Dhaka Bangladesh to organophosphate esters and halogenated flame retardants using silicone wristbands and T-shirts. Sci. Total Environ. 720, 137480. https://doi.org/10.1016/j.scitotenv.2020.137480

Wei, G.-L., Li, D.-Q., Zhuo, M.-N., Liao, Y.-S., Xie, Z.-Y., Guo, T.-L., Li, J.-J., Zhang, S.-Y., Liang, Z.-Q., 2015. Organophosphorus flame retardants and plasticizers: Sources, occurrence, toxicity and human exposure. Environ. Pollut. 196, 29–46. https://doi.org/10.1016/j.envpol.2014.09.012 Wei, W., Bonvallot, N., Gustafsson, Å., Raffy, G., Glorennec, P., Krais, A., Ramalho, O., Le Bot, B., Mandin, C., 2018. Bioaccessibility and bioavailability of environmental semi- volatile organic compounds via inhalation: A review of methods and models. Environ. Int. 113, 202–213. https://doi.org/10.1016/j.envint.2018.01.024 Wei, W., Mandin, C., Ramalho, O., 2017. Reactivity of Semivolatile Organic Compounds with Hydroxyl Radicals, Nitrate Radicals, and Ozone in Indoor Air. Int. J. Chem. Kinet. 49, 506–521. https://doi.org/10.1002/kin.21093 Weschler, C.J., Nazaroff, W.W., 2014. Dermal Uptake of Organic Vapors Commonly Found in Indoor Air. Environ. Sci. Technol. 48, 1230–1237. https://doi.org/10.1021/es405490a Weschler, C.J., Nazaroff, W.W., 2012. SVOC exposure indoors: Fresh look at dermal pathways. Indoor Air. https://doi.org/10.1111/j.1600-0668.2012.00772.x Weschler, C.J., Nazaroff, W.W., 2010. SVOC partitioning between the gas phase and settled dust indoors. Atmos. Environ. 44, 3609–3620. https://doi.org/10.1016/j.atmosenv.2010.06.029 Weschler, C.J., Nazaroff, W.W., 2008. Semivolatile organic compounds in indoor environments. Atmos. Environ. 42, 9018–9040. https://doi.org/10.1016/j.atmosenv.2008.09.052 Whitman, W.G., 1962. The two film theory of gas absorption. Int. J. Heat Mass Transf. 5, 429– 433. https://doi.org/10.1016/0017-9310(62)90032-7 Wielsøe, M., Kern, P., Bonefeld-Jørgensen, E.C., 2017. Serum levels of environmental pollutants is a risk factor for breast cancer in Inuit: a case control study. Environ. Heal. 16, 56. https://doi.org/10.1186/s12940-017-0269-6 Wong, C.S.C., Duzgoren-Aydin, N.S., Aydin, A., Wong, M.H., 2007. Evidence of excessive releases of metals from primitive e-waste processing in Guiyu, China. Environ. Pollut. 148, 62–72. https://doi.org/10.1016/j.envpol.2006.11.006 Wu, C.-C., Bao, L.-J., Tao, S., Zeng, E.Y., 2016. Dermal Uptake from Airborne Organics as an Important Route of Human Exposure to E-Waste Combustion Fumes. Environ. Sci. Technol. 50, 6599–6605. https://doi.org/10.1021/acs.est.5b05952 Xu, F., Zhang, G., Wang, J., Zhang, W., Liu, L., Lin, K., 2015. Polybrominated diphenyl ethers in air and fallouts from an e-waste polluted region in southeast China: insight into levels, compositional profiles, and seasonal variation. Environ. Sci. Pollut. Res. 22, 19676–19686. https://doi.org/10.1007/s11356-015-5168-1 Xu, Y., Cohen Hubal, E.A., Clausen, P.A., Little, J.C., 2009. Predicting Residential Exposure to Phthalate Plasticizer Emitted from Vinyl Flooring: A Mechanistic Analysis. Environ. Sci. Technol. 43, 2374–2380. https://doi.org/10.1021/es801354f Xu, Y., Cohen Hubal, E.A., Little, J.C., 2010. Predicting residential exposure to phthalate plasticizer emitted from vinyl flooring: Sensitivity, uncertainty, and implications for biomonitoring. Environ. Health Perspect. 118, 253–258. https://doi.org/10.1289/ehp.0900559 Yang, C., Harris, S.A., Jantunen, L.M., Kvasnicka, J., Nguyen, L. V., Diamond, M.L., 2020a. Phthalates: Relationships between Air, Dust, Electronic Devices, and Hands with Implications for Exposure. Environ. Sci. Technol. 54, acs.est.0c00229. https://doi.org/10.1021/acs.est.0c00229

Yang, C., Harris, S.A., Jantunen, L.M., Siddique, S., Kubwabo, C., Tsirlin, D., Latifovic, L., Fraser, B., St-Jean, M., De La Campa, R., You, H., Kulka, R., Diamond, M.L., 2018. Are cell phones an indicator of personal exposure to organophosphate flame retardants and plasticizers? Environ. Int. in press, 1–13. https://doi.org/10.1016/j.envint.2018.10.021 Yang, C., Jílková, S.R., Melymuk, L., Harris, S.A., Jantunen, L.M., Pertili, J., Winn, L., Diamond, M.L., 2020b. Are We Exposed to Halogenated Flame Retardants from both Primary and Secondary Sources? Environ. Sci. Technol. Lett. 7, 585–593. https://doi.org/10.1021/acs.estlett.0c00268 Young, A.S., Allen, J.G., Kim, U.-J.J., Seller, S., Webster, T.F., Kannan, K., Ceballos, D.M., 2018. Phthalate and Organophosphate Plasticizers in Nail Polish: Evaluation of Labels and Ingredients. Environ. Sci. Technol. 52, acs.est.8b04495. https://doi.org/10.1021/acs.est.8b04495 Zabiegała, B., Zygmunt, B., Przyk, E., Namieśnik, J., 2000. Applicability of silicone membrane passive samplers for monitoring of indoor air quality. Anal. Lett. 33, 1361–1372. https://doi.org/10.1080/00032710008543127 Zeng, X., Yang, C., Chiang, J.F., Li, J., 2017. Innovating e-waste management: From macroscopic to microscopic scales. Sci. Total Environ. 575, 1–5. https://doi.org/10.1016/j.scitotenv.2016.09.078 Zhang, H., Yolton, K., Webster, G.M., Sjödin, A., Calafat, A.M., Dietrich, K.N., Xu, Y., Xie, C., Braun, J.M., Lanphear, B.P., Chen, A., 2016. Prenatal PBDE and PCB Exposures and Reading, Cognition, and Externalizing Behavior in Children. Environ. Health Perspect. 125, 7–16. https://doi.org/10.1289/EHP478 Zhang, X., Diamond, M.L., Robson, M., Harrad, S., 2011. Sources, emissions, and fate of polybrominated diphenyl ethers and polychlorinated biphenyls indoors in Toronto, Canada. Environ. Sci. Technol. 45, 3268–3274. https://doi.org/10.1021/es102767g Zhang, Z., Sun, Z.-Z., Xiao, X., Zhou, S., Wang, X.X.-C., Gu, J., Qiu, L.-L., Zhang, X.-H., Xu, Q., Zhen, B., Wang, X.X.-C., Wang, S.-L., 2013a. Mechanism of BDE209-induced impaired glucose homeostasis based on gene microarray analysis of adult rat liver. Arch. Toxicol. 87, 1557–1567. https://doi.org/10.1007/s00204-013-1059-8 Zhang, Z., Zhang, X., Sun, Z., Dong, H., Qiu, L., Gu, J., Zhou, J., Wang, X., Wang, S.L., 2013b. Cytochrome P450 3A1 Mediates 2,2′,4,4′-Tetrabromodiphenyl Ether-Induced Reduction of Spermatogenesis in Adult Rats. PLoS One 8. https://doi.org/10.1371/journal.pone.0066301 Zheng, X., Xu, F., Chen, K., Zeng, Y., Luo, X., Chen, S., Mai, B., Covaci, A., 2015. Flame retardants and organochlorines in indoor dust from several e-waste recycling sites in South China: Composition variations and implications for human exposure. Environ. Int. 78, 1–7. https://doi.org/10.1016/j.envint.2015.02.006 Zota, A.R., Rudel, R.A., Morello-Frosch, R.A., Brody, J.G., 2008. Elevated House Dust and Serum Concentrations of PBDEs in California: Unintended Consequences of Furniture Flammability Standards? Environ. Sci. Technol. 42, 8158–8164. https://doi.org/10.1021/es801792z

Chapter 3 – The use of silicone passive samplers for measuring exposure of e-waste workers to flame retardants

Abstract

Silicone passive samplers were assessed for measuring personal exposure to 37 flame retardants (FRs) at three Québec e-waste recycling facilities. Silicone brooches (n = 45), wristbands (n = 28), and armbands (n = 9) worn during a ~8 hour work shift accumulated detectable amounts of 95-100% of target compounds. Brooch concentrations were significantly correlated with those from active air samplers from which we conclude that they could be used to approximate inhalation exposure and other exposures related to air concentrations such as dermal exposure. The generic sampling rate of the brooch (19 ± 11 m3 day-1 dm-2) was 13 and 22 times greater than estimated for home and office environments, respectively, likely due to the dusty work environment and greater movement of e-waste workers. BDE-209 concentrations in brooches and wristbands were moderately and significantly (p > 0.05) correlated with levels in blood plasma; OPEs in brooches and wristbands were weakly and insignificantly correlated with their metabolite biomarkers in post-shift spot urine samples. Silicone brooches and wristbands deployed over a single shift in a dusty occupational setting can be useful for indicating exposure to compounds with relatively long biological half-lives, but its use for compounds with relatively short half-lives is not clear and would require either a longer deployment time or an integrated biomarker measure.

3.1 Introduction

The mass of electrical and electronic waste (e-waste) produced worldwide is growing rapidly. In 2019, more than 53.6 million metric tonnes (Mt) of e-waste were generated globally

(Balde et al., 2017). With a doubling time of approximately 16 years, the amount of e-waste generated annually is predicted to reach 74.7 Mt by 2030 (Balde et al., 2017; Fortia et al., 2020).

The Americas contributed almost 25% of e-waste produced in 2019, with an estimated 727 kilotonnes generated by Canada (Balde et al., 2017). Exports of e-waste from high- to low- and medium-income countries continues to be highly problematic for receiving countries that are dealing with their own burgeoning e-waste. Since 2002, the Basel Convention has been coordinating international efforts to promote environmentally sound management of e-waste and to stop the flow of illegal shipments of e-waste (Basel Convention, 2011). In response to this, the formal e-waste recycling industry in high income countries has grown dramatically(Ceballos and

Dong, 2016).

E-waste recycling workers in both informal and formal e-waste sites are exposed to many hazardous chemicals including metals and flame retardants (FRs) (Asante et al., 2012; Gravel et al., 2019c; Mäkinen et al., 2009; Rosenberg et al., 2011; Singh et al., 2018; Wong et al., 2007).

Exposure to some FRs among the general population has been associated with a range of adverse human health effects such as neurodevelopmental and reproductive effects arising from fetal exposure (Braun et al., 2014; Factor-Litvak et al., 2014; Harley et al., 2010; North et al., 2014).

Evidence is now emerging that some FRs can cause changes in hormone levels (Gravel et al.,

2020; Igharo et al., 2018) and oxidative stress levels (Lu et al., 2017) of e-waste workers in formal and informal e-waste sectors. FRs such as polybrominated diphenyl ethers (PBDEs), hexabromocyclododecane (HBCDD) and some others have been restricted for use in new products

under the Stockholm Convention, as well as under regional (e.g., European Union) and national regulations (Blum et al., 2019). These regulations and policies have reduced exposure from new products among the general population, but not among e-waste workers who continue to handle older products containing these now-banned chemicals (Nguyen et al., 2019; Stubbings et al.,

2019a). Our previous work found that e-waste workers in a formal facility located in Ontario

(Canada) were exposed to elevated levels of banned PBDEs and a wide range of alternative FRs

(Nguyen et al., 2019; Stubbings et al., 2019a). The Ontario workers were estimated to be more highly exposed to these FRs through elevated air concentrations than e-waste handlers working in informal settings in several low income countries (Nguyen et al., 2019; Wang et al., 2020). E- waste workers in high-income countries have also been shown to have vulnerabilities related to working conditions, employment conditions and other sociodemographic factors (Ceballos et al.,

2020).

Silicone (or polydimethylsiloxane, PDMS) passive samplers as brooches and wristbands, have gained popularity for measuring semi-volatile organic compounds (SVOCs), including FRs, in air (Okeme et al., 2018d, 2018b, 2016b; Tromp et al., 2019) and to assess human exposure to

SVOCs from multiple routes, i.e., inhalation, dermal absorption, and hand-to-mouth contact

(Dixon et al., 2018; Hammel et al., 2016, 2018; O’Connell et al., 2014; Wang et al., 2019, 2020)

Silicone passive samplers are advantageous due to ease of deployment, low expense and high uptake capacity for capturing gas-phase SVOCs (Okeme et al., 2016b; Tromp et al., 2019; Wang et al., 2019). The silicone brooch was introduced by Okeme et al. (2018a) as a promising personal passive air sampler relying on diffusion of gas-phase SVOCs through a static air layer (Okeme et al., 2018b; Zabiegała et al., 2000). They found that the silicone brooch also accumulates particle- sorbed SVOCs, although the efficiency of accumulation was not investigated. Further, they

reported that silicone brooches could capture personal exposure to phthalates and organophosphorus esters (OPEs) over a total deployment time of approximately 24 hours (Okeme et al., 2018b). Wang et al. (2019) found that levels of SVOCs collected by a silicone brooch pinned on the lapel near the breathing zone closely approximated those measured using a reference active air sampler, suggesting that the brooch could be used to approximate inhalation exposure.

The use of silicone wristbands has become popular for qualitatively assessing human exposure to SVOCs via various routes since the method was first introduced by O’Connell et al.

(2014) to assess the exposure of roofers to polycyclic aromatic hydrocarbons (PAHs). Several studies have found moderate statistically significant correlations between levels of some FRs accumulated by wristbands worn in a residential setting, and their corresponding biomarkers in serum (Hammel et al., 2018) and urine (Craig et al., 2019; Dixon et al., 2018; Hammel et al.,

2016). The exposure routes represented by wristbands remain unclear. Wang et al. (2019) in a pilot study comparing the profiles of semi-volatile organic compounds (SVOCs) including FRs in personal active air samplers, hand wipes (back of hand), silicone brooches and wristbands, found that SVOC levels in brooches most closely approximated those in active air samplers, while the strongest correlations were for wristbands or brooches vs active air samplers plus hand wipes.

From this, the authors suggested that the brooch and wristband samplers reflected inhalation and dermal exposure pathways. This is logical since SVOCs in air are subject to inhalation as well as sorption to all surfaces, including skin for which uptake is then controlled by skin permeability

(Frederiksen et al., 2018; Xu et al., 2009; Yang et al., 2020a).

Workers, including those in e-waste recycling facilities, can be highly exposed to a wide range of contaminants, as noted above. However, measuring occupational exposure can be challenging because of difficulties with recruiting participants, as well as the expense and burden

of wearing active samplers. Silicone brooches or wristbands are promising sampling methods in occupational environments because they are unobtrusive, inexpensive and easy to deploy. For example, the pilot study of Craig et al. (2019) among 10 US nail technicians, found that several phthalates, phthalate alternatives, and OPEs were captured by wristbands over an eight hour work period but only the levels of di(2-ethylhexyl) terephthalate (DEHTP) on wristbands were moderately associated with its metabolite in urine. Wang et al. (2020) reported that concentrations of FRs in wristbands worn by 15 Bangladeshi e-waste recyclers for 24 hours were 2 – 130 times higher than those reported for US non-occupationally exposed participants for 7-day deployment

(Romanak et al., 2019). However, Wang et al.(Wang et al., 2020) did not have measurements of internal exposure.

Our goal was to evaluate the use of personal silicone passive samplers for capturing FRs in formal Canadian e-waste recycling facilities in order to assess workers’ internal and external exposure. We report results from silicone passive samplers worn as brooches, wristbands and armbands, and compare these results to both personal active air samplers and biomarkers previously reported by Gravel et al. (2019c) and Gravel et al. (2020), respectively.

3.2 Materials and Methods

3.2.1 Study design

Results presented here are part of a larger cross-sectional study whose primary aim was to examine the exposure to total airborne particulate matter (PM), metals and FRs among workers in the formal e-waste recycling industry. Further, the study also sought to assess endocrine effects of these exposures and to describe occupational health and safety practices among e-waste workers. Gravel et al. (2019c) presented full details of the study design. The present study included

a subset of 45 e-waste workers who were recruited from three e-waste recycling facilities in the province of Québec, Canada. All three facilities processed mixed e-waste including cathode ray tube televisions, monitors, computers and small electronics (e.g., telephones, toasters, curling irons). Two small facilities had less than 24 employees and one large facility had 65 employees.

Each worker performed different main tasks including sorting, dismantling, supervising, operating crushers or driving forklifts. Seventy-seven percent of workers wore long-sleeved protective clothing and fabric gloves but not N95 respirators or nitrile gloves.

All study protocols and materials related to the study were approved by the Université de

Montréal health research ethics board. All participating workers signed an informed consent form and received financial compensation. Following sampling, an industrial hygiene assessment report was sent to the directors of each facility.

3.2.2 Sampling strategy

Sampling was conducted between May and October 2017 on Wednesday and Thursday of the same week to limit the influence of FR exposure from non-occupational settings (e.g., from homes during the weekend) and allowed time to process biomonitoring samples on Friday. Each worker wore a personal active air sampler, a silicone brooch, and a silicone band either on the wrist or the arm, depending on whether the worker wore Kevlar® cut-resistant sleeves (Figure

A3.1 and A3.2). We observed that all workers who wore such sleeves and thus wore a passive sampler as an armband, handled large e-waste materials such as televisions, computers and screens. Workers who wore wristbands mainly dismantled small e-waste (e.g. phones, radios) and performed other tasks (e.g. sorting, supervising and driving forklifts). Five out of 45 workers only agreed to wear active air samplers and silicone brooches. Samplers were worn on Wednesdays for

a full-day work shift with sampling times varying between 6 to 10 hours. The average of sampling time was ~8 hours. Spot urine samples were collected at the end of worker’s shift on Wednesday afternoon (Gravel et al., 2020). Blood samples were collected in the afternoon on Thursday by a registered nurse (Gravel et al., 2020). Workers also completed a questionnaire on Thursday.

Personal silicone passive and active samplers. Prior to sampling, all personal silicone passive samplers (silicone brooches, wristbands and armbands) and personal active air samplers were pre-cleaned according to methods reported in section A3.1 in Appendix 2.

The silicone brooch consisted of a silicone strip (length 9 cm x width 5.5 cm x thickness

0.1 cm; exposed surface area: 49.5 cm2; volume: 4.95 cm3; Specialty Silicone Products, Inc.,

Ballston Spa, NY) stapled on a pre-cleaned aluminium housing that was pinned close to the breathing zone of the worker (Figures A3.1 and A3.2 in Appendix 2). Okeme et al. (2018a) have described the design of the silicone brooch.

A silicone band (length 16 cm x width 3 cm x thickness 0.1 cm; exposed surface area: 48 cm2; volume: 4.8 cm3; Specialty Silicone Products, Inc., Ballston Spa, NY) was worn directly on the wrist (n = 5) or attached to the sleeve of the worker’s protective clothing around the wrist as a wristband (n =23) (Figure A3.1 in Appendix 2). When that worker wore cut resistant sleeves, the silicone band was attached to the sleeve of the worker’s protective clothing just above the elbow as an armband (Figure A3.2 in Appendix 2). A larger pre-cleaned silicone strip (length 18 cm x width 4 cm x thickness 0.1 cm; exposed surface area: 72 cm2; volume: 7.2 cm3, Specialty Silicone

Products, Inc., Ballston Spa, NY) acted as a barrier between clothing and the wrist/armbands to avoid cross-contamination resulting from contact between the wrist/armband and worker’s protective clothing, which was not washed daily.

After retrieval, all silicone brooches, wristbands and armbands were stored on ice in their original 250 or 450 mL amber glass container, then transferred to 40 mL amber glass vials for storage at -20 oC until analysis.

Five (11%) participants wore only silicone brooches (no wristband or armband). Two wristbands and one armband were discarded because the storage jars broke during transport. A total of 45 silicone brooches, 28 silicone wristbands and 9 armbands were collected and analyzed.

Personal active air samples were collected with OSHA Versatile Sampler (OVS) tubes

(Sigma Aldrich, Canada) attached to a worker’s clothes within their breathing zone (Figure A3.1 and Figure A3.2 in Appendix 2) and connected to Gilian GilAir-3 air sampling pumps (Sensidyne

LP, Florida, USA), at a sampling flow rate of 2 L/min. More details are given by Gravel et al.

(2019c).

Urine and plasma. As described by Gravel et al. (2020), spot urine samples for OPE analyses were collected in 500 mL polyethylene bottles (Fisher Scientific no. 03-415-502).

Samples were transported on ice to the Institut de recherche Robert-Sauvé en santé et en sécurité du travail (IRSST) laboratory and then transferred into 50 mL polyethylene centrifuge tubes

(Corning™, Lowell, MA) and frozen at -70°C until analysis at the Centre de toxicology du Québec

(CTQ) of the Institut national de santé publique du Québec (INSPQ).

Blood samples for PBDEs analysis were collected in vacuum sealed blood collection tubes

(BD Vacutainer®, Becton Dickinson, Franklin Lakes, NJ). The tubes were transported and centrifuged within 4h of collection for isolation of the plasma. Plasma was then transferred into 2 mL silane pre-treated chromatography vials (Supelco® Analytical, Pa, USA), then frozen at

-20°C until analysis at the CTQ.

3.2.3 Extraction and analysis

The unwashed silicone samplers were transferred to 40 mL amber vials before extraction with acetonitrile by using extraction method of Okeme et al. (2018a). Full names, CAS numbers, molecular weights and log-transformed octanol-air coefficients (log KOA) of the 37 target compounds are listed in Table A3.1 in Appendix 2. All silicone samplers and blanks were analyzed using gas chromatography mass spectrometry (GC-MS) in electron capture negative ionization (ECNI) mode for PBDEs and novel halogenated flame retardants (NHFRs) or electron impact (EI) mode for OPEs (Agilent Technologies Inc.; Mississauga, Canada). Full details of sample extraction and instrumental analysis are given in sections A3.2, A3.3 and tables A3.2,

A3.3 in Appendix 2.

Urine and plasma samples were extracted and analyzed using the methods described by

Gravel et al. (2020). Concentrations in urine and plasma samples were standardized using urine specific gravity and total blood lipids, respectively (Gravel et al., 2020). Full names and detection frequencies of targeted PBDEs in plasma, OPE metabolites in urine and their known parent compounds are listed in Table A3.4 in Appendix 2. Urinary OPE metabolites and plasma samples were analyzed by ultra-performance liquid chromatography (UPLC Waters Acquity) with a tandem mass spectrometer (MS/MMS Waters Xevo TQ-XS) (Waters; Milford, MA, USA) and

GC-MS (Agilent Technologies Inc.; Mississauga, Canada), respectively.

3.2.4 Quality Assurance and Quality Control (QA/QC)

Field blanks were collected on each sampling day and analyzed with laboratory blanks.

Field blanks were exposed at the sampling sites for one minute, then placed in the pre-cleaned jars

and transported back to the laboratory together with the samples. Prior to extraction, all silicone

13 samplers and blanks were spiked with surrogate standards to assess extraction efficiencies. C6-

13 PBBZ and C6-HBB were used as surrogate standards for novel halogenated flame retardants

(AccuStandard Inc., USA), F-BDE-100, F-BDE-154, F-BDE-208 for PBDEs (AccuStandard Inc.,

13 USA) and d12-TCEP, d15-TDCIPP, C18-TPhP for OPEs (Table A3.3 in Appendix 2; Wellington

Laboratories, Canada). Averages of field blank levels of each matrix were calculated for blank correction according to the criteria described by Saini et al. (2015). Blank levels were low and

13 13 thus no blank correction was necessary. Surrogate recoveries for C6-PBBZ and C6-HBB were

71 ± 10% and 76 ± 11% (mean ± SD) respectively, for F-BDE-100, F-BDE-154, F-BDE-208 were

77 ± 9%, 80 ± 8 % and 70 ± 12% (mean ± SD), respectively, and for d12-TCEP, d15-TDCiPP,

13 C18-TPhP were 100 ± 25%, 117 ± 29 % and 105 ± 20% (mean ± SD). Sample values were not recovery-corrected as the values were between 50 and 150% according to Vykoukalová et al.

(2017) Full details of QA/QC are provided in section A3.4 in Appendix 2.

3.2.5 Estimation and evaluation of silicone brooch sampling rates

A synopsis of the theory of passive air sampling for the silicone brooch is given in section

3 -1 A3.5 in Appendix 2. The sampling rate (푅푠, m day ) of the silicone brooch was derived by using the time specific method (Bohlin et al., 2010b; Pernilla Bohlin et al., 2014). First, for each participant, the mass of each compound (푀푆𝑖푙𝑖푐표푛푒 퐵푟표표푐ℎ, ng) accumulated by the silicone brooch was divided by its corresponding personal active air sampler-derived concentration in bulk air

-3 3 (퐶푃퐴퐴, ng m ) to obtain its equivalent air volume (푉푒푞, m ) (Eq.1). The equivalent air volume was then divided by the silicone brooch exposure time (t , day) to obtain the corresponding sampling rate (Eq.2).

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푀푆𝑖푙𝑖푐표푛푒 퐵푟표표푐ℎ 푉푒푞 = (Eq.1) 퐶푃퐴퐴

V 푅 = eq (Eq.2) 푠 t

We estimated a generic sampling rate (푅푠’) as the average of compound-specific sampling rates of the brooch.

To assess the consistency of the sampling rate of the brooch during the average 8-hour deployment, we estimated the time for the brooch to collect 25% of its equilibrium capacity (i.e. the upper limit of linear uptake phase) (푡25, hour) by using the following equation adapted from

Shoeib and Harner (2002) and (Okeme et al. (2016a):

′ 퐾푆𝑖푙𝑖푐표푛 퐵푟표표푐ℎ−퐴𝑖푟,퐸푥푝 푡25 = − (푉푆𝑖푙𝑖푐표푛푒 퐵푟표표푐ℎ ) 푙푛(0.25) (Eq. 3) 푅푠

3 ′ where 푉푆𝑖푙𝑖푐표푛푒 퐵푟표표푐ℎ (m ) is the volume of a silicone brooch; 퐾푆𝑖푙𝑖푐표푛푒 −퐴𝑖푟, 퐸푥푝 (dimensionless)

3 -1 is the silicone-to-air partition coefficient, and 푅푠 (m day ) is the sampling rate of the silicone

′ brooch for an individual compound. Values of 퐾푆𝑖푙𝑖푐표푛 퐵푟표표푐ℎ−퐴𝑖푟, 퐸푥푝 were taken from Okeme et al. (2016a).

3.2.6 Data Analysis

Data analysis, including descriptive statistics and correlation analysis, was performed using

R version 3.4.2. Concentrations of analytes in all silicone passive samplers were normalized to exposed surface area of each sampler type and sampling time in hours for comparison

(normalizing for deployment time was done to account for different deployment times). Exposed surface area was calculated for the outward facing layer of the brooch, wristband and armband.

For each matrix, only compounds with a detection frequency >60% were used for further analysis. Thus, four compounds including pentabromoethyl benzene (PBEB), ethylhexyl-

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tetrabromobenzoate (EHTBB), decabromodiphenylethane (DBDPE), BDE-71 and BDE-85 with detection frequencies <60% in active air samples were excluded from correlation analyses. Four out of seven OPE metabolites found in urine samples of nine workers who wore armbands had detection frequencies <60%. Therefore, results from armbands were not used included in correlation analysis.

Quantile-quantile plots and the Shapiro-Wilk tests were used to assess the normality of the data; exposure measures from silicone samplers were approximately log-normally distributed.

Normality was marginally improved by log transformation. To avoid assumptions about normality, Spearman’s rank correlation was used to test the relationship between the concentrations of FRs in silicone samplers vs. active air samples and silicone samples vs. paired biomarkers. Spearman’s rank correlation was also used to test the relationship between the concentrations of FRs in silicone brooches vs wristbands and silicone brooches vs. armbands. A correlation was considered statistically significant with p < 0.05. We considered Spearman’s correlation coefficients of 0.00 – 0.19 to be very weak, 0.20 – 0.39 to be weak, 0.40 – 0.59 to be moderate, 0.60 – 0.79 to be strong, and 0.80 – 1.0 to be very strong.

To facilitate graphical presentation, values below limit of detection (non-detects) of individual compounds in each matrix were imputed using NDExpo from ExpoStats (2015). This imputation toolkit uses Bayesian statistics based on the assumption of log-normal distribution of exposures, which allow for the optimized treatment of non-detects.

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3.3 Results and Discussion

3.3.1 Levels of FRs in personal passive samplers

Detection frequencies of FRs in wristbands, armbands and their paired brooches are provided in Table A3.5 in Appendix 2. All three types of silicone samplers accumulated NHFRs,

PBDEs and OPEs, except tri-o-cresyl phosphate (ToCP) and tris(2-ethylhexyl) phosphate (TEHP) which were not detected in either brooch or armband samples, respectively. Detection frequencies for most FRs were higher in wristbands than in brooches and armbands, presumably because the wristbands were closer to contaminated surfaces such as workbenches and equipment being disassembled. Accumulation rates were not significantly influenced by whether the wristband was worn either directly on the wrist or on the cuff of the worker’s protective suit (Table A3.6 in

Appendix 2). Not surprisingly, higher detection frequencies of FRs in brooches were found here compared to studies by Okeme et al. (2018a) and Wang et al. (2019) in office and home environments, respectively. Most PBDEs in silicone brooches had detection frequencies >80%, except for BDE-85 and BDE-138. In contrast to these results where deployments were 6-10 hours, no PBDEs were detected in silicone brooches deployed in an office environment for 24-hours

Okeme et al. (2018a), presumably due to higher air concentrations of FRs in the e-waste environment compared to those in office and home environments.

Levels of 27 FRs with >60% detection frequency in paired brooches, wristbands and armbands are shown in Table 3.1 (n = 28 for brooches co-deployed with wristbands and n = 9 for brooches co-deployed with armbands). In the three types of silicone samplers, the abundance pattern of FRs decreased from PBDEs > OPEs > NHFRs with BDE-209 as the most abundant compound. A similar profile of FRs was found in personal active air samplers reported by Gravel

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Table 3.1: Detection frequencies (DF), geometric mean (GM), median, minimum (Min) and maximum (Max) concentrations (ng dm- 2 h-1) of 27 FRs detected in more than 60% of paired silicone brooches, wristbands and armbands.

Brooches co-deployed with Wristbands Brooches co-deployed with armbands Armbands wristbands (n = 28) (n = 28) (n = 9) (n =9)

Compounds DF GM Median Range DF GM Median Range DF GM Median Range DF GM Median Range Novel halogenated flame retardants (NHFRs) ATE 96 0.1 0.1 0.02 - 0.4 100 0.1 0.1 0.02 - 0.3 100 0.1 0.1 0.1 - 0.1 89 0.04 0.04 0.01 - 0.2 PBBZ 100 0.1 0.1 0.001 - 0.3 100 0.1 0.1 0.01 - 0.7 100 0.1 0.2 0.1 - 0.2 100 0.1 0.1 0.05 - 0.3 PBT 86 0.1 0.1 0.01 - 1.5 100 0.1 0.1 0.003 - 0.7 100 0.3 0.2 0.1 - 0.5 100 0.3 0.3 0.1 - 1.2 PBEB 89 0.1 0.1 0.01 - 0.2 86 0.05 0.1 0.01 - 0.2 100 0.1 0.1 0.1 - 0.3 100 0.1 0.1 0.04 - 0.2 HBB 100 1.1 1.8 0.01 - 14 100 1.7 2.1 0.2 - 13 100 4.0 4.0 2.1 - 6.0 100 4.0 4.2 1.8 - 7.8 EHTBB 100 0.8 0.6 0.1 - 13 96 1.4 1.2 0.05 - 36 100 0.9 0.9 0.4 - 1.6 100 0.7 0.8 0.1 - 2.1 BEHTBP 100 6.8 5.0 1.3 - 421 93 18 12 0.2 - 1,190 100 4.4 4.5 2.9 - 6.2 100 5.9 5.9 1.6 - 15 OBIND 86 9.5 12 0.5 - 45 93 6.7 10 0.3 - 63 100 34 27 19 - 76 100 36 45 6.8 - 113 DBDPE 82 58 77 15 - 180 82 53 67 7.0 - 214 100 121 122 89 - 154 100 193 192 61 - 998 s-DP 100 3.9 4.8 0.3 - 22 100 5.6 5.0 0.7 - 23 100 11 10 8.1 - 18 100 12 14 3.7 - 21 a-DP 100 6.4 7.8 0.3 - 33 100 8.0 8.4 0.8 - 45 100 16 13 11 - 34 100 17 19 5.0 - 32 ∑11 NHFRs 87 109 95 106 192 182 269 281 Polybrominated diphenyl ethers (PBDEs) BDE-47 96 0.7 0.6 0.1 - 5.0 96 1.0 0.9 0.1 - 7.9 100 1.0 1.1 0.8 - 1.8 100 1.3 1.5 0.6 - 1.8 BDE-49 82 0.4 0.4 0.1 - 2.0 96 0.5 0.5 0.1 - 5.7 100 0.5 0.8 0.6 - 1.3 100 0.9 0.9 0.4 - 2.5 BDE-66 89 0.1 0.1 0.01 - 0.4 96 0.1 0.1 0.001 - 0.5 100 0.1 0.2 0.1 - 0.3 100 0.3 0.3 0.1 - 0.5 BDE-71 93 0.1 0.1 0.004 - 1.0 96 0.1 0.2 0.001 - 0.6 100 0.1 0.3 0.2 - 1.6 100 0.2 0.2 0.1 - 0.7 BDE-99 100 1.0 0.9 0.2 - 10 100 1.3 1.5 0.1 - 10 100 1.3 1.4 1.0 - 3.0 100 1.4 1.7 0.3 - 2.6 BDE-154 100 0.2 0.3 0.04 - 1.0 100 0.3 0.4 0.02 - 1.5 100 0.3 0.6 0.2 - 13.1 100 0.6 0.7 0.2 - 2.0 BDE-183 100 3.2 4.4 0.2 - 11 100 4.7 5.5 0.3 - 16 100 4.7 7.1 4.8 - 17.6 100 9.2 9.1 2.7 - 54 BDE-209 100 957 2,500 2.9 - 7,660 100 1,360 2,670 22 - 12,200 1,360 3,550 2,860 - 5,650 100 8,320 5,980 3,220 - 35,600 ∑8 PBDEs 963 2,510 1,370 2,680 1,370 3,560 8,330 5,990 Organophosphate esters (OPEs) TCEP 100 25 23 3.6 - 1,200 96 29 42 2.3 - 132 100 42 46 22 - 63 78 34 36 16 - 63 TCIPP 100 44 46 2.1 - 2,080 96 50 59 8.9 - 288 100 30 27 19 - 56 67 27 36 10 - 59 TDCIPP 100 20 22 3.0 - 61 100 31 38 1.2 - 243 100 40 33 24 - 90 100 51 63 18 - 87 TPhP 100 53 64 2.9 - 1,680 96 48 60 3.5 - 198 100 148 157 85 - 208 78 96 91 55 - 154 EHDPP 100 4.1 3.2 0.6 - 235 96 4.1 4.8 0.2 - 125 100 13 14 3.7 - 101 78 6.9 7.1 1.1 - 73 TBOEP 100 204 198 41 - 3,020 96 182 187 37 - 791 100 105 101 85 - 144 78 102 138 43 - 195 TmCP 100 2.4 2.0 0.2 - 200 93 2.5 3.1 0.1 - 16 100 6.1 5.1 3.6 - 12 78 2.9 3.4 0.8 - 8.7 T2IPPP 71 0.3 0.3 0.1 - 1.4 61 0.2 0.2 0.004 - 9.0 100 0.8 0.9 0.3 - 2.3 67 0.4 0.5 0.03 - 11

∑8 OPEs 353 359 347 394 385 384 320 375 ∑ FRs 1,40 27 2,980 1,810 3,180 1,950 4,130 8,920 6,650 0

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et al. (2019c) and air samples at the workbenches in an Ontario e-waste study conducted in 2017

(Nguyen et al., 2019).

Median concentrations of each FR in wristbands were comparable to levels in paired brooches for most compounds. Among NHFRs and OPEs, the most abundant compound was tris(2-butoxyethyl)phosphate (TBOEP) with median values in wristbands and brooches of 187 and 198 ng dm-2 h-1, respectively. BDE-209 was the most abundant compound found in wristbands and corresponding brooches where it accounted for >80% of ∑27 FR concentrations in both sampler types. Median concentrations of BDE-209 in wristbands and paired brooches were 2,670 and 2,500 ng dm-2 h-1, respectively.

The median concentration of each FR in armbands was up to 2 times higher than those found in corresponding brooches, except for tribromophenyl allyl ether (ATE) for which the concentration in paired brooches exceeded the armband by 4 times. However, ATE only accounted for ~0.002 % of ∑27 FRs concentrations found in both samplers. BDE-209 was also the most abundant compound found in armbands and their paired brooches collected from nine workers, accounting for >85% of ∑27 FRs in both sampler types, with median concentrations of ~ 6,000 and 3,550 ng dm-2 h-1, respectively. Concentrations of BDE-209 in the paired brooches from workers who wore armbands (those handling large e-waste such as televisions and screens) were

~1.5 times higher than those from workers who wore wristbands and who handled smaller e- waste. Similarly, BDE-209 concentrations in armbands were ~2.2 times higher than in wristbands, that we attributed to workers wearing armbands dismantling larger e-waste than those workers handling smaller e-waste who wore wristbands (Abbasi et al., 2016; Stubbings et al., 2019a; Yang et al., 2020b).

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Higher concentrations of BDE-209 found in armbands and brooches of the workers handling televisions and large electronics vs those handling smaller devices is consistent with the use of BDE-209 at high levels especially in television casings (Abbasi et al., 2016; Yang et al.,

2020b). Stubbings et al. (2019) also reported that levels of BDE-209 in e-waste bins holding televisions were ~ 1.3 times greater than in bins holding miscellaneous items in an Ontario e- waste facility. Among NHFRs, the highest concentration found in armbands and paired brooches were of DBDPE with median values of 192 and 122 ng dm-2 h-1, respectively. DBDPE has also been used extensively at high concentrations in television casings (Yang et al., 2020b).

The comparison of FR levels in wristbands and brooches found here and in previous studies is limited by differences in the units reported. Here, we only compared our results with studies reporting in a similar unit (ng dm-2 h-1) or that provided the information of the exposed surface area with sampling time for calculating the air concentration from chemical mass. Levels of FRs in wristbands and brooches here were higher than those in other environments. Total median concentrations of 8 PBDEs in wristbands reported here were 14 times higher than those in wristbands with the same design worn by Bangladeshi e-waste workers (Wang et al., 2020).

This result, of higher apparent exposures among workers in formal compared to informal e-waste sites, was also found with Ontario e-waste workers, which we attributed to greater ventilation in informal, outdoor workshops (Nguyen et al., 2019). Compared to results for brooches worn by participants from the general population for 72 hours (Romanak et al., 2019), concentrations of all FRs, except for BDE-47 and EHTBB, were up to 13,000 times higher. In addition, levels of tris(2-chloroisopropyl)phosphate (TCIPP) in brooches here were ~4.6 times higher than those in brooches worn by office workers (Okeme et al., 2018b). Higher levels of FRs in brooches from this study compared to those in the literature is likely caused by the higher levels of gas- and

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particle-phase FRs and greater movement of e-waste workers compared to office workers and participants at home. Greater physical movement is expected to reduce the thickness of the air- side boundary layer (Shoeib and Harner, 2002), thereby increasing the diffusion rate and accumulation of gas-phase FRs.

3.3.2 Comparison of personal silicone passive samplers with active air samples

Table 3.2 compares concentrations of paired samples of personal silicone passive samplers

(brooches, wristbands and armbands) vs. active air samples, for selected FRs. Among the three types of silicone samplers, the brooch most closely approximated the personal active air samplers.

Stronger and more statistically significant correlations were found between active air samples and brooches, compared to wristbands and armbands. Specifically, 16 out of 23 compounds in brooches showed strong and very strong statistically significant correlations with the personal active air samplers (Spearman’s rho = 0.68 to 0.83, p < 0.05). Results here were consistent with the findings of Wang et al. (2019), who found stronger correlations between active air samplers and brooches compared to active air samplers and wristbands. From this, we conclude that the brooch could be used for assessing inhalation exposure to these FRs and other exposures related to air concentrations such as dermal absorption.

Eight compounds in armbands, mostly OPEs, showed very strong and significant relationship with the personal active air samplers (Spearman’s rho = 0.7 to 0.9, p < 0.05). No strong associations were found between wristbands and personal active air samplers. Only seven compounds, mostly NHFRs, showed moderate correlations between wristbands and personal active air samplers (Spearman’s rho = 0.41 to 0.59, p < 0.05). Similar trends for correlations between brooches vs wristbands and brooches vs. armbands are shown in Table A3.7 in Appendix

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2. Less than 15% of FRs in brooches showed moderate and strong associations with those in paired wristbands and armbands (Spearman’s rho = 0.4 – 0.8). These results suggest that wristbands and armbands capture FRs not only from air but also from other sources, such as direct contact with dust and the contaminated surface of e-wastes.

Table 3.2. Correlations between concentrations (ng m-3 for personal active air samplers and ng dm-2 h-1 for silicone brooches, wristbands and armbands) of FRs with detection frequencies >60% in paired sample matrices as indicated by Spearman’s correlation coefficients (rho). Numbers in bold indicate a statistically significant correlation with p-value < 0.05.

Compounds PAAS vs Brooches PAAS vs Wristbands PAAS vs Armbands Novel halogenated flame retardants (NHFRs) ATE 0.58 0.29 0.67 PBBZ 0.83 0.38 0.80 PBT 0.82 0.54 0.32 HBB 0.87 0.50 0.35 s-DP 0.71 0.59 -0.42 a-DP 0.79 0.20 0.53 BEHTBP 0.58 0.47 0.52 OBIND 0.73 0.15 0.55 Polybrominated diphenyl ethers (PBDEs) BDE-47 0.68 0.02 0.47 BDE-49 0.69 0.37 -0.02 BDE-66 0.74 0.34 0.53 BDE-99 0.70 -0.01 0.80 BDE-154 0.69 -0.10 0.68 BDE-183 0.73 0.14 0.73 BDE-209 0.71 0.42 0.45 Organophosphate esters (OPEs) TCEP 0.23 0.38 0.70 TCIPP 0.76 0.23 0.88 TPhP 0.67 0.41 0.47 EHDPP 0.78 0.22 0.90 TmCP 0.46 -0.04 0.80 TBOEP -0.03 -0.19 0.33 TDClPP 0.56 0.26 0.78 T2IPPP 0.52 0.46 0.77

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3.3.3 Correlation between FRs in silicone samplers and biomonitoring data

We hypothesized that FRs captured by personal passive samplers could be used as an indication of internal burden. Seven PBDE congeners and eight OPE metabolites were detected in plasma and urine, respectively (Table A3.4 in Appendix 2). We only considered BDE-209 since had a detection frequency > 60% in plasma (Table A3.4 in Appendix 2). All OPEs, except for

TBOEP, were considered because of their high detection frequencies in urine. We note that this comparison contains many uncertainties; internal biomarkers such as urinary metabolites and blood levels reflect exposures from all routes (i.e., inhalation, dust ingestion, dermal transfer) in occupational and non-occupational environments, as well as dietary exposure. The comparison of external vs. internal exposure is also complicated by differences in biological half-lives of compounds, as OPEs have short half-lives (from minutes to a day or two) (Hou et al., 2016), and

PBDEs have longer half-lives (from several days to years) (Thuresson et al., 2006). BDE-209 in plasma and OPE urinary metabolites were not associated with the years Gravel et al. (2019a) or months participants worked in the e-waste recycling industry (Figure A3.3, Table A3.8 in

Appendix 2).

We found that BDE-209 in plasma was moderately and significantly correlated with levels in brooches (Spearman’s rho = 0.44, p < 0.05) and wristbands (Spearman’s rho = 0.40, p < 0.05,

Figure 3.1). This is consistent with Gravel et al. (2019b) who found that air levels of BDE-209 significantly predicted BDE-209 levels in plasma. In contrast, Hammel et al. (2018), who studied

30 non-occupational participants, found moderate and significant correlations between wristbands worn for 7 days and paired plasma samples for penta-BDEs including BDE-47, -99, -100, and

153, but not BDE-209 because of the low detection levels in plasma. We speculate that the e- waste workers have been, and continue to be, exposed to elevated levels of BDE-209, which is

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the most abundant FR in e-waste facilities (Gravel et al., 2019c; Muenhor et al., 2010; Nguyen et al., 2019; Rosenberg et al., 2011), with a high detection frequency of 93% in plasma samples

(Table A3.4 in Appendix 2). The long half-life of BDE-209 in blood (15 days) and continual exposure to high levels may thus contribute to the brooch and wristband reflecting internal BDE-

209 exposure.

Figure 3.1: Log-transformed BDE-209 in blood plasma versus (a) log-transformed BDE-209 in brooch (n = 45), (b) log-transformed BDE-209 in wristband (n = 28), and (c) log- transformed BDE-209 in armband (n=9). Rho is Spearman’s rank correlation coefficient and p is the probability values.

The correlations between all OPE metabolite levels in urine vs. brooches and wristbands were weak and not statistically significant (Table 3.3, Figure A3.4 in Appendix 2). Most correlations between active samplers and urinary data for OPEs, except for tris(2-chloroethyl) phosphate (TCEP) and its metabolite bis(2-chloroethyl) carboxymethyl phosphate (BCECMP), were also weak and statistically insignificant Traore et al. (2018). In comparison, Hammel et al.

(2016) reported moderate to strong, statistically significant correlations for tris(1,3-dichloro-2-

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propyl) phosphate (TDCIPP) and TCIPP between levels in wristbands and urinary metabolites among 40 participants who wore wristbands for 5 days and provided 3 spot urine samples which were mixed to form an average sample prior to analysis (Hammel et al., 2016).

Table 3.3. Spearman’s rank correlation coefficients (rho) and p-values (p) for OPEs levels measured in brooches (n = 45) and wristbands (n = 28) with OPE metabolites in their paired specific-gravity-corrected urine samples (n = 45).

Parent compounds Brooches Wristbands Urinary metabolites (n = 45) (n = 28) rho p rho p TCEP BDECMP 0.29 0.05 0.17 0.38

TCIPP BCiPCEP 0.18 0.24 0.15 0.45 BCiPHiPP 0.05 0.74 0.33 0.09 ∑BCiPCEP and BCiPHiPP 0.10 0.53 0.24 0.21

TDCIPP BDCiPP 0.03 0.84 0.34 0.08

TPhP pOH-DPhP 0.05 0.73 0.26 0.19 DPhP 0.07 0.63 0.07 0.73

EHDPP DPhP 0.12 0.43 0.23 0.23

∑TPhP and EHDPP DPhP 0.09 0.54 0.008 0.97

The longer monitoring time of 5 days with several spot urine samples may have better reflected time-integrated exposure, whereas we collected only one spot urine sample at the end of a worker’s shift. Similarly to our results, Craig et al. (2019) reported no association between levels of TCEP, TDCIPP, TCIPP and triphenyl phosphate (TPhP) on wristbands worn on nail salon

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workers’ wrists (n = 10) and wristbands pinned to their lapels (n = 10) (the same location where brooches were worn in this study) and paired metabolite levels in spot urine samples collected during a 9-hour deployment time, a duration comparable to the current study. We speculate that the lack of correlations found between OPEs in the personal passive samplers, active air samplers and spot urine samples was attributable to the single spot urine sample not adequately reflecting

OPE internal burdens that could fluctuate because of the relatively short metabolic half-lives

(Percy et al., 2020), as well as daily variability in OPE exposure experienced by e-waste workers.

3.3.4 Evaluation of sampling rates of silicone brooch

Sampling rates (푅푠) of the brooch are presented in Table A3.9 in Appendix 2 for seven compounds which were detected in 100 % of both brooches and personal active air samplers. The

3 -1 average compound-specific 푅푠, ranged from 2.8 ± 7.2 for TCIPP to 20 ± 15 m day for TDCIPP.

The generic sampling rate (푅푠’) of the brooch for the seven FRs (calculated as the average) was

3 -1 3 -1 -2 9.3 ± 5.4 m day , and the Rs’ was 19 ± 11 m day dm when normalized to the exposed area of brooch. It is important to note that the sampling rate depends on the level of activity of the worker

(i.e., local wind current at the surface of the sampler) (Okeme et al., 2018b; Tromp et al., 2019), dust levels which differ according to the movement of workers when performing different tasks, and the presence of fans nearby to increase the thermal comfort of workers on warm days.

The 푅푠’ in this study was ~ 13 and 22 times higher than that calculated by Okeme et al.,

(2018b) for a stationary silicone sampler in a home environment and by Okeme et al. (2018a) for a personal brooch sampler in an office environment, respectively. The higher 푅푠’ estimated here for the silicone brooch, as compared to those measured in office and home environments, was

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consistent with the dusty e-waste environment and increased air circulation (due to worker movement) around the sampler, as mentioned above.

Table A3.10 in Appendix 2 reports the estimated length of time for seven compounds in the brooch to reach 25% of equilibrium capacity or the upper limit of the linear uptake phase of the brooch for those compounds in the gas phase. The shortest and longest time for brooch to reach 25% its equilibrium was estimated as ~600 days for TDCIPP and 29,200 days for anti-

Dechlorane Plus (a-DP). Hence, the average of 8 hours used for sampling in this study was well within the linear uptake phase for all selected compounds and a constant uptake rate can be expected. In this calculation we did not account for particle deposition to the sampler’s surface area and the exchange of compounds between particles and sampler, which is not expected to reach equilibrium with the sampler, as for gas-phase compounds.

3.3.5 Strengths and Limitations

This study provides a better understanding of the use of silicone wristbands and brooches as personal passive samplers with a relatively short-term deployment in occupational settings.

Silicone brooches, wristbands and armbands worn for an average of 8 hours accumulated detectable amounts of most target FRs in this occupational setting. Among the three types of silicone samplers, the brooch most closely approximated the personal active air samplers since stronger correlations for more FRs were found between active air samples and brooches compared to wristbands and armbands. Hence, we suggest that the brooch could give a reasonable estimate of inhalation exposure for FRs and other exposures related to air concentrations (e.g. dermal absorption). The uptake or sampling rate of the silicone brooch reported here (first for an industrial setting) were well within the linear uptake phase, and as such, the generic sampling rate of the

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brooch (19 ± 11 m3 day-1 dm-2) should be consistent over deployment periods and applicable to industrial settings similar to that studied here.

Our study also assessed the relationship between internal biomonitoring and external exposure measures to better understand the use of personal passive samplers for assessing internal exposure to FRs. Our findings suggest that brooches and wristbands are promising surrogates of internal levels of exposure for an FR such as BDE-209, which is exceedingly abundant in e-waste facilities and hence continuous exposure is presumed, and with a long metabolic half-life where a spot blood sample reflects long-term exposure. The use of these passive samplers for short-lived compounds like OPEs is less clear. Similar to BDE-209, OPE concentrations were also high in the facility and we presume that workers were constantly exposed. However, our test may not have been adequate because we relied on a single spot urine sample for biomarker measurement, as discussed below. It is worth noting that exposure levels measured using personal active air samplers also were not strongly correlated with internal exposure levels, except for BDE-209

(Gravel et al., 2019b; Traore et al., 2018).

Our study had several limitations. Biomonitoring data are influenced by other routes of exposure such as diet and environmental exposures outside of the workplace, for which we did not collect information. As noted above, a single spot urine sample was used, which may not be representative of the exposure captured by the personal passive samplers or active air samplers, especially for quickly metabolized compounds. Active air samplers represent an average, integrated exposure across the sampling period (work shift in this study), whereas spot urine levels are not integrated over the same period and may be influenced by the timing of collection. Future work should test the use of passive samplers against the change in internal exposure (using pre- and post-work shift measures) to better assess how they correlate with exposure over the course

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of a work shift. Furthermore, silicone rubber, as an air sampling medium, more efficiently accumulates SVOCs (e.g., FRs) in the gas than particle phase,33 which could be problematic in dusty environments such as an e-waste recycling facility (Wang et al., 2020). Here, we did not examine particle deposition to the surface of silicone samplers and the exchange of chemicals between the particles and samplers.

Acknowledgments

We thank the managers and workers of the facilities that participated in this study.

Funding was provided by Institut de recherche Robert-Sauvé en santé et en sécurité du travail

(grant no. 2015-0083) and Natural Sciences and Engineering Research Council of Canada

(NSERC RGPIN-2017-06654). Marc-Andre Verner is a recipient of a Research Scholar J1

Award from the Fonds de recherche du Québec – Santé (FRQS). We thank Sarah Bernstein for help preparing the sampling materials.

References

Abbasi, G., Buser, A.M., Soehl, A., Murray, M.W., Diamond, M.L., 2015. Stocks and flows of PBDEs in products from use to waste in the U.S. and canada from 1970 to 2020. Environ. Sci. Technol. 49, 1521–1528. https://doi.org/10.1021/es504007v Abbasi, G., Saini, A., Goosey, E., Diamond, M.L., 2016. Product screening for sources of halogenated flame retardants in Canadian house and office dust. Sci. Total Environ. 545– 546, 299–307. https://doi.org/10.1016/j.scitotenv.2015.12.028 Abdallah, M.A.-E., Pawar, G., Harrad, S., 2015a. Evaluation of 3D-human skin equivalents for assessment of human dermal absorption of some brominated flame retardants. Environ. Int. 84, 64–70. https://doi.org/10.1016/j.envint.2015.07.015 Abdallah, M.A.-E., Pawar, G., Harrad, S., 2015b. Effect of Bromine Substitution on Human Dermal Absorption of Polybrominated Diphenyl Ethers. Environ. Sci. Technol. 49, 10976– 10983. https://doi.org/10.1021/acs.est.5b03904 Abou-Elwafa Abdallah, M., Pawar, G., Harrad, S., 2016. Human dermal absorption of chlorinated organophosphate flame retardants; implications for human exposure. Toxicol.

115

Appl. Pharmacol. 291, 28–37. https://doi.org/10.1016/j.taap.2015.12.004 ACGIH, 2018. TLVs ® and BEIs ® : Threshold limit values for chemical substances and physical agents biological exposure indices. American Conference of Governmental Industrial Hygienists, Cincinnati, OH, OH. ACGIH, 2001. Documentation of threshold limit values for substances in work environment. American Conference of Governmental Industrial Hygienists, Cincinnati, OH, OH. Ait, Y., Araki, A., Kawai, T., Tsuboi, T., Saito, I., Yoshioka, E., Kanazawa, A., 2014. Science of the Total Environment Associations of phthalate concentrations in fl oor dust and multi- surface dust with the interior materials in Japanese dwellings. Sci. Total Environ. 468–469, 147–157. https://doi.org/10.1016/j.scitotenv.2013.07.107 Akormedi, M., Asampong, E., Fobil, J.N., 2013. Working conditions and environmental exposures among electronic waste workers in Ghana. Int. J. Occup. Environ. Health 19, 278–286. https://doi.org/10.1179/2049396713Y.0000000034 Allen, J.G., McClean, M.D., Stapleton, H.M., Nelson, J.W., Webster, T.F., 2007. Personal Exposure to Polybrominated Diphenyl Ethers (PBDEs) in Residential Indoor Air. Environ. Sci. Technol. 41, 4574–4579. https://doi.org/10.1021/es0703170 Allen, J.O., Dookeran, N.M., Smith, K.A., Sarofim, A.F., Taghizadeh, K., Lafleur, A.L., 1996. Measurement of polycyclic aromatic hydrocarbons associated with size-segregated atmospheric aerosols in Massachusetts. Environ. Sci. Technol. 30, 1023–1031. https://doi.org/10.1021/es950517o Andersen, C., Krais, A.M., Eriksson, A.C., Jakobsson, J., Löndahl, J., Nielsen, J., Lindh, C.H., Pagels, J., Gudmundsson, A., Wierzbicka, A., 2018. Inhalation and Dermal Uptake of Particle and Gas-Phase Phthalates—A Human Exposure Study. Environ. Sci. Technol. 52, 12792–12800. https://doi.org/10.1021/acs.est.8b03761 Asante, K.A., Agusa, T., Biney, C.A., Agyekum, W.A., Bello, M., Otsuka, M., Itai, T., Takahashi, S., Tanabe, S., 2012. Multi-trace element levels and arsenic speciation in urine of e-waste recycling workers from Agbogbloshie, Accra in Ghana. Sci. Total Environ. 424, 63–73. https://doi.org/10.1016/j.scitotenv.2012.02.072 ATSDR, 2012. Toxicological Profile for Phosphate Ester Flame Retardants. ATSDR, 2005. Public Health Assessment Guidance Manual (2005 Update). Atlanta, Georgia. ATSDR, 2004. Toxicological profile for polybrominated biphenyl and polybrominated diphenyl ethers 1–599. Awasthi, A.K., Wang, M., Wang, Z., Awasthi, M.K., Li, J., 2018. E-waste management in India: A mini-review. Waste Manag. Res. 36, 408–414. https://doi.org/10.1177/0734242X18767038 Bakhiyi, B., Gravel, S., Ceballos, D., Flynn, M.A., Zayed, J., 2018. Has the question of e-waste opened a Pandora’s box? An overview of unpredictable issues and challenges. Environ. Int. 110, 173–192. https://doi.org/https://doi.org/10.1016/j.envint.2017.10.021 Balde, C.P., Forti, V., Gray, V., Kuehr, R., Stegmann, P., 2017. The global e-waste monitor 2017, United Nations University. https://doi.org/10.1016/j.proci.2014.05.148 Baldé, C.P., Wang, F., Kuehr, R., Huisman, J., 2015. The Global E-waste Monitor 2014: Quantitites, flows and resources. Bonn, Germany. https://doi.org/ISBN 978-92-808-4556-3 Bartkow, M.E., Booij, K., Kennedy, K.E., Müller, J.F., Hawker, D.W., 2005. Passive air sampling theory for semivolatile organic compounds. Chemosphere 60, 170–176. https://doi.org/10.1016/j.chemosphere.2004.12.033 Basel Convention, 2011. Electrical and electronic equipment when becoming waste (e-waste)

116

such as personal computers, printers, televisions, mobile phones, refrigerators and air- conditioning units is one of the fastest growing waste streams in the world today. [WWW Document]. URL http://www.basel.int/Implementation/Ewaste/Overview/tabid/4063/Default.aspx (accessed 3.8.20). Beaucham, C.C., Ceballos, D., Page, E.H., Mueller, C., Calafat, A.M., Sjodin, A., Ospina, M., Guardia, M. La, Glassford, E., 2018. Evaluation of Exposure to Metals , Flame Retardants , and Nanomaterials at an Electronics Recycling Company 1–80. Behl, M., Hsieh, J.H., Shafer, T.J., Mundy, W.R., Rice, J.R., Boyd, W.A., Freedman, J.H., Hunter, E.S., Jarema, K.A., Padilla, S., Tice, R.R., 2015. Use of alternative assays to identify and prioritize organophosphorus flame retardants for potential developmental and neurotoxicity. Neurotoxicol. Teratol. 52, 181–193. https://doi.org/10.1016/j.ntt.2015.09.003 Behl, M., Rice, J.R., Smith, M. V., Co, C.A., Bridge, M.F., Hsieh, J.-H., Freedman, J.H., Boyd, W.A., 2016. Editor’s Highlight: Comparative Toxicity of Organophosphate Flame Retardants and Polybrominated Diphenyl Ethers to Caenorhabditis elegans. Toxicol. Sci. 154, 241–252. https://doi.org/10.1093/toxsci/kfw162 Bergh, C., Torgrip, R., Emenius, G., Östman, C., 2011. Organophosphate and phthalate esters in air and settled dust - a multi-location indoor study. Indoor Air 21, 67–76. https://doi.org/10.1111/j.1600-0668.2010.00684.x Betts, K.S., 2002. Rapidly rising PBDE levels in North America. Environ. Sci. Technol. 36, 50A-52A. https://doi.org/10.1021/es022197w Bi, C., Liang, Y., Xu, Y., 2015. Fate and Transport of Phthalates in Indoor Environments and the Influence of Temperature: A Case Study in a Test House. Environ. Sci. Technol. 49, 9674–9681. https://doi.org/10.1021/acs.est.5b02787 Bidleman, T.F., 1988. Atmospheric processes. Environ. Sci. Technol. 22, 361–367. https://doi.org/10.1021/es00169a002 Blum, A., Behl, M., Birnbaum, L.S., Diamond, M.L., Phillips, A., Singla, V., Sipes, N.S., Stapleton, H.M., Venier, M., 2019. Organophosphate Ester Flame Retardants: Are They a Regrettable Substitution for Polybrominated Diphenyl Ethers? Environ. Sci. Technol. Lett. 6, 638–649. https://doi.org/10.1021/acs.estlett.9b00582 Bohlin, P., Audy, O., Škrdlíková, L., Kukučka, P., Přibylová, P., Prokeš, R., Vojta, Š., Klánová, J., 2014. Outdoor passive air monitoring of semi volatile organic compounds (SVOCs): a critical evaluation of performance and limitations of polyurethane foam (PUF) disks. Environ. Sci. Process. Impacts 16, 433–444. https://doi.org/10.1039/C3EM00644A Bohlin, Pernilla, Audy, O., Škrdlíková, L., Kukučka, P., Vojta, Š., Přibylová, P., Prokeš, R., Čupr, P., Klánová, J., 2014. Evaluation and guidelines for using polyurethane foam (PUF) passive air samplers in double-dome chambers to assess semi-volatile organic compounds (SVOCs) in non-industrial indoor environments. Environ. Sci. Process. Impacts 16, 2617– 2626. https://doi.org/10.1039/C4EM00305E Bohlin, P., Jones, K.C., Levin, J.-O., Lindahl, R., Strandberg, B., 2010a. Field evaluation of a passive personal air sampler for screening of PAH exposure in workplaces. J. Environ. Monit. 12, 1437. https://doi.org/10.1039/c0em00018c Bohlin, P., Jones, K.C., Strandberg, B., 2010b. Field evaluation of polyurethane foam passive air samplers to assess airborne PAHs in occupational environments. Environ. Sci. Technol. 44, 749–754. https://doi.org/10.1021/es902318g Bohlin, P., Jones, K.C., Strandberg, B., 2007. Occupational and indoor air exposure to persistent

117

organic pollutants: A review of passive sampling techniques and needs. J. Environ. Monit. 9, 501. https://doi.org/10.1039/b700627f Bornehag, C.G., Nanberg, E., 2010. Phthalate exposure and asthma in children 33, 333–345. https://doi.org/10.1111/j.1365-2605.2009.01023.x Braun, J.M., Kalkbrenner, A.E., Just, A.C., Yolton, K., Calafat, A.M., Sjödin, A., Hauser, R., Webster, G.M., Chen, A., Lanphear, B.P., 2014. Gestational Exposure to Endocrine- Disrupting Chemicals and Reciprocal Social, Repetitive, and Stereotypic Behaviors in 4- and 5-Year-Old Children: The HOME Study. Environ. Health Perspect. 122, 513–520. https://doi.org/10.1289/ehp.1307261 Breul, S., Van Landuyt, K.L., Reichl, F.X., Högg, C., Hoet, P., Godderis, L., Van Meerbeek, B., Cokic, S.M., 2020. Filtration efficiency of surgical and FFP3 masks against composite dust. Eur. J. Oral Sci. 128, 233–240. https://doi.org/10.1111/eos.12697 Brown, J., Gordon, T., Price, O., Asgharian, B., 2013. Thoracic and respirable particle deinitions for human health risk assessment. Part. Fibre Toxicol. 10, 1–12. Cahill, T.M., Groskova, D., Charles, M.J., Sanborn, J.R., Denison, M.S., Baker, L., 2007. Atmospheric concentrations of polybrominated diphenyl ethers at near-source sites. Environ. Sci. Technol. 41, 6370–6377. https://doi.org/10.1021/es070844j Callesen, M., Bekö, G., Weschler, C.J., Langer, S., Brive, L., Clausen, G., Toftum, J., Sigsgaard, T., Høst, A., Kold, T., 2014. International Journal of Hygiene and Phthalate metabolites in urine and asthma , allergic rhinoconjunctivitis and atopic dermatitis in preschool children. Int. J. Hyg. Environ. Health 217, 645–652. https://doi.org/10.1016/j.ijheh.2013.12.001 Cao, Z., Xu, F., Covaci, A., Wu, M., Wang, H., Yu, G., Wang, B., Deng, S., Huang, J., Wang, X., 2014. Distribution patterns of brominated, chlorinated, and phosphorus flame retardants with particle size in indoor and outdoor dust and implications for human exposure. Environ. Sci. Technol. 48, 8839–8846. https://doi.org/10.1021/es501224b Carignan, C.C., Mínguez-Alarcón, L., Butt, C.M., Williams, P.L., Meeker, J.D., Stapleton, H.M., Toth, T.L., Ford, J.B., Hauser, R., 2017. Urinary Concentrations of Organophosphate Flame Retardant Metabolites and Pregnancy Outcomes among Women Undergoing in Vitro Fertilization. Environ. Health Perspect. 125, 087018. https://doi.org/10.1289/EHP1021 Carignan, C.C., Mínguez-Alarcón, L., Williams, P.L., Meeker, J.D., Stapleton, H.M., Butt, C.M., Toth, T.L., Ford, J.B., Hauser, R., 2018. Paternal urinary concentrations of organophosphate flame retardant metabolites, fertility measures, and pregnancy outcomes among couples undergoing in vitro fertilization. Environ. Int. 111, 232–238. https://doi.org/10.1016/j.envint.2017.12.005 Castorina, R., Bradman, A., Stapleton, H.M., Butt, C., Avery, D., Harley, K.G., Gunier, R.B., Holland, N., Eskenazi, B., 2017. Current-use flame retardants: Maternal exposure and neurodevelopment in children of the CHAMACOS cohort. Chemosphere 189, 574–580. https://doi.org/10.1016/j.chemosphere.2017.09.037 Ceballos, D.M., Côté, D., Bakhiyi, B., Flynn, M.A., Zayed, J., Gravel, S., Herrick, R.F., Labrèche, F., 2020. Overlapping vulnerabilities in workers of the electronics recycling industry formal sector: A commentary. Am. J. Ind. Med. 63, 955–962. https://doi.org/10.1002/ajim.23173 Ceballos, D.M., Dong, Z., 2016. The formal electronic recycling industry: Challenges and opportunities in occupational and environmental health research. Environ. Int. 95, 157–166. https://doi.org/10.1016/j.envint.2016.07.010

118

CEPA, 1999. Canadian Environmental Protection Act. Cequier, E., Sakhi, A.K., Marcé, R.M., Becher, G., Thomsen, C., 2015. Human exposure pathways to organophosphate triesters — A biomonitoring study of mother–child pairs. Environ. Int. 75, 159–165. https://doi.org/10.1016/j.envint.2014.11.009 Chan, J.K.Y., Wong, M.H., 2013. A review of environmental fate, body burdens, and human health risk assessment of PCDD/Fs at two typical electronic waste recycling sites in China. Sci. Total Environ. 463–464, 1111–1123. https://doi.org/10.1016/j.scitotenv.2012.07.098 Cherrie, J.W., 2003. CommentaryThe Beginning of the Science Underpinning Occupational Hygiene. Ann. Occup. Hyg. 47, 179–185. https://doi.org/10.1093/annhyg/meg030 City of Toronto, 2019. Search for an Establishment Monitored by BodySafe [WWW Document]. URL https://www.toronto.ca/community-people/health-wellness-care/health- programs-advice/bodysafe/search-for-an-establishment-space-holder-for-map/ (accessed 7.18.19). Consumer Product Safety Commission, 2008. Consumer Product Safety Improvement Act of 2008. Craig, J.A., Ceballos, D.M., Fruh, V., Petropoulos, Z.E., Allen, J.G., Calafat, A.M., Ospina, M., Stapleton, H.M., Hammel, S., Gray, R., Webster, T.F., 2019. Exposure of Nail Salon Workers to Phthalates, Di(2-ethylhexyl) Terephthalate, and Organophosphate Esters: A Pilot Study. Environ. Sci. Technol. 53, 14630–14637. https://doi.org/10.1021/acs.est.9b02474 de Winter-Sorkina, R., Bakker, M.., Wolterink, G., Zielmaker, M.J., 2006. Brominated flame retardants: occurrence, dietary intake and risk assessment [WWW Document]. URL https://www.rivm.nl/bibliotheek/rapporten/320100002.pdf (accessed 6.7.18). Delgado-Saborit, J.M., Stark, C., Harrison, R.M., 2014. Use of a versatile high efficiency multiparallel denuder for the sampling of PAHs in ambient air: Gas and particle phase concentrations, particle size distribution and artifact formation. Environ. Sci. Technol. 48, 499–507. https://doi.org/10.1021/es402937d Dixon, H.M., Scott, R.P., Holmes, D., Calero, L., Kincl, L.D., Waters, K.M., Camann, D.E., Calafat, A.M., Herbstman, J.B., Anderson, K.A., 2018. Silicone wristbands compared with traditional polycyclic aromatic hydrocarbon exposure assessment methods. Anal. Bioanal. Chem. 410, 3059–3071. https://doi.org/10.1007/s00216-018-0992-z Eakin, J.M., Champoux, D., MacEachen, E., 2017. Health and safety in small workplaces: refocusing upstream. Can. J. Public Health 101 Suppl, S29-33. EC, 2018. Waste Electrical & Electronic Equipment (WEEE) [WWW Document]. Eur. Comm. https://doi.org/10.1016/j.geb.2005.03.002 Ekelund, M., Azhdar, B., Gedde, U.W., 2010. Evaporative loss kinetics of di(2- ethylhexyl)phthalate (DEHP) from pristine DEHP and plasticized PVC. Polym. Degrad. Stab. 95, 1789–1793. https://doi.org/10.1016/j.polymdegradstab.2010.05.007 Eriksson, P., Jakobsson, E., Fredriksson, A., 2001. Brominated flame retardants: a novel class of developmental toxicants in our environment? Environ. Health Perspect. 109, 903–908. https://doi.org/10.1289/ehp.01109903 Estill, C.F., Slone, J., Mayer, A., Chen, I.-C., La Guardia, M.J., 2020. Worker exposure to flame retardants in manufacturing, construction and service industries. Environ. Int. 135, 105349. https://doi.org/10.1016/j.envint.2019.105349 European Commission, 2014. COMMUNICATION FROM THE COMMISSION on the

119

finalisation of the restriction process on the four phthalates (DEHP, DBP, BBP and DIBP) under Regulation (EC) No 1907/2006 of the European Parliament and of the Council concerning Registration, Evaluation, Authori. Off. J. Eur. Union 73, 1–4. ExpoStats, 2015. NDExpo – Treatment of non-detects in industrial hygiene samples [WWW Document]. URL http://www.expostats.ca/site/app-local/NDExpo/ (accessed 2.20.20). Factor-Litvak, P., Insel, B., Calafat, A.M., Liu, X., Perera, F., Rauh, V.A., Whyatt, R.M., 2014. Persistent Associations between Maternal Prenatal Exposure to Phthalates on Child IQ at Age 7 Years. PLoS One 9, e114003. https://doi.org/10.1371/journal.pone.0114003 Federman, M.N., Harrington, D.E., Krynski, K.J., 2006. Vietnamese Manicurists: Are Immigrants Displacing Natives or Finding New Nails to Polish? ILR Rev. 59, 302–318. https://doi.org/10.1177/001979390605900207 Fisher, M., Arbuckle, T.E., MacPherson, S., Braun, J.M., Feeley, M., Gaudreau, É., 2019. Phthalate and BPA Exposure in Women and Newborns through Personal Care Product Use and Food Packaging. Environ. Sci. Technol. 53, 10813–10826. https://doi.org/10.1021/acs.est.9b02372 Flanagan, M.E., Seixas, N., Majar, M., Camp, J., Morgan, M., 2003. Silica Dust Exposures During Selected Construction Activities. AIHA J. 64, 319–328. https://doi.org/10.1080/15428110308984823 Fortia, V., Balde, C.P., Kuehr, R., Bel, G., 2020. The Global E-waste Monitor 2020: Quantitites, flows and circular economy potential [WWW Document]. URL https://collections.unu.edu/view/UNU:7737 (accessed 10.13.20). Fraser, A.J., Webster, T.F., McClean, M.D., 2009. Diet Contributes Significantly to the Body Burden of PBDEs in the General U.S. Population. Environ. Health Perspect. 117, 1520– 1525. https://doi.org/10.1289/ehp.0900817 Frazzoli, C., Orisakwe, O.E., Dragone, R., Mantovani, A., 2010. Diagnostic health risk assessment of electronic waste on the general population in developing countries’ scenarios. Environ. Impact Assess. Rev. 30, 388–399. https://doi.org/10.1016/j.eiar.2009.12.004 Frederiksen, M., Stapleton, H.M., Vorkamp, K., Webster, T.F., Jensen, N.M., Sørensen, J.A., Nielsen, F., Knudsen, L.E., Sørensen, L.S., Clausen, P.A., Nielsen, J.B., 2018. Dermal uptake and percutaneous penetration of organophosphate esters in a human skin ex vivo model. Chemosphere 197, 185–192. https://doi.org/10.1016/j.chemosphere.2018.01.032 Fromme, H., Becher, G., Hilger, B., Völkel, W., 2016. Brominated flame retardants - Exposure and risk assessment for the general population. Int. J. Hyg. Environ. Health 219, 1–23. https://doi.org/10.1016/j.ijheh.2015.08.004 Gaspar, F.W., Castorina, R., Maddalena, R.L., Nishioka, M.G., McKone, T.E., Bradman, A., 2014. Phthalate exposure and risk assessment in California child care facilities. Environ. Sci. Technol. 48, 7593–7601. https://doi.org/10.1021/es501189t Gevao, B., Al-Bahloul, M., Al-Ghadban, A.N., Ali, L., Al-Omair, A., Helaleh, M., Al-Matrouk, K., Zafar, J., 2006. Polybrominated diphenyl ethers in indoor air in Kuwait: Implications for human exposure. Atmos. Environ. 40, 1419–1426. https://doi.org/10.1016/j.atmosenv.2005.10.053 Gioia, R., Steinnes, E., Thomas, G.O., Mejier, S.N., Jones, K.C., 2006. Persistent organic pollutants in European background air: derivation of temporal and latitudinal trends. J. Environ. Monit. 8, 700. https://doi.org/10.1039/b604821h Giovanoulis, G., Bui, T., Xu, F., Papadopoulou, E., Padilla-Sanchez, J.A., Covaci, A., Haug,

120

L.S., Cousins, A.P., Magnér, J., Cousins, I.T., de Wit, C.A., 2018. Multi-pathway human exposure assessment of phthalate esters and DINCH. Environ. Int. 112, 115–126. https://doi.org/10.1016/j.envint.2017.12.016 Glazer, L., Hawkey, A.B., Wells, C.N., Drastal, M., Odamah, K.-A., Behl, M., Levin, E.D., 2018. Developmental Exposure to Low Concentrations of Organophosphate Flame Retardants Causes Life-Long Behavioral Alterations in Zebrafish. Toxicol. Sci. 165, 487– 498. https://doi.org/10.1093/toxsci/kfy173 Godwin, A.D., 2017. Plasticizers, in: Applied Plastics Engineering Handbook. Elsevier, pp. 533–553. Godwin, A.D., 2010. Uses of Phthalates and Other Plasticizers [WWW Document]. URL https://www.cpsc.gov/s3fs-public/godwin.pdf (accessed 10.21.20). Gong, M., Weschler, C.J., Zhang, Y., 2016. Impact of Clothing on Dermal Exposure to Phthalates: Observations and Insights from Sampling Both Skin and Clothing. Environ. Sci. Technol. 50, 4350–4357. https://doi.org/10.1021/acs.est.6b00113 Goodyer, C.G., Poon, S., Aleksa, K., Hou, L., Atehortua, V., Carnevale, A., Jednak, R., Emil, S., Bagli, D., Dave, S., Hales, B.F., Chevrier, J., 2017. A case-control study of maternal polybrominated diphenyl ether (PBDE) exposure and cryptorchidism in Canadian populations. Environ. Health Perspect. 125, 1–9. https://doi.org/10.1289/EHP522 Gouin, T., Harner, T., Blanchard, P., Mackay, D., 2005. Passive and Active Air Samplers as Complementary Methods for Investigating Persistent Organic Pollutants in the Great Lakes Basin. Environ. Sci. Technol. 39, 9115–9122. https://doi.org/10.1021/es051397f Goverment of Canada, 2017. Phthalates Regulations Règlement sur les phtalates 21–23. Government of Canada, 2019. Cosmetic Ingredient Hotlist [WWW Document]. URL https://www.canada.ca/en/health-canada/services/consumer-product- safety/cosmetics/cosmetic-ingredient-hotlist-prohibited-restricted- ingredients/hotlist.html#tbl1 (accessed 5.4.20). Government of Canada, 2016. Toxic substances list: PBDEs [WWW Document]. Government of Canada, 2012. Regulations Amending the Prohibition of Certain Toxic Substances Regulations, 2012 [WWW Document]. Canada Gaz. Part II. URL http://www.gazette.gc.ca/rp-pr/p2/2016/2016-10-05/pdf/g2-15020.pdf (accessed 2.18.21). Government of Ontario, 2018. Waste management [WWW Document]. URL https://www.ontario.ca/page/waste-management (accessed 12.9.18). Graham, P.R., 1973. Phthalate ester plasticizers—why and how they are used. Environ. Health Perspect. 3, 3–12. https://doi.org/10.1289/ehp.73033 Grant, K., Goldizen, F.C., Sly, P.D., Brune, M.-N., Neira, M., van den Berg, M., Norman, R.E., 2013. Health consequences of exposure to e-waste: a systematic review. Lancet Glob. Heal. 1, e350–e361. https://doi.org/10.1016/S2214-109X(13)70101-3 Gravel, S., Bakhiyi, B., Lavoué, J., Verner, M.-A., Zayed, J., Labreche, F., 2019a. Electronic waste recycling exposure and hormone levels in workers., in: 27th EPICOH International Symposium on Epidemiology in Occupational Health. Wellington, NewZealand. Gravel, S., Diamond, M.L., Jantunen, L.M., Verner, M.-A., Zayed, J., Labrèche, F., 2019b. Is airborne concentration of BDE209 associated with serum concentration in recycling workers?, in: 9th International Symposium on Flame Retardants BFR 2019. Montreal, Canada. Gravel, S., Lavoué, J., Bakhiyi, B., Diamond, M.L., Jantunen, L.M., Lavoie, J., Roberge, B., Verner, M.-A., Zayed, J., Labrèche, F., 2019c. Halogenated flame retardants and

121

organophosphate esters in the air of electronic waste recycling facilities: Evidence of high concentrations and multiple exposures. Environ. Int. 128, 244–253. https://doi.org/10.1016/j.envint.2019.04.027 Gravel, S., Lavoué, J., Bakhiyi, B., Lavoie, J., Roberge, B., Patry, L., Bouchard, M.F., Verner, M., Zayed, J., Labrèche, F., 2020. Multi-exposures to suspected endocrine disruptors in electronic waste recycling workers: Associations with thyroid and reproductive hormones. Int. J. Hyg. Environ. Health 225, 113445. https://doi.org/10.1016/j.ijheh.2019.113445 Guo, J., Lin, K., Deng, J., Fu, X., Xu, Z., 2015. Polybrominated diphenyl ethers in indoor air during waste TV recycling process. J. Hazard. Mater. 283, 439–446. https://doi.org/10.1016/j.jhazmat.2014.09.044 Guo, Y., Kannan, K., 2013. A survey of phthalates and parabens in personal care products from the United States and its implications for human exposure. Environ. Sci. Technol. 47, 14442–14449. https://doi.org/10.1021/es4042034 Guo, Y., Kannan, K., 2011. Comparative Assessment of Human Exposure to Phthalate Esters from House Dust in China and the United States. Environ. Sci. Technol. 45, 3788–3794. https://doi.org/10.1021/es2002106 Hammel, S., Hoffman, K., Webster, T.F., Anderson, K.A., Stapleton, H.M., 2016. Measuring Personal Exposure to Organophosphate Flame Retardants using Silicone Wristbands and Hand Wipes. Environ. Sci. Technol. acs.est.6b00030. https://doi.org/10.1021/acs.est.6b00030 Hammel, S.C., Phillips, A.L., Hoffman, K., Stapleton, H.M., 2018. Evaluating the Use of Silicone Wristbands To Measure Personal Exposure to Brominated Flame Retardants. Environ. Sci. Technol. 52, acs.est.8b03755. https://doi.org/10.1021/acs.est.8b03755 Harley, K.G., Marks, A.R., Chevrier, J., Bradman, A., Sjödin, A., Eskenazi, B., 2010. PBDE Concentrations in Women’s Serum and Fecundability. Environ. Health Perspect. 118, 699– 704. https://doi.org/10.1289/ehp.0901450 Harner, T., Bartkow, M., Holoubek, I., Klanova, J., Wania, F., Gioia, R., Moeckel, C., Sweetman, A.J., Jones, K.C., 2006. Passive air sampling for persistent organic pollutants: Introductory remarks to the special issue. Environ. Pollut. 144, 361–364. https://doi.org/10.1016/j.envpol.2005.12.044 Hartmann, P.C., Burgi, D., Giger, W., 2004. Organophosphate flame retardants and plasticizers in indoor air. Chemosphere 57, 781–787. https://doi.org/10.1016/j.chemosphere.2004.08.051 Hays, S.M., Kirman, C.R., 2017. Risk assessment and Biomonitoring Equivalent for 2- ethylhexyl-2,3,4,5 tetrabromobenzoate (TBB) and tetrabromobenzoic acid (TBBA). Regul. Toxicol. Pharmacol. 89, 186–192. https://doi.org/10.1016/j.yrtph.2017.07.022 Hazrati, S., Harrad, S., 2006. Causes of Variability in Concentrations of Polychlorinated Biphenyls and Polybrominated Diphenyl Ethers in Indoor air. Environ. Sci. Technol. 40, 7584–7589. https://doi.org/10.1021/es0617082 Heacock, M., Kelly, C.B., Asante, K.A., Birnbaum, L.S., Bergman, Å.L., Bruné, M.-N., Buka, I., Carpenter, D.O., Chen, A., Huo, X., Kamel, M., Landrigan, P.J., Magalini, F., Diaz- Barriga, F., Neira, M., Omar, M., Pascale, A., Ruchirawat, M., Sly, L., Sly, P.D., Van den Berg, M., Suk, W.A., 2015. E-Waste and Harm to Vulnerable Populations: A Growing Global Problem. Environ. Health Perspect. 124, 550–555. https://doi.org/10.1289/ehp.1509699 Heudorf, U., Mersch-Sundermann, V., Angerer, J., 2007. Phthalates: Toxicology and exposure.

122

Int. J. Hyg. Environ. Health 210, 623–634. https://doi.org/10.1016/j.ijheh.2007.07.011 Hill, K.L., Hamers, T., Kamstra, J.H., Willmore, W.G., Letcher, R.J., 2018. Organophosphate triesters and selected metabolites enhance binding of thyroxine to human transthyretin in vitro. Toxicol. Lett. 285, 87–93. https://doi.org/10.1016/j.toxlet.2017.12.030 Hites, R.A., 2004. Polybrominated Diphenyl Ethers in the Environment and in People: A Meta- Analysis of Concentrations. Environ. Sci. Technol. 38, 945–956. https://doi.org/10.1021/es035082g Hoffman, K., Butt, C.M., Webster, T.F., Preston, E. V., Hammel, S.C., Makey, C., Lorenzo, A.M., Cooper, E.M., Carignan, C., Meeker, J.D., Hauser, R., Soubry, A., Murphy, S.K., Price, T.M., Hoyo, C., Mendelsohn, E., Congleton, J., Daniels, J.L., Stapleton, H.M., 2017a. Temporal Trends in Exposure to Organophosphate Flame Retardants in the United States. Environ. Sci. Technol. Lett. 4, 112–118. https://doi.org/10.1021/acs.estlett.6b00475 Hoffman, K., Lorenzo, A., Butt, C.M., Hammel, S.C., Henderson, B.B., Roman, S.A., Scheri, R.P., Stapleton, H.M., Sosa, J.A., 2017b. Exposure to flame retardant chemicals and occurrence and severity of papillary thyroid cancer: A case-control study. Environ. Int. 107, 235–242. https://doi.org/10.1016/j.envint.2017.06.021 Holmes, A.K., Koller, K.R., Kieszak, S.M., Sjodin, A., Calafat, A.M., Sacco, F.D., Varner, D.W., Lanier, A.P., Rubin, C.H., 2014. Case–control study of breast cancer and exposure to synthetic environmental chemicals among Alaska Native women. Int. J. Circumpolar Health 73, 25760. https://doi.org/10.3402/ijch.v73.25760 Hou, R., Xu, Y., Wang, Z., 2016. Review of OPFRs in animals and humans: Absorption, bioaccumulation, metabolism, and internal exposure research. Chemosphere 153, 78–90. https://doi.org/10.1016/j.chemosphere.2016.03.003 Hubinger, J.C., Havery, D.C., 2006. Analysis of consumer cosmetic products for phthalate esters. J. Cosmet. Sci. 57, 127–37. Hutter, H.-P., Haluza, D., Piegler, K., Hohenblum, P., Fröhlich, M., Scharf, S., Uhl, M., Damberger, B., Tappler, P., Kundi, M., Wallner, P., Moshammer, H., 2013. Semivolatile compounds in schools and their influence on cognitive performance of children. Int. J. Occup. Med. Environ. Health 26, 628–635. https://doi.org/10.2478/s13382-013-0125-z IARC Working Group on the Evaluation of Carcinogenic Risks to Humans, 2013. Some chemicals present in industrial and consumer products, food and drinking-water. IARC Monogr. Eval. Carcinog. Risks Hum. 101, 9–549. Igharo, O.G., Anetor, J.I., Osibanjo, O., Osadolor, H.B., Odazie, E.C., Uche, Z.C., 2018. Endocrine disrupting metals lead to alteration in the gonadal hormone levels in Nigerian e- waste workers. Universa Med. 37, 65. https://doi.org/10.18051/UnivMed.2018.v37.65-74 Iqbal, M., Syed, J.H., Breivik, K., Chaudhry, M.J.I., Li, J., Zhang, G., Malik, R.N., 2017. E- Waste Driven Pollution in Pakistan: The First Evidence of Environmental and Human Exposure to Flame Retardants (FRs) in Karachi City. Environ. Sci. Technol. 51, 13895– 13905. https://doi.org/10.1021/acs.est.7b03159 Jacobson, M.H., Barr, D.B., Marcus, M., Muir, A.B., Lyles, R.H., Howards, P.P., Pardo, L., Darrow, L.A., 2016. Serum polybrominated diphenyl ether concentrations and thyroid function in young children. Environ. Res. 149, 222–230. https://doi.org/10.1016/j.envres.2016.05.022 Jarema, K.A., Hunter, D.L., Shaffer, R.M., Behl, M., Padilla, S., 2015. Acute and developmental behavioral effects of flame retardants and related chemicals in zebrafish. Neurotoxicol. Teratol. 52, 194–209. https://doi.org/10.1016/j.ntt.2015.08.010

123

Julander, A., Westberg, H., Engwall, M., van Bavel, B., 2005. Distribution of brominated flame retardants in different dust fractions in air from an electronics recycling facility. Sci. Total Environ. 350, 151–160. https://doi.org/10.1016/j.scitotenv.2005.01.015 Kahhat, R., Williams, E., 2012. Materials flow analysis of e-waste: Domestic flows and exports of used computers from the United States. Resour. Conserv. Recycl. 67, 67–74. https://doi.org/10.1016/j.resconrec.2012.07.008 Kammerer, F., 2017. Safe Drinking Water and Toxic Enforcement Act of 1986. Environ. Heal. 1–22. Kile, M.L., Scott, R.P., O’Connell, S.G., Lipscomb, S., MacDonald, M., McClelland, M., Anderson, K.A., Gibson, E.A., Stapleton, H.M., Calero, L., Holmes, D., Burke, K., Martinez, R., Cortes, B., Nematollahi, A., Evans, D., Anderson, K.A., Herbstman, J.B., Fisher, M., Arbuckle, T.E., MacPherson, S., Braun, J.M., Feeley, M., Gaudreau, É., Dixon, H.M., Scott, R.P., Holmes, D., Calero, L., Kincl, L.D., Waters, K.M., Camann, D.E., Calafat, A.M., Herbstman, J.B., Anderson, K.A., Bohlin, P., Jones, K.C., Levin, J.O., Lindahl, R., Strandberg, B., 2019. Using silicone wristbands to evaluate preschool children’s exposure to flame retardants. Chemosphere 219, 567–573. https://doi.org/10.1007/s00216-018-0992-z Kim, E.-H., Jeon, B.-H., Kim, J., Kim, Y.-M., Han, Y., Ahn, K., Cheong, H.-K., 2017. Exposure to phthalates and bisphenol A are associated with atopic dermatitis symptoms in children: a time-series analysis. Environ. Heal. 16, 24. https://doi.org/10.1186/s12940-017-0225-5 Kim, Y.H., Wyrzykowska-Ceradini, B., Touati, A., Krantz, Q.T., Dye, J.A., Linak, W.P., Gullett, B., Gilmour, M.I., 2015. Characterization of Size-Fractionated Airborne Particles Inside an Electronic Waste Recycling Facility and Acute Toxicity Testing in Mice. Environ. Sci. Technol. 49, 11543–11550. https://doi.org/10.1021/acs.est.5b03263 Koniecki, D., Wang, R., Moody, R.P., Zhu, J., 2011. Phthalates in cosmetic and personal care products: Concentrations and possible dermal exposure. Environ. Res. 111, 329–336. https://doi.org/10.1016/j.envres.2011.01.013 Kuo, L., Cade, S.E., Cullinan, V., Schultz, I.R., 2019. Polybrominated diphenyl ethers (PBDEs) in plasma from E-waste recyclers, outdoor and indoor workers in the Puget Sound, WA region. Chemosphere 219, 209–216. https://doi.org/10.1016/j.chemosphere.2018.12.006 Kuriyama, S.N., Talsness, C.E., Grote, K., Chahoud, I., 2005. Developmental exposure to low- dose PBDE-99: Effects on male fertility and neurobehavior in rat offspring. Environ. Health Perspect. 113, 149–154. https://doi.org/10.1289/ehp.7421 La Guardia, M.J., Hale, R.C., Harvey, E., 2006. Detailed Polybrominated Diphenyl Ether (PBDE) Congener Composition of the Widely Used Penta-, Octa-, and Deca-PBDE Technical Flame-retardant Mixtures. Environ. Sci. Technol. 40, 6247–6254. https://doi.org/10.1021/es060630m Labunska, I., Harrad, S., Wang, M., Santillo, D., Johnston, P., 2014. Human Dietary Exposure to PBDEs Around E-Waste Recycling Sites in Eastern China. Environ. Sci. Technol. 48, 5555–5564. https://doi.org/10.1021/es500241m Lam, J., Lanphear, B.P., Bellinger, D., Axelrad, D.A., McPartland, J., Sutton, P., Davidson, L., Daniels, N., Sen, S., Woodruff, T.J., 2017. Developmental PBDE Exposure and IQ/ADHD in Childhood: A Systematic Review and Meta-analysis. Environ. Health Perspect. 125. https://doi.org/10.1289/EHP1632 Lenters, V., Portengen, L., Rignell-Hydbom, A., Jönsson, B.A.G., Lindh, C.H., Piersma, A.H., Toft, G., Bonde, J.P., Heederik, D., Rylander, L., Vermeulen, R., 2016. Prenatal Phthalate,

124

Perfluoroalkyl Acid, and Organochlorine Exposures and Term Birth Weight in Three Birth Cohorts: Multi-Pollutant Models Based on Elastic Net Regression. Environ. Health Perspect. 124, 365–372. https://doi.org/10.1289/ehp.1408933 Li, F., Xie, Q., Li, X., Li, N., Chi, P., Chen, J., Wang, Z., Hao, C., 2010. Hormone Activity of Hydroxylated Polybrominated Diphenyl Ethers on Human Thyroid Receptor-β: In Vitro and In Silico Investigations. Environ. Health Perspect. 118, 602–606. https://doi.org/10.1289/ehp.0901457 Lilienthal, H., Hack, A., Roth-Härer, A., Grande, S.W., Talsness, C.E., 2006. Effects of developmental exposure to 2,2′,4,4′, 5-pentabromodiphenyl ether (PBDE-99) on sex steroids, sexual development, and sexually dimorphic behavior in rats. Environ. Health Perspect. 114, 194–201. https://doi.org/10.1289/ehp.8391 Lippmann, M., 1998. The 1997 US EPA Standards for Particulate Matter and Ozone, in: Air Pollution and Health. pp. 75–100. https://doi.org/10.1039/9781847550095-00075 Little, J.C., Weschler, C.J., Nazaroff, W.W., Liu, Z., Cohen Hubal, E.A., 2012. Rapid Methods to Estimate Potential Exposure to Semivolatile Organic Compounds in the Indoor Environment. Environ. Sci. Technol. 46, 11171–11178. https://doi.org/10.1021/es301088a Liu, C., Zhang, Y., Weschler, C.J., 2017. Exposure to SVOCs from Inhaled Particles: Impact of Desorption. Environ. Sci. Technol. 51, 6220–6228. https://doi.org/10.1021/acs.est.6b05864 Lu, S.Y., Li, Y.X., Zhang, T., Cai, D., Ruan, J.J., Huang, M.Z., Wang, L., Zhang, J.Q., Qiu, R.L., 2017. Effect of E-waste Recycling on Urinary Metabolites of Organophosphate Flame Retardants and Plasticizers and Their Association with Oxidative Stress. Environ. Sci. Technol. 51, 2427–2437. https://doi.org/10.1021/acs.est.6b05462 Lucas, D., Petty, S.M., Keen, O., Luedeka, B., Schlummer, M., Weber, R., Barlaz, M., Yazdani, R., Riise, B., Rhodes, J., Nightingale, D., Diamond, M.L., Vijgen, J., Lindeman, A., Blum, A., Koshland, C.P., 2017. Methods of Responsibly Managing End-of-Life Foams and Plastics Containing Flame Retardants: Part I. Environ. Eng. Sci. https://doi.org/10.1089/ees.2017.0147 Ma, J., Addink, R., Yun, S., Cheng, J., Wang, W., Kannan, K., 2009. Polybrominated Dibenzo- p -dioxins/Dibenzofurans and Polybrominated Diphenyl Ethers in Soil, Vegetation, Workshop-Floor Dust, and Electronic Shredder Residue from an Electronic Waste Recycling Facility and in Soils from a Chemical Industrial Complex in Ea. Environ. Sci. Technol. 43, 7350–7356. https://doi.org/10.1021/es901713u MacIntosh, D.L., Minegishi, T., Fragala, M.A., Allen, J.G., Coghlan, K.M., Stewart, J.H., McCarthy, J.F., 2012. Mitigation of building-related polychlorinated biphenyls in indoor air of a school. Environ. Heal. A Glob. Access Sci. Source 11, 1–10. https://doi.org/10.1186/1476-069X-11-24 Mäkinen, M.S.E., Mäkinen, M.R.A., Koistinen, J.T.B., Pasanen, A.-L., Pasanen, P.O., Kalliokoski, P.J., Korpi, A.M., 2009. Respiratory and Dermal Exposure to Organophosphorus Flame Retardants and Tetrabromobisphenol A at Five Work Environments. Environ. Sci. Technol. 43, 941–947. https://doi.org/10.1021/es802593t Marek, R.F., Thorne, P.S., Herkert, N.J., Awad, A.M., Hornbuckle, K.C., 2017. Airborne PCBs and OH-PCBs Inside and Outside Urban and Rural U.S. Schools. Environ. Sci. Technol. 51, 7853–7860. https://doi.org/10.1021/acs.est.7b01910 Meeker, J.D., Cooper, E.M., Stapleton, H.M., Hauser, R., 2013. Exploratory analysis of urinary metabolites of phosphorus-containing flame retardants in relation to markers of male reproductive health. Endocr. Disruptors 1, e26306. https://doi.org/10.4161/endo.26306

125

Meeker, J.D., Stapleton, H.M., 2009. House Dust Concentrations of Organophosphate Flame Retardants in Relation to Hormone Levels and Semen Quality Parameters. Environ. Health Perspect. 118, 318–323. https://doi.org/10.1289/ehp.0901332 Meironyté, D., Norén, K., Bergman, Å., 1999. Analysis of polybrominated diphenyl ethers in swedish human milk. A time-related trend study, 1972–1997. J. Toxicol. Environ. Heal. - Part A 58, 329–341. https://doi.org/10.1080/009841099157197 Melymuk, L., Robson, M., Helm, P.A., Diamond, M.L., 2011. Evaluation of passive air sampler calibrations: Selection of sampling rates and implications for the measurement of persistent organic pollutants in air. Atmos. Environ. 45, 1867–1875. https://doi.org/10.1016/j.atmosenv.2011.01.011 Mendelsohn, E., Hagopian, A., Hoffman, K., Butt, C.M., Lorenzo, A., Congleton, J., Webster, T.F., Stapleton, H.M., 2016. Nail polish as a source of exposure to triphenyl phosphate. Environ. Int. 86, 45–51. https://doi.org/10.1016/j.envint.2015.10.005 Moeckel, C., Harner, T., Nizzetto, L., Strandberg, B., Lindroth, A., Jones, K.C., 2009. Use of depuration compounds in passive air samplers: Results from active sampling-supported field deployment, potential uses, and recommendations. Environ. Sci. Technol. 43, 3227– 3232. https://doi.org/10.1021/es802897x Morrison, G.C., Weschler, C.J., Bekö, G., Koch, H.M., Salthammer, T., Schripp, T., Toftum, J., Clausen, G., 2016. Role of clothing in both accelerating and impeding dermal absorption of airborne SVOCs. J. Expo. Sci. Environ. Epidemiol. 26, 113–118. https://doi.org/10.1038/jes.2015.42 Muenhor, D., Harrad, S., Ali, N., Covaci, A., 2010. Brominated flame retardants (BFRs) in air and dust from electronic waste storage facilities in Thailand. Environ. Int. 36, 690–698. https://doi.org/10.1016/j.envint.2010.05.002 Nalli, S., Horn, O.J., Grochowalski, A.R., Cooper, D.G., Nicell, J.A., 2006. Origin of 2- ethylhexanol as a VOC. Environ. Pollut. 140, 181–185. https://doi.org/10.1016/j.envpol.2005.06.018 National Academies of Sciences Engineering and Medicine, 2017. Application of Systematic Review Methods in an Overall Strategy for Evaluating Low-Dose Toxicity from Endocrine Active Chemicals. The National Academies Press, Washington,DC. https://doi.org/10.17226/24758 Nguyen, L. V., Diamond, M.L., Venier, M., Stubbings, W.A., Romanak, K., Bajard, L., Melymuk, L., Jantunen, L.M., Arrandale, V.H., 2019. Exposure of Canadian electronic waste dismantlers to flame retardants. Environ. Int. 129, 95–104. https://doi.org/10.1016/j.envint.2019.04.056 Nguyen, L. V., Gravel, S., Labrèche, F., Bakhiyi, B., Verner, M.A., Zayed, J., Jantunen, L.M., Arrandale, V.H., Diamond, M.L., 2020. Can Silicone Passive Samplers be Used for Measuring Exposure of e-Waste Workers to Flame Retardants? Environ. Sci. Technol. 54, 15277–15286. https://doi.org/10.1021/acs.est.0c05240 North, M.L., Takaro, T.K., Diamond, M.L., Ellis, A.K., 2014. Effects of phthalates on the development and expression of allergic disease and asthma. Ann. Allergy, Asthma Immunol. 112, 496–502. https://doi.org/10.1016/j.anai.2014.03.013 NTP, 1991. Toxicology and Carcinogenesis Studies of TRIS(2- CHLOROETHYL)PHOSPHATE (CAS NO. 115-96-8) in F344 / N Rats. Natl. Toxicol. Program Tech. Rep. Ser. 409, 1–171. O’Connell, S.G., Kincl, L.D., Anderson, K.A., 2014. Silicone Wristbands as Personal Passive

126

Samplers. Environ. Sci. Technol. 48, 3327–3335. https://doi.org/10.1021/es405022f Okeme, J.O., Nguyen, L. V., Lorenzo, M., Dhal, S., Pico, Y., Arrandale, V.H., Diamond, M.L., 2018a. Polydimethylsiloxane (silicone rubber) brooch as a personal passive air sampler for semi-volatile organic compounds. Chemosphere 208, 1002–1007. https://doi.org/10.1016/j.chemosphere.2018.05.196 Okeme, J.O., Nguyen, L. V., Lorenzo, M., Dhal, S., Pico, Y., Arrandale, V.H., Diamond, M.L., 2018b. Polydimethylsiloxane (silicone rubber) brooch as a personal passive air sampler for semi-volatile organic compounds. Chemosphere 208, 1002–1007. https://doi.org/10.1016/j.chemosphere.2018.05.196 Okeme, J.O., Parnis, J.M., Poole, J., Diamond, M.L., Jantunen, L.M., 2016a. Polydimethylsiloxane-air partition ratios for semi-volatile organic compounds by GC-based measurement and COSMO-RS estimation: Rapid measurements and accurate modelling. Chemosphere 156, 204–211. https://doi.org/10.1016/j.chemosphere.2016.04.094 Okeme, J.O., Rodgers, T.F.M., Jantunen, L.M., Diamond, M.L., 2018c. Examining the Gas- Particle Partitioning of Organophosphate Esters: How Reliable Are Air Measurements? Environ. Sci. Technol. 52, 13834–13844. https://doi.org/10.1021/acs.est.8b04588 Okeme, J.O., Saini, A., Yang, C., Zhu, J., Smedes, F., Klánová, J., Diamond, M.L., 2016b. Calibration of polydimethylsiloxane and XAD-Pocket passive air samplers (PAS) for measuring gas- and particle-phase SVOCs. Atmos. Environ. 143, 202–208. https://doi.org/10.1016/j.atmosenv.2016.08.023 Okeme, J.O., Yang, C., Abdollahi, A., Dhal, S., Harris, S.A., Jantunen, L.M., Tsirlin, D., Diamond, M.L., 2018d. Passive air sampling of flame retardants and plasticizers in Canadian homes using PDMS, XAD-coated PDMS and PUF samplers. Environ. Pollut. 239, 109–117. https://doi.org/10.1016/j.envpol.2018.03.103 Okonski, K., Degrendele, C., Melymuk, L., Landlová, L., Kukučka, P., Vojta, Š., Kohoutek, J., Čupr, P., Klánová, J., 2014. Particle Size Distribution of Halogenated Flame Retardants and Implications for Atmospheric Deposition and Transport. Environ. Sci. Technol. 48, 14426–14434. https://doi.org/10.1021/es5044547 Ospina, M., Jayatilaka, N.K., Wong, L.-Y., Restrepo, P., Calafat, A.M., 2018. Exposure to organophosphate flame retardant chemicals in the U.S. general population: Data from the 2013–2014 National Health and Nutrition Examination Survey. Environ. Int. 110, 32–41. https://doi.org/10.1016/j.envint.2017.10.001 Park, S.A., Gwak, S., Choi, S., 2014. Assessment of occupational symptoms and chemical exposures for nail salon technicians in Daegu City, Korea. J. Prev. Med. Public Heal. 47, 169–176. https://doi.org/10.3961/jpmph.2014.47.3.169 Pawar, G., 2017. Exploring the utility of 3-D skin models to evaluate trans-dermal uptake of flame retardants from indoor dust and consumer product. University of Birmingham. Pelucchi, C., Negri, E., Gallus, S., Boffetta, P., Tramacere, I., La Vecchia, C., 2009. Long-term particulate matter exposure and mortality: a review of European epidemiological studies. BMC Public Health 9, 453. https://doi.org/10.1186/1471-2458-9-453 Percy, Z., Vuong, A.M., Ospina, M., Calafat, A.M., La Guardia, M.J., Xu, Y., Hale, R.C., Dietrich, K.N., Xie, C., Lanphear, B.P., Braun, J.M., Cecil, K.M., Yolton, K., Chen, A., 2020. Organophosphate esters in a cohort of pregnant women: Variability and predictors of exposure. Environ. Res. 184, 109255. https://doi.org/10.1016/j.envres.2020.109255 Pettersson-Julander, A., van Bavel, B., Engwall, M., Westberg, H., 2004. Personal air sampling and analysis of polybrominated diphenyl ethers and other bromine containing compounds

127

at an electronic recycling facility in Sweden. J. Environ. Monit. 6, 874. https://doi.org/10.1039/b408381d Philippat, C., Bennett, D., Calafat, A.M., Picciotto, I.H., Xu, F., Giovanoulis, G., Van Waes, S., Padilla-Sanchez, J.A., Papadopoulou, E., Magnér, J., Haug, L.S., Neels, H., Covaci, A., 2016. Exposure to select phthalates and phenols through use of personal care products among Californian adults and their children. Environ. Res. 50, 7752–7760. https://doi.org/10.1021/acs.est.6b00246 Pinson, A., Bourguignon, J.P., Parent, A.S., 2016. Exposure to endocrine disrupting chemicals and neurodevelopmental alterations. Andrology 4, 706–722. https://doi.org/10.1111/andr.12211 Pope III, C.A., 2002. Lung Cancer, Cardiopulmonary Mortality, and Long-term Exposure to Fine Particulate Air Pollution. JAMA 287, 1132. https://doi.org/10.1001/jama.287.9.1132 Quach, T., Gunier, R., Tran, A., Von Behren, J., Doan-Billings, P.-A., Nguyen, K.-D., Okahara, L., Lui, B.Y.-B., Nguyen, M., Huynh, J., Reynolds, P., 2011. Characterizing Workplace Exposures in Vietnamese Women Working in California Nail Salons. Am. J. Public Health 101, S271–S276. https://doi.org/10.2105/AJPH.2010.300099 Radke, E.G., Braun, J.M., Meeker, J.D., Cooper, G.S., Agency, U.S.E.P., States, U., 2018. Phthalate exposure and male reproductive outcomes : A systematic review of the human epidemiological evidence. Environ. Int. 121, 764–793. https://doi.org/10.1016/j.envint.2018.07.029 Rakkestad, K.E., Dye, C.J., Yttri, K.E., Holme, J.A., Hongslo, J.K., Schwarze, P.E., Becher, R., 2007. Phthalate levels in Norwegian indoor air related to particle size fraction. J. Environ. Monit. 9, 1419. https://doi.org/10.1039/b709947a Rengasamy, S., Eimer, B., Shaffer, R.E., 2010. Simple respiratory protection - Evaluation of the filtration performance of cloth masks and common fabric materials against 20-1000 nm size particles. Ann. Occup. Hyg. 54, 789–798. https://doi.org/10.1093/annhyg/meq044 Richman, K.E., Butt, C.M., Young, C.J., 2018. Size-resolved particle measurements of polybrominated diphenyl ethers indoors: Implications for sources and human exposure. Environ. Toxicol. Chem. 37, 481–490. https://doi.org/10.1002/etc.3981 Robinson, B.H., 2009. E-waste: An assessment of global production and environmental impacts. Sci. Total Environ. 408, 183–191. https://doi.org/10.1016/j.scitotenv.2009.09.044 Rodes, C.E., Kamens, R.M., Wiener, R.W., 1991. The Significance and Characteristics of the Personal Activity Cloud on Exposure Assessment Measurements for Indoor Contaminants. Indoor Air 1, 123–145. https://doi.org/10.1111/j.1600-0668.1991.03-12.x Romanak, K.A., Wang, S., Stubbings, W.A., Hendryx, M., Venier, M., Salamova, A., 2019. Analysis of brominated and chlorinated flame retardants, organophosphate esters, and polycyclic aromatic hydrocarbons in silicone wristbands used as personal passive samplers. J. Chromatogr. A 1588, 41–47. https://doi.org/10.1016/j.chroma.2018.12.041 Romero-Franco, M., Hernández-Ramírez, R.U., Calafat, A.M., Cebrián, M.E., Needham, L.L., Teitelbaum, S., Wolff, M.S., López-Carrillo, L., 2011. Personal care product use and urinary levels of phthalate metabolites in Mexican women. Environ. Int. 37, 867–871. https://doi.org/10.1016/j.envint.2011.02.014 Rosenberg, C., Hämeilä, M., Tornaeus, J., Säkkinen, K., Puttonen, K., Korpi, A., Kiilunen, M., Linnainmaa, M., Hesso, A., 2011. Exposure to Flame Retardants in Electronics Recycling Sites. Ann. Occup. Hyg. 55, 658–665. https://doi.org/10.1093/annhyg/mer033 Saini, A., Okeme, J.O., Goosey, E., Diamond, M.L., 2015. Calibration of two passive air

128

samplers for monitoring phthalates and brominated flame-retardants in indoor air. Chemosphere 137, 166–173. https://doi.org/10.1016/j.chemosphere.2015.06.099 Saini, A., Okeme, J.O., Mark Parnis, J., McQueen, R.H., Diamond, M.L., 2016. From air to clothing: characterizing the accumulation of semi-volatile organic compounds to fabrics in indoor environments. Indoor Air. https://doi.org/10.1111/ina.12328 SCHETTLER, T., 2006. Human exposure to phthalates via consumer products. Int. J. Androl. 29, 134–139. https://doi.org/10.1111/j.1365-2605.2005.00567.x Schreder, E.D., Uding, N., La Guardia, M.J., 2016. Inhalation a significant exposure route for chlorinated organophosphate flame retardants. Chemosphere 150, 499–504. https://doi.org/10.1016/j.chemosphere.2015.11.084 Schwartz, J., Neas, L.M., 2000. Fine particles are more strongly associated than coarse particleswithacute respiratoryhealtheffectsinschoolchildren. Epidemiology 11, 6–10. Shi, T., Chen, S.-J., Luo, X.-J., Zhang, X.-L., Tang, C.-M., Luo, Y., Ma, Y.-J., Wu, J.-P., Peng, X.-Z., Mai, B.-X., 2009. Occurrence of brominated flame retardants other than polybrominated diphenyl ethers in environmental and biota samples from southern China. Chemosphere 74, 910–916. https://doi.org/10.1016/j.chemosphere.2008.10.047 Shoeib, M., Harner, T., 2002. Characterization and Comparison of Three Passive Air Samplers for Persistent Organic Pollutants. Environ. Sci. Technol. 36, 4142–4151. https://doi.org/10.1021/es020635t Sindiku, O., Babayemi, J., Osibanjo, O., Schlummer, M., Schluep, M., Watson, A., Weber, R., 2015. Polybrominated diphenyl ethers listed as Stockholm Convention POPs, other brominated flame retardants and heavy metals in e-waste polymers in Nigeria. Environ. Sci. Pollut. Res. 22, 14489–14501. https://doi.org/10.1007/s11356-014-3266-0 Singh, M., Thind, P.S., John, S., 2018. Health risk assessment of the workers exposed to the heavy metals in e-waste recycling sites of Chandigarh and Ludhiana, Punjab, India. Chemosphere 203, 426–433. https://doi.org/10.1016/j.chemosphere.2018.03.138 Sjödin, A., Carlsson, H., Thuresson, K., Sjölin, S., Bergman, Å., Östman, C., 2001. Flame Retardants in Indoor Air at an Electronics Recycling Plant and at Other Work Environments. Environ. Sci. Technol. 35, 448–454. https://doi.org/10.1021/es000077n Slotkin, T.A., Skavicus, S., Stapleton, H.M., Seidler, F.J., 2017. Brominated and organophosphate flame retardants target different neurodevelopmental stages, characterized with embryonic neural stem cells and neuronotypic PC12 cells. Toxicology 390, 32–42. https://doi.org/10.1016/j.tox.2017.08.009 Smil, V., 2017. PLANET OF THE COWS. IEEE Spectr. 54, 24. Snedeker, S.M., 2014. Toxicants in Food Packaging and Household Plastics, Molecular and Integrative Toxicology. Springer London, London. https://doi.org/10.1007/978-1-4471- 6500-2 Staaf, T., Ostman, C., 2005. Organophosphate triesters in indoor environments. J. Environ. Monit. 7, 883–887. https://doi.org/10.1039/b506631j Stapleton, H.M., Allen, J.G., Kelly, S.M., Konstantinov, A., Klosterhaus, S., Watkins, D., McClean, M.D., Webster, T.F., 2008a. Alternate and New Brominated Flame Retardants Detected in U.S. House Dust. Environ. Sci. Technol. 42, 6910–6916. https://doi.org/10.1021/es801070p Stapleton, H.M., Kelly, S.M., Allen, J.G., McClean, M.D., Webster, T.F., Stapleton, M.H., Kelly, S.M., Allen, J.G., McClean, M.D., Webster, T.F., Stapleton, H.M., Kelly, S.M., Allen, J.G., McClean, M.D., Webster, T.F., 2008b. Measurement of Polybrominated

129

Diphenyl Ethers on Hand Wipes: Estimating Exposure from Hand-to-Mouth Contact. Environ. Sci. Technol. 42, 3329–3334. https://doi.org/10.1021/es7029625 Statistics Canada, 2016. EnviroStats Trash talking: Dealing with Canadian household e-waste. [WWW Document]. URL http://www.statcan.gc.ca/pub/16-002-x/2016001/article/14570- eng.htm (accessed 7.15.18). Stubbings, W.A., Nguyen, L. V., Romanak, K., Jantunen, L., Melymuk, L., Arrandale, V., Diamond, M.L., Venier, M., 2019a. Flame retardants and plasticizers in a Canadian waste electrical and electronic equipment (WEEE) dismantling facility. Sci. Total Environ. 675, 594–603. https://doi.org/10.1016/j.scitotenv.2019.04.265 Stubbings, W.A., Nguyen, L. V., Romanak, K., Jantunen, L., Melymuk, L., Arrandale, V., Diamond, M.L., Venier, M., 2019b. Flame retardants and plasticizers in a Canadian waste electrical and electronic equipment (WEEE)dismantling facility. Sci. Total Environ. 675, 594–603. https://doi.org/10.1016/j.scitotenv.2019.04.265 Suzuki, G., Tue, N.M., Malarvannan, G., Sudaryanto, A., Takahashi, S., Tanabe, S., Sakai, S., Brouwer, A., Uramaru, N., Kitamura, S., Takigami, H., 2013. Similarities in the Endocrine- Disrupting Potencies of Indoor Dust and Flame Retardants by Using Human Osteosarcoma (U2OS) Cell-Based Reporter Gene Assays. Environ. Sci. Technol. 47, 2898–2908. https://doi.org/10.1021/es304691a Swedish Chemicals Inspectorate, 2003. Brominated flame retardants – Prospects of a national ban. KemI Report 4/03. Takigami, H., Suzuki, G., Hirai, Y., Sakai, S., 2008. Transfer of brominated flame retardants from components into dust inside television cabinets. Chemosphere 73, 161–169. https://doi.org/10.1016/j.chemosphere.2008.06.032 Tansel, B., 2017. From electronic consumer products to e-wastes: Global outlook, waste quantities, recycling challenges. Environ. Int. 98, 35–45. https://doi.org/10.1016/j.envint.2016.10.002 Thuresson, K., Höglund, P., Hagmar, L., Sjödin, A., Bergman, Å., Jakobsson, K., 2006. Apparent Half-Lives of Hepta- to Decabrominated Diphenyl Ethers in Human Serum as Determined in Occupationally Exposed Workers. Environ. Health Perspect. 114, 176–181. https://doi.org/10.1289/ehp.8350 Tran, T.M., Kannan, K., 2015. Occurrence of Phthalate Diesters in Particulate and Vapor Phases in Indoor Air and Implications for Human Exposure in Albany, New York, USA. Arch. Environ. Contam. Toxicol. 68, 489–499. https://doi.org/10.1007/s00244-015-0140-0 Tran, T.M., Le, H.T., Minh, T.B., Kannan, K., 2017. Occurrence of phthalate diesters in indoor air from several Northern cities in Vietnam, and its implication for human exposure. Sci. Total Environ. 601–602, 1695–1701. https://doi.org/10.1016/j.scitotenv.2017.06.016 Traore, I.T., Gravel, S., Diamond, M.L., Jantunen, L., Nguyen, L.V., Yang, C., Bernstein, S., Zayed, J., Labrèche, F., Verner, M.-A., 2018. Urinary Metabolites of Organophosphate Esters (OPEs) in Electronic Waste Recycling Workers from the Province of Quebec, Canada. ISEE Conf. Abstr. 2018, isesisee.2018.P01.3100. https://doi.org/10.1289/isesisee.2018.P01.3100 Tromp, P.C., Beeltje, H., Okeme, J.O., Vermeulen, R., Pronk, A., Diamond, M.L., 2019. Calibration of polydimethylsiloxane and polyurethane foam passive air samplers for measuring semi volatile organic compounds using a novel exposure chamber design. Chemosphere 227, 435–443. https://doi.org/10.1016/j.chemosphere.2019.04.043 Tue, N.M., Takahashi, S., Suzuki, G., Isobe, T., Viet, P.H., Kobara, Y., Seike, N., Zhang, G.,

130

Sudaryanto, A., Tanabe, S., 2013. Contamination of indoor dust and air by polychlorinated biphenyls and brominated flame retardants and relevance of non-dietary exposure in Vietnamese informal e-waste recycling sites. Environ. Int. 51, 160–167. https://doi.org/10.1016/j.envint.2012.11.006 U.S.Bureau of Labor, 2020. Occupational Outlook Handbook [WWW Document]. UCLA Labor Center, 2018. Nail Files: A study of nail salon workers and industry in United States. UNEP, 2019. A New Circular Vision for Electronics Time for a Global Reboot 24. UNEP, 2016. GEO-6 North America Regional Assessment [WWW Document]. URL http://wedocs.unep.org/bitstream/handle/20.500.11822/7611/GEO_North_America_201611 .pdf?sequence=1&isAllowed=y (accessed 6.27.18). UNEP, 2010. Technical review of the implications of recycling commercial pentabromodiphenyl ether and commercial octabromodi- phenyl ether. UNEP, 2008. Report of the Persistent Organic Pollutants Review Committee on the work of its fourth meeting. United States Department of Labor, 2017. Occupational Employment and Wages, May 2017 [WWW Document]. URL https://www.bls.gov/oes/current/oes395092.htm#st US EPA, 2018a. IRIS Assessments [WWW Document]. URL https://cfpub.epa.gov/ncea/iris2/atoz.cfm (accessed 6.27.18). US EPA, 2018b. Chemistry Dashboard [WWW Document]. URL https://comptox.epa.gov/dashboard (accessed 6.27.18). US EPA, 2018c. 2,2’,4,4’,5-Pentabromodiphenyl ether (BDE-99) [WWW Document]. URL https://cfpub.epa.gov/ncea/iris2/chemicalLanding.cfm?substance_nmbr=1008 (accessed 6.27.18). US EPA, 2011. September 2011 EXPOSURE FACTORS HANDBOOK : 2011 EDITION National Center for Environmental Assessment Office of Research and Development U . S . Environmental Protection Agency Washington , DC 20460 Exposure Factors Handbook. Exposure. USEPA, 2020. CHEMICALS KNOWN TO THE STATE TO CAUSE CANCER OR REPRODUCTIVE TOXICITY January 3, 2020. Veen, I. Van Der, Boer, J. De, 2012. Chemosphere Phosphorus flame retardants : Properties , production , environmental occurrence , toxicity and analysis. Chemosphere 88, 1119– 1153. https://doi.org/10.1016/j.chemosphere.2012.03.067 Venier, M., Ma, Y., Hites, R.A., 2012. Brominated flame retardants in the Great Lakes atmosphere. Environ. Sci. Technol. 46, 8653–8660. https://doi.org/dx.doi.org/10.1021/es3015919 Viberg, H., Fredriksson, A., Eriksson, P., 2004. Investigations of strain and/or gender differences in developmental neurotoxic effects of polybrominated diphenyl ethers in mice. Toxicol. Sci. 81, 344–353. https://doi.org/10.1093/toxsci/kfh215 Viberg, H., Fredriksson, A., Jakobsson, E., Orn, U., Erikson, P., 2003. Neurobehavioral derangements in adult mice receiving decabrominated diphenyl ether (PBDE 209) during a defined period of neonatal brain development. Toxicol. Sci. 76, 112–120. https://doi.org/10.1093/toxsci/kfg210 Vojta, Š., Bečanová, J., Melymuk, L., Komprdová, K., Kohoutek, J., Kukučka, P., Klánová, J., 2017. Screening for halogenated flame retardants in European consumer products, building materials and wastes. Chemosphere 168, 457–466.

131

https://doi.org/10.1016/j.chemosphere.2016.11.032 Vuong, A.M., Braun, J.M., Webster, G.M., Thomas Zoeller, R., Hoofnagle, A.N., Sjödin, A., Yolton, K., Lanphear, B.P., Chen, A., 2018. Polybrominated diphenyl ether (PBDE) exposures and thyroid hormones in children at age 3 years. Environ. Int. 117, 339–347. https://doi.org/10.1016/j.envint.2018.05.019 Vuong, A.M., Yolton, K., Xie, C., Webster, G.M., Sjödin, A., Braun, J.M., Dietrich, K.N., Lanphear, B.P., Chen, A., 2017. Childhood polybrominated diphenyl ether (PBDE) exposure and neurobehavior in children at 8 years. Environ. Res. 158, 677–684. https://doi.org/10.1016/j.envres.2017.07.028 Vykoukalová, M., Venier, M., Vojta, Š., Melymuk, L., Bečanová, J., Romanak, K., Prokeš, R., Okeme, J.O., Saini, A., Diamond, M.L., Klánová, J., 2017. Organophosphate esters flame retardants in the indoor environment. Environ. Int. 106, 97–104. https://doi.org/10.1016/j.envint.2017.05.020 Wallace, L., 2000. Correlations of personal exposure to particles with outdoor air measurements: A review of recent studies. Aerosol Sci. Technol. 32, 15–25. https://doi.org/10.1080/027868200303894 Wallner, P., Kundi, M., Hohenblum, P., Scharf, S., Hutter, H., 2016. Phthalate Metabolites, Consumer Habits and Health Effects. Int. J. Environ. Res. Public Health 13, 717. https://doi.org/10.3390/ijerph13070717 Wan, Y., Diamond, M.L., Siegel, J.A., 2020. Elevated Concentrations of Semivolatile Organic Compounds in Social Housing Multiunit Residential Building Apartments. Environ. Sci. Technol. Lett. 7, 191–197. https://doi.org/10.1021/acs.estlett.0c00068 Wang, D.G., Alaee, M., Byer, J.D., Brimble, S., Pacepavicius, G., 2013. Human health risk assessment of occupational and residential exposures to dechlorane plus in the manufacturing facility area in China and comparison with e-waste recycling site. Sci. Total Environ. 445–446, 329–336. https://doi.org/10.1016/j.scitotenv.2012.12.059 Wang, S., Romanak, K.A., Stubbings, W.A., Arrandale, V.H., Hendryx, M., Diamond, M.L., Salamova, A., Venier, M., 2019. Silicone wristbands integrate dermal and inhalation exposures to semi-volatile organic compounds (SVOCs). Environ. Int. 132, 105104. https://doi.org/10.1016/j.envint.2019.105104 Wang, Y., Peris, A., Rifat, M.R., Ahmed, S.I., Aich, N., Nguyen, L. V., Urík, J., Eljarrat, E., Vrana, B., Jantunen, L.M., Diamond, M.L., 2020. Measuring exposure of e-waste dismantlers in Dhaka Bangladesh to organophosphate esters and halogenated flame retardants using silicone wristbands and T-shirts. Sci. Total Environ. 720, 137480. https://doi.org/10.1016/j.scitotenv.2020.137480 Wei, G.-L., Li, D.-Q., Zhuo, M.-N., Liao, Y.-S., Xie, Z.-Y., Guo, T.-L., Li, J.-J., Zhang, S.-Y., Liang, Z.-Q., 2015. Organophosphorus flame retardants and plasticizers: Sources, occurrence, toxicity and human exposure. Environ. Pollut. 196, 29–46. https://doi.org/10.1016/j.envpol.2014.09.012 Wei, W., Bonvallot, N., Gustafsson, Å., Raffy, G., Glorennec, P., Krais, A., Ramalho, O., Le Bot, B., Mandin, C., 2018. Bioaccessibility and bioavailability of environmental semi- volatile organic compounds via inhalation: A review of methods and models. Environ. Int. 113, 202–213. https://doi.org/10.1016/j.envint.2018.01.024 Wei, W., Mandin, C., Ramalho, O., 2017. Reactivity of Semivolatile Organic Compounds with Hydroxyl Radicals, Nitrate Radicals, and Ozone in Indoor Air. Int. J. Chem. Kinet. 49, 506–521. https://doi.org/10.1002/kin.21093

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Weschler, C.J., Nazaroff, W.W., 2014. Dermal Uptake of Organic Vapors Commonly Found in Indoor Air. Environ. Sci. Technol. 48, 1230–1237. https://doi.org/10.1021/es405490a Weschler, C.J., Nazaroff, W.W., 2012. SVOC exposure indoors: Fresh look at dermal pathways. Indoor Air. https://doi.org/10.1111/j.1600-0668.2012.00772.x Weschler, C.J., Nazaroff, W.W., 2010. SVOC partitioning between the gas phase and settled dust indoors. Atmos. Environ. 44, 3609–3620. https://doi.org/10.1016/j.atmosenv.2010.06.029 Weschler, C.J., Nazaroff, W.W., 2008. Semivolatile organic compounds in indoor environments. Atmos. Environ. 42, 9018–9040. https://doi.org/10.1016/j.atmosenv.2008.09.052 Whitman, W.G., 1962. The two film theory of gas absorption. Int. J. Heat Mass Transf. 5, 429– 433. https://doi.org/10.1016/0017-9310(62)90032-7 Wielsøe, M., Kern, P., Bonefeld-Jørgensen, E.C., 2017. Serum levels of environmental pollutants is a risk factor for breast cancer in Inuit: a case control study. Environ. Heal. 16, 56. https://doi.org/10.1186/s12940-017-0269-6 Wong, C.S.C., Duzgoren-Aydin, N.S., Aydin, A., Wong, M.H., 2007. Evidence of excessive releases of metals from primitive e-waste processing in Guiyu, China. Environ. Pollut. 148, 62–72. https://doi.org/10.1016/j.envpol.2006.11.006 Wu, C.-C., Bao, L.-J., Tao, S., Zeng, E.Y., 2016. Dermal Uptake from Airborne Organics as an Important Route of Human Exposure to E-Waste Combustion Fumes. Environ. Sci. Technol. 50, 6599–6605. https://doi.org/10.1021/acs.est.5b05952 Xu, F., Zhang, G., Wang, J., Zhang, W., Liu, L., Lin, K., 2015. Polybrominated diphenyl ethers in air and fallouts from an e-waste polluted region in southeast China: insight into levels, compositional profiles, and seasonal variation. Environ. Sci. Pollut. Res. 22, 19676–19686. https://doi.org/10.1007/s11356-015-5168-1 Xu, Y., Cohen Hubal, E.A., Clausen, P.A., Little, J.C., 2009. Predicting Residential Exposure to Phthalate Plasticizer Emitted from Vinyl Flooring: A Mechanistic Analysis. Environ. Sci. Technol. 43, 2374–2380. https://doi.org/10.1021/es801354f Xu, Y., Cohen Hubal, E.A., Little, J.C., 2010. Predicting residential exposure to phthalate plasticizer emitted from vinyl flooring: Sensitivity, uncertainty, and implications for biomonitoring. Environ. Health Perspect. 118, 253–258. https://doi.org/10.1289/ehp.0900559 Yang, C., Harris, S.A., Jantunen, L.M., Kvasnicka, J., Nguyen, L. V., Diamond, M.L., 2020a. Phthalates: Relationships between Air, Dust, Electronic Devices, and Hands with Implications for Exposure. Environ. Sci. Technol. 54, acs.est.0c00229. https://doi.org/10.1021/acs.est.0c00229 Yang, C., Harris, S.A., Jantunen, L.M., Siddique, S., Kubwabo, C., Tsirlin, D., Latifovic, L., Fraser, B., St-Jean, M., De La Campa, R., You, H., Kulka, R., Diamond, M.L., 2018. Are cell phones an indicator of personal exposure to organophosphate flame retardants and plasticizers? Environ. Int. in press, 1–13. https://doi.org/10.1016/j.envint.2018.10.021 Yang, C., Jílková, S.R., Melymuk, L., Harris, S.A., Jantunen, L.M., Pertili, J., Winn, L., Diamond, M.L., 2020b. Are We Exposed to Halogenated Flame Retardants from both Primary and Secondary Sources? Environ. Sci. Technol. Lett. 7, 585–593. https://doi.org/10.1021/acs.estlett.0c00268 Young, A.S., Allen, J.G., Kim, U.-J.J., Seller, S., Webster, T.F., Kannan, K., Ceballos, D.M., 2018. Phthalate and Organophosphate Plasticizers in Nail Polish: Evaluation of Labels and Ingredients. Environ. Sci. Technol. 52, acs.est.8b04495.

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https://doi.org/10.1021/acs.est.8b04495 Zabiegała, B., Zygmunt, B., Przyk, E., Namieśnik, J., 2000. Applicability of silicone membrane passive samplers for monitoring of indoor air quality. Anal. Lett. 33, 1361–1372. https://doi.org/10.1080/00032710008543127 Zeng, X., Yang, C., Chiang, J.F., Li, J., 2017. Innovating e-waste management: From macroscopic to microscopic scales. Sci. Total Environ. 575, 1–5. https://doi.org/10.1016/j.scitotenv.2016.09.078 Zhang, H., Yolton, K., Webster, G.M., Sjödin, A., Calafat, A.M., Dietrich, K.N., Xu, Y., Xie, C., Braun, J.M., Lanphear, B.P., Chen, A., 2016. Prenatal PBDE and PCB Exposures and Reading, Cognition, and Externalizing Behavior in Children. Environ. Health Perspect. 125, 7–16. https://doi.org/10.1289/EHP478 Zhang, X., Diamond, M.L., Robson, M., Harrad, S., 2011. Sources, emissions, and fate of polybrominated diphenyl ethers and polychlorinated biphenyls indoors in Toronto, Canada. Environ. Sci. Technol. 45, 3268–3274. https://doi.org/10.1021/es102767g Zhang, Z., Sun, Z.-Z., Xiao, X., Zhou, S., Wang, X.X.-C., Gu, J., Qiu, L.-L., Zhang, X.-H., Xu, Q., Zhen, B., Wang, X.X.-C., Wang, S.-L., 2013a. Mechanism of BDE209-induced impaired glucose homeostasis based on gene microarray analysis of adult rat liver. Arch. Toxicol. 87, 1557–1567. https://doi.org/10.1007/s00204-013-1059-8 Zhang, Z., Zhang, X., Sun, Z., Dong, H., Qiu, L., Gu, J., Zhou, J., Wang, X., Wang, S.L., 2013b. Cytochrome P450 3A1 Mediates 2,2′,4,4′-Tetrabromodiphenyl Ether-Induced Reduction of Spermatogenesis in Adult Rats. PLoS One 8. https://doi.org/10.1371/journal.pone.0066301 Zheng, X., Xu, F., Chen, K., Zeng, Y., Luo, X., Chen, S., Mai, B., Covaci, A., 2015. Flame retardants and organochlorines in indoor dust from several e-waste recycling sites in South China: Composition variations and implications for human exposure. Environ. Int. 78, 1–7. https://doi.org/10.1016/j.envint.2015.02.006 Zota, A.R., Rudel, R.A., Morello-Frosch, R.A., Brody, J.G., 2008. Elevated House Dust and Serum Concentrations of PBDEs in California: Unintended Consequences of Furniture Flammability Standards? Environ. Sci. Technol. 42, 8158–8164. https://doi.org/10.1021/es801792z

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Chapter 4 – Occupational exposure of Canadian nail salon workers to FRs and plasticizers including phthalates and organophosphorus esters (OPEs)

Abstracts

Personal exposure of nail salon workers to 10 phthalates and 19 organophosphate esters was studied at 18 Toronto nail salons. Active air samplers (n = 60) and silicone passive samplers, including brooches (n = 58) and wristbands (n = 60), were worn by nail salon workers for an average of ~8 working hours. The highest phthalate concentrations in active air samples were of diethyl phthalate (DEP, median: 471 ng m-3), followed by diisobutyl phthalate (DiBP, median:

337 ng m-3) and di-n-butyl phthalate (DnBP, median: 331 ng m-3). Surprisingly, the most abundant

OPEs in active air samples were tris(2-choloisopropyl) phosphate (TCIPP median: 303 ng m-3), followed by tris(2-choloethyl)phosphate (TCEP, median: 139 ng m-3). Both TCEP and TCIPP were better known as flame retardants and rarely found in personal care products. Air concentrations of phthalates and OPEs were not associated with number of services performed during the shift. Within a single work shift, passive silicone brooches and wristbands accumulated detectable amounts of 16 (55%) and 19 (66%) compounds, respectively. A significant relationships found between levels of some phthalates and OPEs in silicone brooches and wristbands versus those in active air samplers (p < 0.05). Stronger correlations tended to be observed between active air samplers vs. brooches compared to wristbands. Our findings suggest that silicone brooches and wristbands can be useful as a qualitative screening tool for measuring exposure to phthalates and OPEs in occupational settings.

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4.1 Introduction

Nail care services in North America are popular and have grown more numerous over the past three decades. The number of US licensed nail manicurists and pedicurists was projected to increase ~10% from 2018 to 2028 to reach 172,000 (U.S.Bureau of Labor, 2020). Nail salons are small businesses that are highly concentrated in urban settings. Toronto, Canada’s largest city, has approximately 1,500 licensed establishments providing nail services (City of Toronto, 2019).

Most nail salon workers are women who are often are immigrants and working in precarious employment (Federman et al., 2006; UCLA Labor Center, 2018). Likely because of the expansion of the industry and the perceived vulnerability of the group, but also because nail salons are a public space, there has been increased public attention on the hazards in nail salons in recent years.

Previous research has demonstrated that nail technicians are at increased risk of respiratory and skin diseases, likely as a result of their workplace exposure to chemicals including acrylates, wet work and phthalates (Koniecki et al., 2011; Park et al., 2014; Quach et al., 2011) . Specifically, diverse personal care products (e.g. nail polish, perfume, skin lotion, and etc.) commonly used in nail salons contain plasticizers and fragrance keepers such as phthalates.(Guo and Kannan, 2013;

Mendelsohn et al., 2016; Young et al., 2018). Recent studies have also identified organophosphate esters (OPEs) as additives to products that could be used in nail salons such as nail polish

(Mendelsohn et al., 2016; Young et al., 2018). Exposure to some phthalates and OPEs has been associated with health effects such as neurodevelopmental and reproductive effects (Carignan et al., 2018; Castorina et al., 2017; Factor-Litvak et al., 2014). Because of health concerns, Canada has prohibited the use of six phthalates in children’s toys (Goverment of Canada, 2017) and diethylhexyl phthalate (DEHP) in cosmetics since 2009 (Government of Canada, 2019).

Furthermore, the European Union banned dibutyl phthalate (DnBP) in cosmetics in 2004 and US

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companies have voluntarily stop producing nail polish containing DnBP by 2006. Tris(1,3- dichloro-2-propyl) phosphate (TDCIPP) and tris(2-chloroethyl) phosphate (TCEP) has been listed as a carcinogens under California Proposition 65 (USEPA, 2020).

There is limited exposure data for phthalates and OPEs among nail technicians. A recent pilot study (n=10) (Craig et al., 2019) found that the urinary metabolites of phthalates and OPEs among nail technicians were generally lower than US adult population. Estill et al. (2020) reported that median levels of triphenyl phosphate (TPhP) collected by personal active air samplers in nail salon were 2, 3 and 10 times lower than those from workers at gymnastics, carpet installation and electronic scrap industry, respectively. Estill et al. (2020) did not analyze other OPEs such as

TCEP and TDCIPP in the nail salon samples. Previous indoor air studies in the US21 and

Vietnam22 found levels of phthalates in beauty salons were higher than homes, offices and kindergartens.

In the occupational environment, exposure is commonly measured with active air samplers, however this method is expensive, burdensome and noisy. Silicone passive samplers, such as brooches and wristbands, avoid those drawbacks and as such, have become increasingly common for identifying personal exposure to semi-volatile organic compounds (SVOCs) including phthalates and OPEs (O’Connell et al., 2014; Okeme et al., 2018b; Wang et al., 2019,

2020). The silicone brooch was first introduced by Okeme et al. (2018b) for capturing phthalates and OPEs in an office environment over a 24-hour deployment period. In the US, Wang et al.

(2019) conducted a pilot study (n=10) in which they deployed brooches, wristbands and active air samplers for 72-hours as well as collecting hand wipes. They found that levels of several classes of SVOCs captured by silicone brooches were strongly correlated to those measured by a co- located active air sampler (Wang et al., 2019). Chemical masses accumulated by wristbands most

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closely corresponded to those collected by brooches plus hand wipes. In the occupational environment, Nguyen et al. (2020) found that flame retardant levels accumulated by silicone brooches were more highly correlated to active air samples compared to wristbands and armbands worn by e-waste workers during 6-10 hour deployment.

Silicone wristbands are hypothesized to capture integrated exposure information from various pathways (Craig et al., 2019; Dixon et al., 2018; Hammel et al., 2016, 2018; Romanak et al., 2019; Wang et al., 2019, 2020). Many studies in non-occupational settings have found moderately significant relationship between levels of flame retardants captured by wristbands and their respective biomarkers in serum (Hammel et al., 2018) and urine where deployment periods were 2, 5 and 7 days (Dixon et al., 2018; Hammel et al., 2016; Kile et al., 2019). Craig et al. (2019) reported a moderate relationship between levels of phthalates, phthalate alternatives and OPEs accumulated by wristbands versus urinary metabolites among nail salon workers ( ~ 9 hour deployment period). Nguyen et al. (2020) also found a moderate relationship between brooches and wristbands worn by e-waste workers for the average of 8 hours but only for polybrominated diphenyl ether, BDE-209 in plasma, but not for OPE metabolites analyzed in an after-shift spot urine sample.

The primary aim of this study was to assess exposure to phthalates and OPEs among nail salon workers in Toronto using active air samplers and silicone brooches and wristbands and whether exposures were associated with specific task. The secondary aim was to evaluate the use of silicone brooches and wristbands for assessing personal exposure phthalates and OPEs against the active air samplers.

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4.2 Materials and Methods

4.2.1 Study design

This study reports the occupational exposure to phthalates and OPEs among nail salon workers in Toronto as part of a larger study that examined a wide range of occupational exposures in nail salons, including ergonomics, psychosocial stress, volatile and semi-volatile organic compounds.

Sampling was conducted between April and September 2018. Salons were recruited in- person by the research team. Salons were invited to participate if their primary activity was nail services (e.g., manicure, pedicure, and artificial nails) although most of the salons also offered other services (e.g., eyebrows/eyelash extension, waxing, tattoo and massage). All participating workers signed an informed consent form and received a small honorarium for participating; salon owners also received an honorarium. All study protocols and materials related to the study were approved by the University of Toronto health research ethics board. Table A4.1 (Appendix 3) summarizes information about the 45 workers from 18 salons who were recruited. Note that 14 workers agreed to participate for 2 days and one worker participated for 3 days and thus data were collected for 60 “service days” (Table A4.2, Appendix 3).

4.2.2 Sampling strategy

An active air sampler (ORBO 49P (OVS), Supelco, Sigma Aldrich, Canada) was worn on the collar of participant’s vest within the breathing zone to collect personal levels of phthalates and OPEs in bulk air (Figure A4.1, Appendix 3). The OVS tube consisted of a glass fiber filter

(GFF-OVS, diameter 13 mm, pore size 0.1 µm) and PUF/XAD-2/PUF sandwich, connected to an

AirCheck XR500 (SKC Inc., Pennsylvania, USA) pump with a flow rate of 2 L min-1. Pumps were

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calibrated pre- and post-deployment each day to assess the drift in flow rate. Four samples out of

60 samples had a flow rate drift > 5% (in occupational hygiene acceptable drift is considered to be <5%). Chemical concentrations of these four samples were statistically indistinguishable from all others and thus were included in the final statistical analysis. Averages of pre- and post- sampling rates were used to calculate air concentrations collected by active air samplers. After sampling, OVS tube were wrapped in aluminum foil and stored in 40 mL amber vials on ice while transporting, then stored at -20 oC in the laboratory until analysis. One sample were discarded because of problems encountered with analysis (e.g., the sample was leaked from the broken GC vial).

Silicone brooches (length 9 cm x width 5.5 cm x thickness 0.1 cm; Specialty Silicone

Products, Inc., Ballston Spa, NY) were attach to an aluminum housing (Figure A4.1, Appendix

3). The design details of the brooch were described by Okeme et al. (2018a). Brooches were worn parallel to the reference active air samplers (OVS, SKC Ltd.). After sampling, silicone brooches were stored in 500 mL amber vial on ice while transporting, then transferred to 40 mL amber vial, then stored at -20 oC until analysis. Two samples were discarded because of problems encountered with analysis; one sample was dropped when transferring and the extract of the other was leaked from the GC vial.

Silicone wristbands (length 16 cm x width 3 cm x thickness 0.1 cm; Specialty Silicone

Products, Inc., Ballston Spa, NY) were worn on the wrist of each worker (Figure A4.1, Appendix

3). After sampling, samples were stored in 250 mL amber vial on ice while transporting, then transferred to 40 mL amber vial to store at -20 ºC until analysis. One sample was lost because its extract leaked from a broken GC vial during analysis.

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Prior to sampling, all media (OVS tubes, silicone brooches and wristbands) were pre- cleaned. Detailed pre-cleaning methods are described in Appendix 3, section A4.1.

At the end of each sampling day participants completed a short questionnaire to collect information about their job tasks that day, including the type and number of services provided

(e.g. manicure, pedicure, artificial nails, etc.).

4.2.3 Extraction and chemical analysis

Prior to extraction, all samples and blanks were spiked with surrogate standards to assess extraction efficiencies. DEP-d4, DnBP-d4 and DEHP-d4 were used as surrogate standards for phthalates (AccuStandards Inc., USA) and TEP-d15, TPrP-d21, TBP-d27, TDCIPP-d15, TCEP- d12 and MTPhP for OPEs (Wellington Laboratories, Canada). Internal standards (Mirex for OPEs and Fluoranthene-d10 for phthalates) were added for volume correction and time reference after extraction.

The GFF-OVSs and PUF/XAD-2/PUF sandwiches in active air samplers were extracted together to report the bulk air concentrations. The OVS tubes were extracted with 15 mL of

Acetone : DCM : Hexane (1:1:1) mixture using a Supelco vacuum chamber (Bellefonte, PA,

USA). Brooches and wristbands were extracted by shaking and soaking with 30mL of Acetonitrile using a Wrist Action Shaker (Burrell Corporation, USA). All extracts were reduced to approximately 0.5 mL in isooctane. Full details of extraction methods are provided in

Supplemental Information S2.

All samples and blanks (see below) were analyzed for phthalates and OPE on an Agilent

6890N/5973 or 5975 gas chromatograph/ inert mass selective detector (GC-MSD) system. Full names, CAS numbers, molecular weights and octanol-air coefficients (KOA) of the 29 target

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compounds are listed in Table A4.3 (Appendix 3). A negative chemical ionization (ENCI) source was used for TDCPP and an electron impact ionization (EI) source for phthalates and all other

OPEs measured here. Full details of instrumental analysis with monitored ions are given in

Appendix 3, section A4.3 and Tables A4.4 – A4.5.

4.2.4 Quality Assurance and Quality Control (QA/QC)

Field blanks were collected each day and analyzed along with laboratory blanks and matrix spikes for each sample matrix. Field blanks were exposed at the sampling salons for one minute, then placed in the pre-cleaned jars and transported back to the laboratory together with the samples. Prior to extraction, all blanks, matrix spikes and samples were spiked with surrogate standards to evaluate extraction efficiencies. The recoveries of matrix spikes varied between 70 -

109 % for phthalates and 75 – 125% for OPEs. DEP-d4, DnBP-d4 and DEHP-d4 were used as surrogate standards for phthalates (AccuStandards Inc., USA). TEP-d15, TPrP-d21, TBP-d27,

TDCIPP-d15, TCEP-d12 and MTPhP for OPEs (Wellington Laboratories, Canada) (full names listed in Table A4.4). Surrogates recoveries for DEP-d4, DnBP-d4 and DEHP-d4 were 84 ± 26%,

89 ± 25% and 82 ± 24% (mean ± SD) respectively. Surrogates recoveries for TEP-d15, TPrP-d21,

TBP-d27, TDCIPP-d15, TCEP-d12 and MTPhP were 113 ± 47%, 140 ± 50%, 101 ± 65 %, 120 ±

46% and 150 ± 51% (mean ± SD), respectively. Results were recovery corrected for individual target compounds. Averages of field blank levels of each sample type were used for assessing the need for blank correction (and discarding samples) according to the criteria described by Saini et al. (2015). No blank correction was necessary, except for Di-n-octyl phthalate (DnOP) and Bis(2- ethylhexyl) tera phthalate (DEHtP) in brooches and wristbands. Full details of the QA/QC are provided in Appendix 3, section A4.3 and Table A4.6.

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4.2.5 Data Analysis

Descriptive and statistical analysis was performed with R version 3.4.2. Only compounds detected in > 70 % of all sample types were included in the statistical analysis.

Results below method detection limits (MDLs) were substituted by one half of MDL

(MDL/2). Concentrations of phthalates and OPEs in brooches and wristbands (ng dm-2 h-1) were obtained by normalizing the mass of a compound accumulated in brooches or wristbands (ng) to surface area of brooches or wristbands (dm2) and deployment time of brooch or wristbands (hour, h). Some workers (n = 14, 31%) participated on two sampling days; only one worker (2%) participated on three sampling days. A sensitivity analysis was conducted to determine the impact of these repeated samples on the results. In this sensitivity analysis, results including data from only each participant’s first visit (n = 45) were compared to results when data from all samples were included (n = 60). There was no difference in results between these two data sets, therefore results including all samples collected are presented.

Detection frequencies, medians, minimum and maximum values of 10 phthalates and 19

OPEs in active air samplers, silicone brooches and wristbands were calculated. Results were compared with those from previous studies in indoor environments such as hair salons, offices, homes, hair and nail salons, e-waste facilities, and commercial recycling facilities.

Quantile-quantile plots and the Shapiro-Wilk tests were used to assess the normality of the data. Since log-transformed concentrations did not improve the normality of distribution for most compounds in all matrices, we used the untransformed data and nonparametric statistical analyses.

Spearman rank’s correlation was used to assess the correlations of target compounds in active air samples vs brooches and active air samplers vs wristbands. We considered Spearman’s correlation coefficients of 0.00 – 0.19 to be very weak, 0.20 – 0.39 to be weak, 0.40 – 0.59 to be moderate,

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0.60 – 0.79 to be strong, and 0.80 – 1.0 to be very strong. Boxplots were plotted to illustrate the air concentrations of phthalates and OPEs for each type of services performed on all sampling days. Differences in concentrations between the number of services of each service type were investigated using the Mann Whitney U and Kruskal-Wallis tests. Differences were considered significant at p < 0.05.

4.3 Results and Discussion

In total, phthalates and OPEs were measured at 18 salons among 45 workers on 60 sampling days (Table A4.1, Appendix 3). In total, results from 60 active air samplers, 58 brooches and 60 wristbands are summarized here. Sampling time ranged from 4 to 9 hours with the average of 8 hours.

Overall, 45 (93%) of participants were female, ranging in age from 21 to 58 years (median

47 years). The median years of work in the industry was 5 (range <1-30 years) and the median hours per week worked in nail salons was 5 (range: 8 – 83 hour). The use of personal protective equipment was common; 56% or workers reported use of surgical/cloth mask, 80% reported use of gloves, and 87% reports use of protective clothing. Detailed types and numbers of services performed on all sampling days were provided in Table A4.2 (Appendix 3).

4.3.1 Levels of phthalates and OPEs in active air samplers and silicone samplers

4.3.1.1 Levels of phthalates and OPEs in active air samplers

Twelve (40%) target compounds including 7 phthalates and 5 OPEs were detected in active air samplers (Table A4.7, Appendix 3). Detection frequencies of those compounds ranged from 5 % for triethylphosphate (TEP) to 100 % for dimethyl phthalate (DMP), diethyl phthalate

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(DEP), diisobutyl phthalate (DiBP) and DnBP. In particular, Bis(2-ethylhexyl) phthalate (DEHP), a phthalate prohibited for use in cosmetics (Government of Canada, 2019), was found in 87% of active air samples. The detection frequency of TCEP was 98% in air samples in contrast to (Estill et al. (2020) who reported TCEP detection in less than 10% in industries including chemical and foam manufacturing, roofing and carpet installation.

-3 Median concentrations of ∑13 phthalates and OPEs were 1,230 and 444 ng m , respectively (Table 4.1). The most abundant compound found in active air samplers was diethyl

-3 phthalate (DEP) with a median of 471 ng m (28% of ∑13 phthalates and OPEs), followed by

DiBP and DnBP with median values of 337 and 331 ng m-3, respectively. These results are similar to the findings of previous studies (Hubinger and Havery, 2006; Koniecki et al., 2011; Young et al., 2018) where DEP, DnBP and DiBP were the most frequently detected phthalates in cosmetic and personal care products . The median level of DEHP (prohibited in cosmetics) was 36 ng m-3.

DEHtP and TPhP, which are suspected to be replacements of DEHP in cosmetics (Craig et al.,

2019; Mendelsohn et al., 2016), were detected in >80% of air samples collected by active air samplers with median values of 15 and 11 ng m-3, respectively.

Only a few phthalates and OPEs are regulated in the occupational environment. Levels of

DMP, DEHP, DEHP, dibutyl phthalate (including isomers DiBP and DnBP), TPhP measured using active sampling in this study were 4 orders of magnitude lower than the threshold limit values (TLVs) for those compounds recommended by American Conference of Governmental

Industrial Hygienists (ACGIH, 2018). However, many TLVs are set based on the risk of one health outcome and do not consider other possible outcomes. Further these limits are constrained by the epidemiological evidence at the time of review, which may not address current health concerns or

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consider the effects on underrepresent workers (e.g., women or visible minorities) (ACGIH,

2018).

Strong and significant correlations (Spearman’s rho = 0.99, p < 0.05) were observed between two structural isomers of dibutyl phthalates (DnBP and DiBP) (Table A4.8). DEP was strongly correlated with DiBP (Spearman’s rho = 0.63, p < 0.05) and DnBP (Spearman’s rho =

0.64, p < 0.05). Strong correlation can indicate that compounds arise from the similar sources

(e.g., personal care products and cosmetics). Most correlations between phthalates and selected

OPEs in personal active air samplers were weak and insignificant (Spearman’s rho < 0.39, p >

0.05), except for DEP which was correlated with TCEP (Spearman’s rho = 0.57, p < 0.05) and

TDCIPP (Spearman’s rho = 0.45, p < 0.05) (Table A4.8, Appendix 3).

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Table 4.1: Detection frequencies (DF), median, minimum and maximum values of selected 9 phthalates and 4 OPEs collected by active air samplers, silicone brooches and wristbands from nail salon technicians in Canada. Only compounds with detection frequencies > 70% in more than 2 samples types are presented.

Active air sampler (n = 60) (ng m-3) Brooch (n = 58) (ng dm-2 h-1) Wristband (n = 60) (ng dm-2 h-1) DF DF DF Compounds (%) Median Min Max (%) Median Min Max (%) Median Min Max DMP 100 43 9.6 256 100 68 20 306 97 16 0.02 55 DEP 100 471 66 13,700 100 72 18 1,470 100 156 16 4,380 DiBP 100 337 67 1,063 100 70 24 362 100 292 44 1,340 DnBP 100 331 67 1,034 97 74 0.1 1,700 98 453 0.1 2,160 DEHP 87 36 0.4 123 98 211 0.1 2,280 100 8,770 946 72,020 DnOP 0 ND ND ND 98 89 0.2 432 98 93 0.3 2,210 DiNP 0 ND ND ND 97 100 5.5 1,328 100 3,230 129 275,000 DEHtP 83 15 0.4 1,030 0 ND ND ND 100 5,800 200 643,000 DiDP 0 ND ND ND 90 67 2.7 1,160 100 2,140 140 69,700

∑9 Phthalates 1,230 751 20,950 TCEP 98 129 0.9 591 93 60 0.2 29,040 98 37 0.2 875 TCIPP 98 303 6.0 1,130 98 114 1.5 676 97 225 1.1 3,420 TDCIPP 77 1.1 0.1 9.3 100 7 0.5 197 100 212 3.4 8,032 TPhP 95 11 1.0 870 98 23 0.4 5,620 100 244 22 1,630

∑4OPEs 444 200 718 ∑ Phthalates & 13 1,680 955 21,700 OPEs ND: non-detected BzBP, TEP, TiPP, TPrP, TBP, TBPO, TPP, TEHP, TPPO, EHDPP, DOPP, ToCP, TmCP, TpCP, T2IPPP are not reported since detection frequencies of those compounds in more than two sample types were lower than 70%. Details of detection frequencies were listed in Table A4.7.

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4.3.1.2 Comparison of phthalates and OPEs levels in air with other indoor environments

Most indoor air studies (Saini et al., 2015; Tran et al., 2017; Tran and Kannan, 2015) of phthalate exposure have reported stationary samples (Table A4.11, Appendix 3). Median levels of phthalates and OPEs collected by personal active air samplers here were generally higher than those reported in office environment (Okeme et al., 2018a; Saini et al., 2015) and lower than other occupational environments such as hair salons (Tran et al., 2017; Tran and Kannan, 2015), e-waste facilities (Gravel et al., 2019c) and commercial recycling facilities (Gravel et al., 2019c).

The median level of DEP (471 ng m-3) measured here was comparable to those reported for Vietnamese hair salons (Tran et al., 2017) but ~3.6 times lower than those found in a small study of US hair and nail salons (Tran and Kannan, 2015). DEP was 2 times higher than in

Canadian offices (Okeme et al., 2018b; Saini et al., 2015). Different trends were observed for

DiBP and DnBP; levels here were comparable to those reported in US hair and nail salons (Tran and Kannan, 2015) but at least 1.6 times higher than those reported in Canadian offices (Okeme et al., 2018b; Saini et al., 2015). The median level of DEHP (36 ng m-3) found here was 2 lower than in Vietnamese hair salons (Tran and Kannan, 2015) and 7 times lower than US nail and hair salons (Tran et al., 2017). DEHP is found in building products (e.g., wall paper, wire and cable insulation) (Heudorf et al., 2007) as well as in nail polish.(Young et al., 2018).

Table A4.11 (Appendix 3) shows that air levels of OPEs exposed among nail salon workers were comparable for TCEP and at least 10 times lower for TDCIPP and TPhP compared to those measured among e-waste workers (Gravel et al., 2019c). Air levels of TPhP, an ingredient in some nail polishes, were ~1.5 times higher in the current study as compared to US nail salon workers (Estill et al., 2020). Further, levels of TCEP, TDCIPP and TPhP were up to 9 times lower than those reported from commercial recycling workers (Gravel et al., 2019c). Higher

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concentrations of OPEs found in e-waste facilities is expected as OPEs are used as flame retardants and plasticizers in electronic and electrical devices and other household products

(Stubbings et al., 2019a; Wei et al., 2015) which are dismantled and processed at these sites.

Results indicate that nail salon workers here exposed to OPEs at lower levels than workers at other occupational environment but higher levels than ambient environments.

4.3.1.3 Levels of phthalates and OPEs in silicone samplers

Nine phthalates and seven OPEs were detected in both silicone brooches and wristbands

(Table A4.7). Among those compounds, eight phthalates and four OPEs were detected in >70% of both silicone samplers. Most compounds detected in silicone wristbands were also found in silicone brooches, except from DEHtP and tri-m-cresyl phosphate (TmCP) which were found in wristbands but not brooches. TCEP had higher detection in the current study than in studies by

Okeme et al. (2018b) and Wang et al. (2019) for office workers and student participants (Table

A4.9, Appendix 3). This is somewhat surprising as TCEP has not been reported as an ingredient in personal care products or cosmetics.

DEHP was the most abundant compound found in both brooches and wristbands with median values of 210 and 8,770 ng dm-2 h-1, respectively. Among OPEs, the highest concentrations found in brooch and wristbands was of tris(2-chloroisopropyl) phosphate (TCIPP) with median values of 114 ng dm-2 h-1 and TPhP with median values of 244 ng dm-2 h-1, respectively. Total median concentration of phthalates and OPEs in wristbands were ~22 times higher than in brooches. It is consistent with the finding of Nguyen et al. (2020) who reported levels of OPEs found in brooches were higher than those measured in wristbands, supporting the suggestion of Wang et al. (2019) that wristbands capture higher levels than brooches.

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One challenge in comparing levels of chemicals measured using passive samplers is that previous studies report various measurement units (Table A4.9, Appendix 3). Here, we use the

-2 -1 unit of ng dm h . Median OPE levels in wristbands from nail salon workers were comparable for TCEP, but at least 3 times higher for TCIPP, TDCIPP and TPhP compared to those for e-waste workers in Canada (Nguyen et al., 2020) and Bangladesh (Wang et al., 2020). The source(s) of the relatively high levels TCIPP, TCEP and TDCIPP in nail salons are not evident. Median levels of individual phthalates and OPEs in wristbands were at least 1.5 times higher for phthalates and at least 51 times higher for OPEs, respectively compared with those reported by Craig et al. (2019) for US nail salons workers. Median levels of TCEP, TCIPP, TDCIPP and TPhP in wristbands reported here were up to 45, 58, 21 and 63 times, respectively, higher than those found in wristbands among non-occupational participants in US homes (Romanak et al., 2019; Wang et al.,

2019).

4.3.2 Relationships between air concentrations and services performed

We hypothesized that the numbers of services performed would be correlated with concentrations of phthalates and OPEs collected by active air samplers. In general, our results did not support that hypothesis (Figures A4.1 – A4.2 and Table A4.10 in Appendix 3). Interestingly, the highest concentrations of DMP, DiBP, DnBP and TCIPP (median: 65, 598, 573 and 521 ng m-3, respectively) were observed on sampling days when no manicure services were performed.

And the highest concentrations of DEP, DEHP, DEHtP, TCEP and TPhP (median: 713, 54, 38,

169 and 14 ng m-3, respectively) were observed on sampling days when no pedicure services were performed. Only air concentrations of DMP, DEP, DiBP and DnBP were significantly (p > 0.05) associated with the numbers of other services (including eyebrows/eyelash service, waxing, facial

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service and massage) performed. Anecdotally, workers were observed to do their own nails when the salon was not busy; this was not recorded in a standardized way and these activities were not treated as services provided in the current analysis.

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Figure 4.1. Boxplots for concentrations of selected phthalates with detection frequencies >70% in air collected by active air samplers according to number of services performed for each worker-day (including any services, manicure, pedicure, artificial nails and others). The horizontal line in the boxes is the median, the top and bottom of the boxes are 75th and 25th percentiles, respectively. The top and bottom whiskers are the maximum and minimum values, respectively. ▲Any services included at least one of the following services: manicure, pedicure, artificial nail and other services. ■Other services included eyebrows/eyelash service, waxing, facial service and massage. *Air concentrations of the group “0 services” were statistically significantly (p < 0.05) lower than those of the group “>1 services” in other services category.

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Figure 4.2. Boxplots for concentrations of selected organophosphorus esters with detection frequencies >70% in air collect by active air samplers according to number of services performed for each worker-day (including any services, manicure, pedicure, artificial nails and others). The horizontal line in the boxes is the median, the top and bottom of the boxes are 75th and 25th percentiles, respectively. The top and bottom whiskers are the maximum and minimum values, respectively. ▲Any services included at least one of the following services: manicure, pedicure, artificial nail and other services. ■Other services included eyebrows/eyelash service, waxing, facial service and massage. 153

4.3.3 Comparison of active air samplers and silicone passive samplers

Relationships between paired samples of active air samplers vs. brooches and active air samplers vs. wristbands were investigated to assess the use of silicone samplers in measuring exposure to phthalates and OPEs nail salons (Table 4.2). Among nine compounds with detection frequencies >70% in all matrices, five out of nine compounds (TCEP, TPhP,

DEP, DnBP and TDCIPP) in brooches had significant associations with the active air samplers

(Spearman’s rho = 0.37 – 0.48, p < 0.05). Our results are inconsistent with Nguyen et al. (2020) for e-waste workers where they found moderate and strong correlations (Spearman’s rho >

0.46, p < 0.05) between active air samplers and brooches for most OPEs, except for TCEP and tris(2-butoxyethyl)phosphate (TBOEP). One explanation is that the ventilation rates in a large e-waste facilities with mechanical ventilation were higher than those in a small and mostly closed-door nail salons, leading to high variability in air concentrations in nail salons. Another explanation is that emissions from the nail products were to a stagnant, poorly mixed air mass because the workers were relatively stationary, allowing higher contaminant levels compared to ambient air relative to more active workers in other occupational settings. The weak and insignificant correlations (Spearman’s rho < 0.39, p >0.05) between active air samples and silicone wristbands found for most compounds was similar to the findings of Nguyen et al.

(2020) for e-waste workers. No trend was observed between median levels of selected compounds in silicone samplers (brooches and wristbands) and their respective octanol-air partitioning coefficient (log Koa) (see Figure A4.2, Appendix 3).

Stronger correlations observed between brooches and wristbands for most compounds

(except from DMP) possibly result from the fact that brooch and wristbands made by the same material and chemically analyze by using the similar procedures. Overall, our results showed that there were significant relationships between chemical sampling for several phthalate and

OPEs by active air samplers vs passive brooches and wristbands.

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Table 4.2. Spearman’s correlation coefficients (rho) and p-values (p) for the concentrations of selected phthalates and OPEs with detection frequencies >70% in paired sample matrices. Numbers in bold are statistically significant with p-value < 0.05.

Active air sampler Active air sampler Brooches vs Compounds vs Brooches vs Wristbands Wristbands rho p rho p rho P Phthalate esters DMP 0.19 0.15 0.54 <0.001 0.42 0.001 DEP 0.43 <0.001 0.37 0.005 0.49 <0.001 DiBP 0.21 0.11 -0.04 0.77 0.01 0.94 DnBP 0.43 0.001 -0.11 0.42 0.1 0.46 DEHP 0.11 0.40 0.26 0.05 0.29 0.03 Organophosphorus esters (OPEs) TCEP 0.37 0.004 0.21 0.11 0.54 <0.001 TCIPP 0.16 0.23 0.06 0.67 0.50 <0.001 TDClPP 0.48 <0.001 0.16 0.21 0.40 0.002 TPhP 0.39 0.003 0.49 <0.001 0.49 <0.001

4.4 Strengths and limitations

The study, is the first full study with 45 participants, reported exposure levels of a wide range of phthalates and OPEs in nail salon environment. This study advanced our understanding of the use of silicone wristbands and brooches as personal passive samplers in occupational settings where deployment times are relatively short. Silicone brooches and wristbands accumulated detectable amounts of 16 (55%) and 19 (66%) phthalates and OPEs, respectively, during the average of 8 hours period. Hence, silicone brooches and wristbands can be useful to use as the screening tool for measuring SVOCs in indoor occupational settings such as nail salons.

Our study had several limitations. This study was unlikely to capture the full scope of variability in work tasks and exposure as there are more than 1,400 establishments licensed to provide nail services in the City of Toronto alone of which we sampled at 18 nail salons. Since we only collected information on the number of services the workers provided to clients, we

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may have missed information on other tasks that could have influenced the observed exposure levels (e.g. doing their own nails, cleaning activities, etc.).

Acknowledgments

Funding was provided by Ontario Ministry of Labour Research Opportunities

Program and Natural Sciences and Engineering Research Council of Canada (NSERC,

RGPAS 429679-12 and RGPIN-2017-06654). We are thankful for the nail technicians and salon owners who chose to participate in this study. We thank the Healthy Nail Salon

Network (HNSN) based at the Parkdale Queen-West Community Health Center in Toronto,

Canada for their support of this research. We also thank Tammy Khuc, Cindy Pham and

Xiaoke Zeng for their role in recruitment and communication, and Sarah Bernstein for laboratory support.

References

Abbasi, G., Buser, A.M., Soehl, A., Murray, M.W., Diamond, M.L., 2015. Stocks and flows of PBDEs in products from use to waste in the U.S. and canada from 1970 to 2020. Environ. Sci. Technol. 49, 1521–1528. https://doi.org/10.1021/es504007v Abbasi, G., Saini, A., Goosey, E., Diamond, M.L., 2016. Product screening for sources of halogenated flame retardants in Canadian house and office dust. Sci. Total Environ. 545–546, 299–307. https://doi.org/10.1016/j.scitotenv.2015.12.028 Abdallah, M.A.-E., Pawar, G., Harrad, S., 2015a. Evaluation of 3D-human skin equivalents for assessment of human dermal absorption of some brominated flame retardants. Environ. Int. 84, 64–70. https://doi.org/10.1016/j.envint.2015.07.015 Abdallah, M.A.-E., Pawar, G., Harrad, S., 2015b. Effect of Bromine Substitution on Human Dermal Absorption of Polybrominated Diphenyl Ethers. Environ. Sci. Technol. 49, 10976–10983. https://doi.org/10.1021/acs.est.5b03904 Abou-Elwafa Abdallah, M., Pawar, G., Harrad, S., 2016. Human dermal absorption of chlorinated organophosphate flame retardants; implications for human exposure. Toxicol. Appl. Pharmacol. 291, 28–37. https://doi.org/10.1016/j.taap.2015.12.004 ACGIH, 2018. TLVs ® and BEIs ® : Threshold limit values for chemical substances and physical agents biological exposure indices. American Conference of Governmental Industrial Hygienists, Cincinnati, OH, OH. ACGIH, 2001. Documentation of threshold limit values for substances in work environment. American Conference of Governmental Industrial Hygienists, Cincinnati, OH, OH.

156

Ait, Y., Araki, A., Kawai, T., Tsuboi, T., Saito, I., Yoshioka, E., Kanazawa, A., 2014. Science of the Total Environment Associations of phthalate concentrations in fl oor dust and multi-surface dust with the interior materials in Japanese dwellings. Sci. Total Environ. 468–469, 147–157. https://doi.org/10.1016/j.scitotenv.2013.07.107 Akormedi, M., Asampong, E., Fobil, J.N., 2013. Working conditions and environmental exposures among electronic waste workers in Ghana. Int. J. Occup. Environ. Health 19, 278–286. https://doi.org/10.1179/2049396713Y.0000000034 Allen, J.G., McClean, M.D., Stapleton, H.M., Nelson, J.W., Webster, T.F., 2007. Personal Exposure to Polybrominated Diphenyl Ethers (PBDEs) in Residential Indoor Air. Environ. Sci. Technol. 41, 4574–4579. https://doi.org/10.1021/es0703170 Allen, J.O., Dookeran, N.M., Smith, K.A., Sarofim, A.F., Taghizadeh, K., Lafleur, A.L., 1996. Measurement of polycyclic aromatic hydrocarbons associated with size- segregated atmospheric aerosols in Massachusetts. Environ. Sci. Technol. 30, 1023– 1031. https://doi.org/10.1021/es950517o Andersen, C., Krais, A.M., Eriksson, A.C., Jakobsson, J., Löndahl, J., Nielsen, J., Lindh, C.H., Pagels, J., Gudmundsson, A., Wierzbicka, A., 2018. Inhalation and Dermal Uptake of Particle and Gas-Phase Phthalates—A Human Exposure Study. Environ. Sci. Technol. 52, 12792–12800. https://doi.org/10.1021/acs.est.8b03761 Asante, K.A., Agusa, T., Biney, C.A., Agyekum, W.A., Bello, M., Otsuka, M., Itai, T., Takahashi, S., Tanabe, S., 2012. Multi-trace element levels and arsenic speciation in urine of e-waste recycling workers from Agbogbloshie, Accra in Ghana. Sci. Total Environ. 424, 63–73. https://doi.org/10.1016/j.scitotenv.2012.02.072 ATSDR, 2012. Toxicological Profile for Phosphate Ester Flame Retardants. ATSDR, 2005. Public Health Assessment Guidance Manual (2005 Update). Atlanta, Georgia. ATSDR, 2004. Toxicological profile for polybrominated biphenyl and polybrominated diphenyl ethers 1–599. Awasthi, A.K., Wang, M., Wang, Z., Awasthi, M.K., Li, J., 2018. E-waste management in India: A mini-review. Waste Manag. Res. 36, 408–414. https://doi.org/10.1177/0734242X18767038 Bakhiyi, B., Gravel, S., Ceballos, D., Flynn, M.A., Zayed, J., 2018. Has the question of e- waste opened a Pandora’s box? An overview of unpredictable issues and challenges. Environ. Int. 110, 173–192. https://doi.org/https://doi.org/10.1016/j.envint.2017.10.021 Balde, C.P., Forti, V., Gray, V., Kuehr, R., Stegmann, P., 2017. The global e-waste monitor 2017, United Nations University. https://doi.org/10.1016/j.proci.2014.05.148 Baldé, C.P., Wang, F., Kuehr, R., Huisman, J., 2015. The Global E-waste Monitor 2014: Quantitites, flows and resources. Bonn, Germany. https://doi.org/ISBN 978-92-808- 4556-3 Bartkow, M.E., Booij, K., Kennedy, K.E., Müller, J.F., Hawker, D.W., 2005. Passive air sampling theory for semivolatile organic compounds. Chemosphere 60, 170–176. https://doi.org/10.1016/j.chemosphere.2004.12.033 Basel Convention, 2011. Electrical and electronic equipment when becoming waste (e- waste) such as personal computers, printers, televisions, mobile phones, refrigerators and air-conditioning units is one of the fastest growing waste streams in the world today. [WWW Document]. URL http://www.basel.int/Implementation/Ewaste/Overview/tabid/4063/Default.aspx (accessed 3.8.20). Beaucham, C.C., Ceballos, D., Page, E.H., Mueller, C., Calafat, A.M., Sjodin, A., Ospina, M., Guardia, M. La, Glassford, E., 2018. Evaluation of Exposure to Metals , Flame Retardants , and Nanomaterials at an Electronics Recycling Company 1–80.

157

Behl, M., Hsieh, J.H., Shafer, T.J., Mundy, W.R., Rice, J.R., Boyd, W.A., Freedman, J.H., Hunter, E.S., Jarema, K.A., Padilla, S., Tice, R.R., 2015. Use of alternative assays to identify and prioritize organophosphorus flame retardants for potential developmental and neurotoxicity. Neurotoxicol. Teratol. 52, 181–193. https://doi.org/10.1016/j.ntt.2015.09.003 Behl, M., Rice, J.R., Smith, M. V., Co, C.A., Bridge, M.F., Hsieh, J.-H., Freedman, J.H., Boyd, W.A., 2016. Editor’s Highlight: Comparative Toxicity of Organophosphate Flame Retardants and Polybrominated Diphenyl Ethers to Caenorhabditis elegans. Toxicol. Sci. 154, 241–252. https://doi.org/10.1093/toxsci/kfw162 Bergh, C., Torgrip, R., Emenius, G., Östman, C., 2011. Organophosphate and phthalate esters in air and settled dust - a multi-location indoor study. Indoor Air 21, 67–76. https://doi.org/10.1111/j.1600-0668.2010.00684.x Betts, K.S., 2002. Rapidly rising PBDE levels in North America. Environ. Sci. Technol. 36, 50A-52A. https://doi.org/10.1021/es022197w Bi, C., Liang, Y., Xu, Y., 2015. Fate and Transport of Phthalates in Indoor Environments and the Influence of Temperature: A Case Study in a Test House. Environ. Sci. Technol. 49, 9674–9681. https://doi.org/10.1021/acs.est.5b02787 Bidleman, T.F., 1988. Atmospheric processes. Environ. Sci. Technol. 22, 361–367. https://doi.org/10.1021/es00169a002 Blum, A., Behl, M., Birnbaum, L.S., Diamond, M.L., Phillips, A., Singla, V., Sipes, N.S., Stapleton, H.M., Venier, M., 2019. Organophosphate Ester Flame Retardants: Are They a Regrettable Substitution for Polybrominated Diphenyl Ethers? Environ. Sci. Technol. Lett. 6, 638–649. https://doi.org/10.1021/acs.estlett.9b00582 Bohlin, P., Audy, O., Škrdlíková, L., Kukučka, P., Přibylová, P., Prokeš, R., Vojta, Š., Klánová, J., 2014. Outdoor passive air monitoring of semi volatile organic compounds (SVOCs): a critical evaluation of performance and limitations of polyurethane foam (PUF) disks. Environ. Sci. Process. Impacts 16, 433–444. https://doi.org/10.1039/C3EM00644A Bohlin, Pernilla, Audy, O., Škrdlíková, L., Kukučka, P., Vojta, Š., Přibylová, P., Prokeš, R., Čupr, P., Klánová, J., 2014. Evaluation and guidelines for using polyurethane foam (PUF) passive air samplers in double-dome chambers to assess semi-volatile organic compounds (SVOCs) in non-industrial indoor environments. Environ. Sci. Process. Impacts 16, 2617–2626. https://doi.org/10.1039/C4EM00305E Bohlin, P., Jones, K.C., Levin, J.-O., Lindahl, R., Strandberg, B., 2010a. Field evaluation of a passive personal air sampler for screening of PAH exposure in workplaces. J. Environ. Monit. 12, 1437. https://doi.org/10.1039/c0em00018c Bohlin, P., Jones, K.C., Strandberg, B., 2010b. Field evaluation of polyurethane foam passive air samplers to assess airborne PAHs in occupational environments. Environ. Sci. Technol. 44, 749–754. https://doi.org/10.1021/es902318g Bohlin, P., Jones, K.C., Strandberg, B., 2007. Occupational and indoor air exposure to persistent organic pollutants: A review of passive sampling techniques and needs. J. Environ. Monit. 9, 501. https://doi.org/10.1039/b700627f Bornehag, C.G., Nanberg, E., 2010. Phthalate exposure and asthma in children 33, 333–345. https://doi.org/10.1111/j.1365-2605.2009.01023.x Braun, J.M., Kalkbrenner, A.E., Just, A.C., Yolton, K., Calafat, A.M., Sjödin, A., Hauser, R., Webster, G.M., Chen, A., Lanphear, B.P., 2014. Gestational Exposure to Endocrine- Disrupting Chemicals and Reciprocal Social, Repetitive, and Stereotypic Behaviors in 4- and 5-Year-Old Children: The HOME Study. Environ. Health Perspect. 122, 513– 520. https://doi.org/10.1289/ehp.1307261 Breul, S., Van Landuyt, K.L., Reichl, F.X., Högg, C., Hoet, P., Godderis, L., Van Meerbeek,

158

B., Cokic, S.M., 2020. Filtration efficiency of surgical and FFP3 masks against composite dust. Eur. J. Oral Sci. 128, 233–240. https://doi.org/10.1111/eos.12697 Brown, J., Gordon, T., Price, O., Asgharian, B., 2013. Thoracic and respirable particle deinitions for human health risk assessment. Part. Fibre Toxicol. 10, 1–12. Cahill, T.M., Groskova, D., Charles, M.J., Sanborn, J.R., Denison, M.S., Baker, L., 2007. Atmospheric concentrations of polybrominated diphenyl ethers at near-source sites. Environ. Sci. Technol. 41, 6370–6377. https://doi.org/10.1021/es070844j Callesen, M., Bekö, G., Weschler, C.J., Langer, S., Brive, L., Clausen, G., Toftum, J., Sigsgaard, T., Høst, A., Kold, T., 2014. International Journal of Hygiene and Phthalate metabolites in urine and asthma , allergic rhinoconjunctivitis and atopic dermatitis in preschool children. Int. J. Hyg. Environ. Health 217, 645–652. https://doi.org/10.1016/j.ijheh.2013.12.001 Cao, Z., Xu, F., Covaci, A., Wu, M., Wang, H., Yu, G., Wang, B., Deng, S., Huang, J., Wang, X., 2014. Distribution patterns of brominated, chlorinated, and phosphorus flame retardants with particle size in indoor and outdoor dust and implications for human exposure. Environ. Sci. Technol. 48, 8839–8846. https://doi.org/10.1021/es501224b Carignan, C.C., Mínguez-Alarcón, L., Butt, C.M., Williams, P.L., Meeker, J.D., Stapleton, H.M., Toth, T.L., Ford, J.B., Hauser, R., 2017. Urinary Concentrations of Organophosphate Flame Retardant Metabolites and Pregnancy Outcomes among Women Undergoing in Vitro Fertilization. Environ. Health Perspect. 125, 087018. https://doi.org/10.1289/EHP1021 Carignan, C.C., Mínguez-Alarcón, L., Williams, P.L., Meeker, J.D., Stapleton, H.M., Butt, C.M., Toth, T.L., Ford, J.B., Hauser, R., 2018. Paternal urinary concentrations of organophosphate flame retardant metabolites, fertility measures, and pregnancy outcomes among couples undergoing in vitro fertilization. Environ. Int. 111, 232–238. https://doi.org/10.1016/j.envint.2017.12.005 Castorina, R., Bradman, A., Stapleton, H.M., Butt, C., Avery, D., Harley, K.G., Gunier, R.B., Holland, N., Eskenazi, B., 2017. Current-use flame retardants: Maternal exposure and neurodevelopment in children of the CHAMACOS cohort. Chemosphere 189, 574– 580. https://doi.org/10.1016/j.chemosphere.2017.09.037 Ceballos, D.M., Côté, D., Bakhiyi, B., Flynn, M.A., Zayed, J., Gravel, S., Herrick, R.F., Labrèche, F., 2020. Overlapping vulnerabilities in workers of the electronics recycling industry formal sector: A commentary. Am. J. Ind. Med. 63, 955–962. https://doi.org/10.1002/ajim.23173 Ceballos, D.M., Dong, Z., 2016. The formal electronic recycling industry: Challenges and opportunities in occupational and environmental health research. Environ. Int. 95, 157– 166. https://doi.org/10.1016/j.envint.2016.07.010 CEPA, 1999. Canadian Environmental Protection Act. Cequier, E., Sakhi, A.K., Marcé, R.M., Becher, G., Thomsen, C., 2015. Human exposure pathways to organophosphate triesters — A biomonitoring study of mother–child pairs. Environ. Int. 75, 159–165. https://doi.org/10.1016/j.envint.2014.11.009 Chan, J.K.Y., Wong, M.H., 2013. A review of environmental fate, body burdens, and human health risk assessment of PCDD/Fs at two typical electronic waste recycling sites in China. Sci. Total Environ. 463–464, 1111–1123. https://doi.org/10.1016/j.scitotenv.2012.07.098 Cherrie, J.W., 2003. CommentaryThe Beginning of the Science Underpinning Occupational Hygiene. Ann. Occup. Hyg. 47, 179–185. https://doi.org/10.1093/annhyg/meg030 City of Toronto, 2019. Search for an Establishment Monitored by BodySafe [WWW Document]. URL https://www.toronto.ca/community-people/health-wellness-

159

care/health-programs-advice/bodysafe/search-for-an-establishment-space-holder-for- map/ (accessed 7.18.19). Consumer Product Safety Commission, 2008. Consumer Product Safety Improvement Act of 2008. Craig, J.A., Ceballos, D.M., Fruh, V., Petropoulos, Z.E., Allen, J.G., Calafat, A.M., Ospina, M., Stapleton, H.M., Hammel, S., Gray, R., Webster, T.F., 2019. Exposure of Nail Salon Workers to Phthalates, Di(2-ethylhexyl) Terephthalate, and Organophosphate Esters: A Pilot Study. Environ. Sci. Technol. 53, 14630–14637. https://doi.org/10.1021/acs.est.9b02474 de Winter-Sorkina, R., Bakker, M.., Wolterink, G., Zielmaker, M.J., 2006. Brominated flame retardants: occurrence, dietary intake and risk assessment [WWW Document]. URL https://www.rivm.nl/bibliotheek/rapporten/320100002.pdf (accessed 6.7.18). Delgado-Saborit, J.M., Stark, C., Harrison, R.M., 2014. Use of a versatile high efficiency multiparallel denuder for the sampling of PAHs in ambient air: Gas and particle phase concentrations, particle size distribution and artifact formation. Environ. Sci. Technol. 48, 499–507. https://doi.org/10.1021/es402937d Dixon, H.M., Scott, R.P., Holmes, D., Calero, L., Kincl, L.D., Waters, K.M., Camann, D.E., Calafat, A.M., Herbstman, J.B., Anderson, K.A., 2018. Silicone wristbands compared with traditional polycyclic aromatic hydrocarbon exposure assessment methods. Anal. Bioanal. Chem. 410, 3059–3071. https://doi.org/10.1007/s00216-018-0992-z Eakin, J.M., Champoux, D., MacEachen, E., 2017. Health and safety in small workplaces: refocusing upstream. Can. J. Public Health 101 Suppl, S29-33. EC, 2018. Waste Electrical & Electronic Equipment (WEEE) [WWW Document]. Eur. Comm. https://doi.org/10.1016/j.geb.2005.03.002 Ekelund, M., Azhdar, B., Gedde, U.W., 2010. Evaporative loss kinetics of di(2- ethylhexyl)phthalate (DEHP) from pristine DEHP and plasticized PVC. Polym. Degrad. Stab. 95, 1789–1793. https://doi.org/10.1016/j.polymdegradstab.2010.05.007 Eriksson, P., Jakobsson, E., Fredriksson, A., 2001. Brominated flame retardants: a novel class of developmental toxicants in our environment? Environ. Health Perspect. 109, 903–908. https://doi.org/10.1289/ehp.01109903 Estill, C.F., Slone, J., Mayer, A., Chen, I.-C., La Guardia, M.J., 2020. Worker exposure to flame retardants in manufacturing, construction and service industries. Environ. Int. 135, 105349. https://doi.org/10.1016/j.envint.2019.105349 European Commission, 2014. COMMUNICATION FROM THE COMMISSION on the finalisation of the restriction process on the four phthalates (DEHP, DBP, BBP and DIBP) under Regulation (EC) No 1907/2006 of the European Parliament and of the Council concerning Registration, Evaluation, Authori. Off. J. Eur. Union 73, 1–4. ExpoStats, 2015. NDExpo – Treatment of non-detects in industrial hygiene samples [WWW Document]. URL http://www.expostats.ca/site/app-local/NDExpo/ (accessed 2.20.20). Factor-Litvak, P., Insel, B., Calafat, A.M., Liu, X., Perera, F., Rauh, V.A., Whyatt, R.M., 2014. Persistent Associations between Maternal Prenatal Exposure to Phthalates on Child IQ at Age 7 Years. PLoS One 9, e114003. https://doi.org/10.1371/journal.pone.0114003 Federman, M.N., Harrington, D.E., Krynski, K.J., 2006. Vietnamese Manicurists: Are Immigrants Displacing Natives or Finding New Nails to Polish? ILR Rev. 59, 302–318. https://doi.org/10.1177/001979390605900207 Fisher, M., Arbuckle, T.E., MacPherson, S., Braun, J.M., Feeley, M., Gaudreau, É., 2019. Phthalate and BPA Exposure in Women and Newborns through Personal Care Product Use and Food Packaging. Environ. Sci. Technol. 53, 10813–10826. https://doi.org/10.1021/acs.est.9b02372

160

Flanagan, M.E., Seixas, N., Majar, M., Camp, J., Morgan, M., 2003. Silica Dust Exposures During Selected Construction Activities. AIHA J. 64, 319–328. https://doi.org/10.1080/15428110308984823 Fortia, V., Balde, C.P., Kuehr, R., Bel, G., 2020. The Global E-waste Monitor 2020: Quantitites, flows and circular economy potential [WWW Document]. URL https://collections.unu.edu/view/UNU:7737 (accessed 10.13.20). Fraser, A.J., Webster, T.F., McClean, M.D., 2009. Diet Contributes Significantly to the Body Burden of PBDEs in the General U.S. Population. Environ. Health Perspect. 117, 1520– 1525. https://doi.org/10.1289/ehp.0900817 Frazzoli, C., Orisakwe, O.E., Dragone, R., Mantovani, A., 2010. Diagnostic health risk assessment of electronic waste on the general population in developing countries’ scenarios. Environ. Impact Assess. Rev. 30, 388–399. https://doi.org/10.1016/j.eiar.2009.12.004 Frederiksen, M., Stapleton, H.M., Vorkamp, K., Webster, T.F., Jensen, N.M., Sørensen, J.A., Nielsen, F., Knudsen, L.E., Sørensen, L.S., Clausen, P.A., Nielsen, J.B., 2018. Dermal uptake and percutaneous penetration of organophosphate esters in a human skin ex vivo model. Chemosphere 197, 185–192. https://doi.org/10.1016/j.chemosphere.2018.01.032 Fromme, H., Becher, G., Hilger, B., Völkel, W., 2016. Brominated flame retardants - Exposure and risk assessment for the general population. Int. J. Hyg. Environ. Health 219, 1–23. https://doi.org/10.1016/j.ijheh.2015.08.004 Gaspar, F.W., Castorina, R., Maddalena, R.L., Nishioka, M.G., McKone, T.E., Bradman, A., 2014. Phthalate exposure and risk assessment in California child care facilities. Environ. Sci. Technol. 48, 7593–7601. https://doi.org/10.1021/es501189t Gevao, B., Al-Bahloul, M., Al-Ghadban, A.N., Ali, L., Al-Omair, A., Helaleh, M., Al- Matrouk, K., Zafar, J., 2006. Polybrominated diphenyl ethers in indoor air in Kuwait: Implications for human exposure. Atmos. Environ. 40, 1419–1426. https://doi.org/10.1016/j.atmosenv.2005.10.053 Gioia, R., Steinnes, E., Thomas, G.O., Mejier, S.N., Jones, K.C., 2006. Persistent organic pollutants in European background air: derivation of temporal and latitudinal trends. J. Environ. Monit. 8, 700. https://doi.org/10.1039/b604821h Giovanoulis, G., Bui, T., Xu, F., Papadopoulou, E., Padilla-Sanchez, J.A., Covaci, A., Haug, L.S., Cousins, A.P., Magnér, J., Cousins, I.T., de Wit, C.A., 2018. Multi-pathway human exposure assessment of phthalate esters and DINCH. Environ. Int. 112, 115– 126. https://doi.org/10.1016/j.envint.2017.12.016 Glazer, L., Hawkey, A.B., Wells, C.N., Drastal, M., Odamah, K.-A., Behl, M., Levin, E.D., 2018. Developmental Exposure to Low Concentrations of Organophosphate Flame Retardants Causes Life-Long Behavioral Alterations in Zebrafish. Toxicol. Sci. 165, 487–498. https://doi.org/10.1093/toxsci/kfy173 Godwin, A.D., 2017. Plasticizers, in: Applied Plastics Engineering Handbook. Elsevier, pp. 533–553. Godwin, A.D., 2010. Uses of Phthalates and Other Plasticizers [WWW Document]. URL https://www.cpsc.gov/s3fs-public/godwin.pdf (accessed 10.21.20). Gong, M., Weschler, C.J., Zhang, Y., 2016. Impact of Clothing on Dermal Exposure to Phthalates: Observations and Insights from Sampling Both Skin and Clothing. Environ. Sci. Technol. 50, 4350–4357. https://doi.org/10.1021/acs.est.6b00113 Goodyer, C.G., Poon, S., Aleksa, K., Hou, L., Atehortua, V., Carnevale, A., Jednak, R., Emil, S., Bagli, D., Dave, S., Hales, B.F., Chevrier, J., 2017. A case-control study of maternal polybrominated diphenyl ether (PBDE) exposure and cryptorchidism in Canadian populations. Environ. Health Perspect. 125, 1–9. https://doi.org/10.1289/EHP522

161

Gouin, T., Harner, T., Blanchard, P., Mackay, D., 2005. Passive and Active Air Samplers as Complementary Methods for Investigating Persistent Organic Pollutants in the Great Lakes Basin. Environ. Sci. Technol. 39, 9115–9122. https://doi.org/10.1021/es051397f Goverment of Canada, 2017. Phthalates Regulations Règlement sur les phtalates 21–23. Government of Canada, 2019. Cosmetic Ingredient Hotlist [WWW Document]. URL https://www.canada.ca/en/health-canada/services/consumer-product- safety/cosmetics/cosmetic-ingredient-hotlist-prohibited-restricted- ingredients/hotlist.html#tbl1 (accessed 5.4.20). Government of Canada, 2016. Toxic substances list: PBDEs [WWW Document]. Government of Canada, 2012. Regulations Amending the Prohibition of Certain Toxic Substances Regulations, 2012 [WWW Document]. Canada Gaz. Part II. URL http://www.gazette.gc.ca/rp-pr/p2/2016/2016-10-05/pdf/g2-15020.pdf (accessed 2.18.21). Government of Ontario, 2018. Waste management [WWW Document]. URL https://www.ontario.ca/page/waste-management (accessed 12.9.18). Graham, P.R., 1973. Phthalate ester plasticizers—why and how they are used. Environ. Health Perspect. 3, 3–12. https://doi.org/10.1289/ehp.73033 Grant, K., Goldizen, F.C., Sly, P.D., Brune, M.-N., Neira, M., van den Berg, M., Norman, R.E., 2013. Health consequences of exposure to e-waste: a systematic review. Lancet Glob. Heal. 1, e350–e361. https://doi.org/10.1016/S2214-109X(13)70101-3 Gravel, S., Bakhiyi, B., Lavoué, J., Verner, M.-A., Zayed, J., Labreche, F., 2019a. Electronic waste recycling exposure and hormone levels in workers., in: 27th EPICOH International Symposium on Epidemiology in Occupational Health. Wellington, NewZealand. Gravel, S., Diamond, M.L., Jantunen, L.M., Verner, M.-A., Zayed, J., Labrèche, F., 2019b. Is airborne concentration of BDE209 associated with serum concentration in recycling workers?, in: 9th International Symposium on Flame Retardants BFR 2019. Montreal, Canada. Gravel, S., Lavoué, J., Bakhiyi, B., Diamond, M.L., Jantunen, L.M., Lavoie, J., Roberge, B., Verner, M.-A., Zayed, J., Labrèche, F., 2019c. Halogenated flame retardants and organophosphate esters in the air of electronic waste recycling facilities: Evidence of high concentrations and multiple exposures. Environ. Int. 128, 244–253. https://doi.org/10.1016/j.envint.2019.04.027 Gravel, S., Lavoué, J., Bakhiyi, B., Lavoie, J., Roberge, B., Patry, L., Bouchard, M.F., Verner, M., Zayed, J., Labrèche, F., 2020. Multi-exposures to suspected endocrine disruptors in electronic waste recycling workers: Associations with thyroid and reproductive hormones. Int. J. Hyg. Environ. Health 225, 113445. https://doi.org/10.1016/j.ijheh.2019.113445 Guo, J., Lin, K., Deng, J., Fu, X., Xu, Z., 2015. Polybrominated diphenyl ethers in indoor air during waste TV recycling process. J. Hazard. Mater. 283, 439–446. https://doi.org/10.1016/j.jhazmat.2014.09.044 Guo, Y., Kannan, K., 2013. A survey of phthalates and parabens in personal care products from the United States and its implications for human exposure. Environ. Sci. Technol. 47, 14442–14449. https://doi.org/10.1021/es4042034 Guo, Y., Kannan, K., 2011. Comparative Assessment of Human Exposure to Phthalate Esters from House Dust in China and the United States. Environ. Sci. Technol. 45, 3788–3794. https://doi.org/10.1021/es2002106 Hammel, S., Hoffman, K., Webster, T.F., Anderson, K.A., Stapleton, H.M., 2016. Measuring Personal Exposure to Organophosphate Flame Retardants using Silicone Wristbands and Hand Wipes. Environ. Sci. Technol. acs.est.6b00030.

162

https://doi.org/10.1021/acs.est.6b00030 Hammel, S.C., Phillips, A.L., Hoffman, K., Stapleton, H.M., 2018. Evaluating the Use of Silicone Wristbands To Measure Personal Exposure to Brominated Flame Retardants. Environ. Sci. Technol. 52, acs.est.8b03755. https://doi.org/10.1021/acs.est.8b03755 Harley, K.G., Marks, A.R., Chevrier, J., Bradman, A., Sjödin, A., Eskenazi, B., 2010. PBDE Concentrations in Women’s Serum and Fecundability. Environ. Health Perspect. 118, 699–704. https://doi.org/10.1289/ehp.0901450 Harner, T., Bartkow, M., Holoubek, I., Klanova, J., Wania, F., Gioia, R., Moeckel, C., Sweetman, A.J., Jones, K.C., 2006. Passive air sampling for persistent organic pollutants: Introductory remarks to the special issue. Environ. Pollut. 144, 361–364. https://doi.org/10.1016/j.envpol.2005.12.044 Hartmann, P.C., Burgi, D., Giger, W., 2004. Organophosphate flame retardants and plasticizers in indoor air. Chemosphere 57, 781–787. https://doi.org/10.1016/j.chemosphere.2004.08.051 Hays, S.M., Kirman, C.R., 2017. Risk assessment and Biomonitoring Equivalent for 2- ethylhexyl-2,3,4,5 tetrabromobenzoate (TBB) and tetrabromobenzoic acid (TBBA). Regul. Toxicol. Pharmacol. 89, 186–192. https://doi.org/10.1016/j.yrtph.2017.07.022 Hazrati, S., Harrad, S., 2006. Causes of Variability in Concentrations of Polychlorinated Biphenyls and Polybrominated Diphenyl Ethers in Indoor air. Environ. Sci. Technol. 40, 7584–7589. https://doi.org/10.1021/es0617082 Heacock, M., Kelly, C.B., Asante, K.A., Birnbaum, L.S., Bergman, Å.L., Bruné, M.-N., Buka, I., Carpenter, D.O., Chen, A., Huo, X., Kamel, M., Landrigan, P.J., Magalini, F., Diaz-Barriga, F., Neira, M., Omar, M., Pascale, A., Ruchirawat, M., Sly, L., Sly, P.D., Van den Berg, M., Suk, W.A., 2015. E-Waste and Harm to Vulnerable Populations: A Growing Global Problem. Environ. Health Perspect. 124, 550–555. https://doi.org/10.1289/ehp.1509699 Heudorf, U., Mersch-Sundermann, V., Angerer, J., 2007. Phthalates: Toxicology and exposure. Int. J. Hyg. Environ. Health 210, 623–634. https://doi.org/10.1016/j.ijheh.2007.07.011 Hill, K.L., Hamers, T., Kamstra, J.H., Willmore, W.G., Letcher, R.J., 2018. Organophosphate triesters and selected metabolites enhance binding of thyroxine to human transthyretin in vitro. Toxicol. Lett. 285, 87–93. https://doi.org/10.1016/j.toxlet.2017.12.030 Hites, R.A., 2004. Polybrominated Diphenyl Ethers in the Environment and in People: A Meta-Analysis of Concentrations. Environ. Sci. Technol. 38, 945–956. https://doi.org/10.1021/es035082g Hoffman, K., Butt, C.M., Webster, T.F., Preston, E. V., Hammel, S.C., Makey, C., Lorenzo, A.M., Cooper, E.M., Carignan, C., Meeker, J.D., Hauser, R., Soubry, A., Murphy, S.K., Price, T.M., Hoyo, C., Mendelsohn, E., Congleton, J., Daniels, J.L., Stapleton, H.M., 2017a. Temporal Trends in Exposure to Organophosphate Flame Retardants in the United States. Environ. Sci. Technol. Lett. 4, 112–118. https://doi.org/10.1021/acs.estlett.6b00475 Hoffman, K., Lorenzo, A., Butt, C.M., Hammel, S.C., Henderson, B.B., Roman, S.A., Scheri, R.P., Stapleton, H.M., Sosa, J.A., 2017b. Exposure to flame retardant chemicals and occurrence and severity of papillary thyroid cancer: A case-control study. Environ. Int. 107, 235–242. https://doi.org/10.1016/j.envint.2017.06.021 Holmes, A.K., Koller, K.R., Kieszak, S.M., Sjodin, A., Calafat, A.M., Sacco, F.D., Varner, D.W., Lanier, A.P., Rubin, C.H., 2014. Case–control study of breast cancer and exposure to synthetic environmental chemicals among Alaska Native women. Int. J. Circumpolar Health 73, 25760. https://doi.org/10.3402/ijch.v73.25760

163

Hou, R., Xu, Y., Wang, Z., 2016. Review of OPFRs in animals and humans: Absorption, bioaccumulation, metabolism, and internal exposure research. Chemosphere 153, 78– 90. https://doi.org/10.1016/j.chemosphere.2016.03.003 Hubinger, J.C., Havery, D.C., 2006. Analysis of consumer cosmetic products for phthalate esters. J. Cosmet. Sci. 57, 127–37. Hutter, H.-P., Haluza, D., Piegler, K., Hohenblum, P., Fröhlich, M., Scharf, S., Uhl, M., Damberger, B., Tappler, P., Kundi, M., Wallner, P., Moshammer, H., 2013. Semivolatile compounds in schools and their influence on cognitive performance of children. Int. J. Occup. Med. Environ. Health 26, 628–635. https://doi.org/10.2478/s13382-013-0125-z IARC Working Group on the Evaluation of Carcinogenic Risks to Humans, 2013. Some chemicals present in industrial and consumer products, food and drinking-water. IARC Monogr. Eval. Carcinog. Risks Hum. 101, 9–549. Igharo, O.G., Anetor, J.I., Osibanjo, O., Osadolor, H.B., Odazie, E.C., Uche, Z.C., 2018. Endocrine disrupting metals lead to alteration in the gonadal hormone levels in Nigerian e-waste workers. Universa Med. 37, 65. https://doi.org/10.18051/UnivMed.2018.v37.65-74 Iqbal, M., Syed, J.H., Breivik, K., Chaudhry, M.J.I., Li, J., Zhang, G., Malik, R.N., 2017. E- Waste Driven Pollution in Pakistan: The First Evidence of Environmental and Human Exposure to Flame Retardants (FRs) in Karachi City. Environ. Sci. Technol. 51, 13895– 13905. https://doi.org/10.1021/acs.est.7b03159 Jacobson, M.H., Barr, D.B., Marcus, M., Muir, A.B., Lyles, R.H., Howards, P.P., Pardo, L., Darrow, L.A., 2016. Serum polybrominated diphenyl ether concentrations and thyroid function in young children. Environ. Res. 149, 222–230. https://doi.org/10.1016/j.envres.2016.05.022 Jarema, K.A., Hunter, D.L., Shaffer, R.M., Behl, M., Padilla, S., 2015. Acute and developmental behavioral effects of flame retardants and related chemicals in zebrafish. Neurotoxicol. Teratol. 52, 194–209. https://doi.org/10.1016/j.ntt.2015.08.010 Julander, A., Westberg, H., Engwall, M., van Bavel, B., 2005. Distribution of brominated flame retardants in different dust fractions in air from an electronics recycling facility. Sci. Total Environ. 350, 151–160. https://doi.org/10.1016/j.scitotenv.2005.01.015 Kahhat, R., Williams, E., 2012. Materials flow analysis of e-waste: Domestic flows and exports of used computers from the United States. Resour. Conserv. Recycl. 67, 67–74. https://doi.org/10.1016/j.resconrec.2012.07.008 Kammerer, F., 2017. Safe Drinking Water and Toxic Enforcement Act of 1986. Environ. Heal. 1–22. Kile, M.L., Scott, R.P., O’Connell, S.G., Lipscomb, S., MacDonald, M., McClelland, M., Anderson, K.A., Gibson, E.A., Stapleton, H.M., Calero, L., Holmes, D., Burke, K., Martinez, R., Cortes, B., Nematollahi, A., Evans, D., Anderson, K.A., Herbstman, J.B., Fisher, M., Arbuckle, T.E., MacPherson, S., Braun, J.M., Feeley, M., Gaudreau, É., Dixon, H.M., Scott, R.P., Holmes, D., Calero, L., Kincl, L.D., Waters, K.M., Camann, D.E., Calafat, A.M., Herbstman, J.B., Anderson, K.A., Bohlin, P., Jones, K.C., Levin, J.O., Lindahl, R., Strandberg, B., 2019. Using silicone wristbands to evaluate preschool children’s exposure to flame retardants. Chemosphere 219, 567–573. https://doi.org/10.1007/s00216-018-0992-z Kim, E.-H., Jeon, B.-H., Kim, J., Kim, Y.-M., Han, Y., Ahn, K., Cheong, H.-K., 2017. Exposure to phthalates and bisphenol A are associated with atopic dermatitis symptoms in children: a time-series analysis. Environ. Heal. 16, 24. https://doi.org/10.1186/s12940-017-0225-5 Kim, Y.H., Wyrzykowska-Ceradini, B., Touati, A., Krantz, Q.T., Dye, J.A., Linak, W.P.,

164

Gullett, B., Gilmour, M.I., 2015. Characterization of Size-Fractionated Airborne Particles Inside an Electronic Waste Recycling Facility and Acute Toxicity Testing in Mice. Environ. Sci. Technol. 49, 11543–11550. https://doi.org/10.1021/acs.est.5b03263 Koniecki, D., Wang, R., Moody, R.P., Zhu, J., 2011. Phthalates in cosmetic and personal care products: Concentrations and possible dermal exposure. Environ. Res. 111, 329– 336. https://doi.org/10.1016/j.envres.2011.01.013 Kuo, L., Cade, S.E., Cullinan, V., Schultz, I.R., 2019. Polybrominated diphenyl ethers (PBDEs) in plasma from E-waste recyclers, outdoor and indoor workers in the Puget Sound, WA region. Chemosphere 219, 209–216. https://doi.org/10.1016/j.chemosphere.2018.12.006 Kuriyama, S.N., Talsness, C.E., Grote, K., Chahoud, I., 2005. Developmental exposure to low-dose PBDE-99: Effects on male fertility and neurobehavior in rat offspring. Environ. Health Perspect. 113, 149–154. https://doi.org/10.1289/ehp.7421 La Guardia, M.J., Hale, R.C., Harvey, E., 2006. Detailed Polybrominated Diphenyl Ether (PBDE) Congener Composition of the Widely Used Penta-, Octa-, and Deca-PBDE Technical Flame-retardant Mixtures. Environ. Sci. Technol. 40, 6247–6254. https://doi.org/10.1021/es060630m Labunska, I., Harrad, S., Wang, M., Santillo, D., Johnston, P., 2014. Human Dietary Exposure to PBDEs Around E-Waste Recycling Sites in Eastern China. Environ. Sci. Technol. 48, 5555–5564. https://doi.org/10.1021/es500241m Lam, J., Lanphear, B.P., Bellinger, D., Axelrad, D.A., McPartland, J., Sutton, P., Davidson, L., Daniels, N., Sen, S., Woodruff, T.J., 2017. Developmental PBDE Exposure and IQ/ADHD in Childhood: A Systematic Review and Meta-analysis. Environ. Health Perspect. 125. https://doi.org/10.1289/EHP1632 Lenters, V., Portengen, L., Rignell-Hydbom, A., Jönsson, B.A.G., Lindh, C.H., Piersma, A.H., Toft, G., Bonde, J.P., Heederik, D., Rylander, L., Vermeulen, R., 2016. Prenatal Phthalate, Perfluoroalkyl Acid, and Organochlorine Exposures and Term Birth Weight in Three Birth Cohorts: Multi-Pollutant Models Based on Elastic Net Regression. Environ. Health Perspect. 124, 365–372. https://doi.org/10.1289/ehp.1408933 Li, F., Xie, Q., Li, X., Li, N., Chi, P., Chen, J., Wang, Z., Hao, C., 2010. Hormone Activity of Hydroxylated Polybrominated Diphenyl Ethers on Human Thyroid Receptor-β: In Vitro and In Silico Investigations. Environ. Health Perspect. 118, 602–606. https://doi.org/10.1289/ehp.0901457 Lilienthal, H., Hack, A., Roth-Härer, A., Grande, S.W., Talsness, C.E., 2006. Effects of developmental exposure to 2,2′,4,4′, 5-pentabromodiphenyl ether (PBDE-99) on sex steroids, sexual development, and sexually dimorphic behavior in rats. Environ. Health Perspect. 114, 194–201. https://doi.org/10.1289/ehp.8391 Lippmann, M., 1998. The 1997 US EPA Standards for Particulate Matter and Ozone, in: Air Pollution and Health. pp. 75–100. https://doi.org/10.1039/9781847550095-00075 Little, J.C., Weschler, C.J., Nazaroff, W.W., Liu, Z., Cohen Hubal, E.A., 2012. Rapid Methods to Estimate Potential Exposure to Semivolatile Organic Compounds in the Indoor Environment. Environ. Sci. Technol. 46, 11171–11178. https://doi.org/10.1021/es301088a Liu, C., Zhang, Y., Weschler, C.J., 2017. Exposure to SVOCs from Inhaled Particles: Impact of Desorption. Environ. Sci. Technol. 51, 6220–6228. https://doi.org/10.1021/acs.est.6b05864 Lu, S.Y., Li, Y.X., Zhang, T., Cai, D., Ruan, J.J., Huang, M.Z., Wang, L., Zhang, J.Q., Qiu, R.L., 2017. Effect of E-waste Recycling on Urinary Metabolites of Organophosphate Flame Retardants and Plasticizers and Their Association with Oxidative Stress. Environ. Sci. Technol. 51, 2427–2437. https://doi.org/10.1021/acs.est.6b05462

165

Lucas, D., Petty, S.M., Keen, O., Luedeka, B., Schlummer, M., Weber, R., Barlaz, M., Yazdani, R., Riise, B., Rhodes, J., Nightingale, D., Diamond, M.L., Vijgen, J., Lindeman, A., Blum, A., Koshland, C.P., 2017. Methods of Responsibly Managing End-of-Life Foams and Plastics Containing Flame Retardants: Part I. Environ. Eng. Sci. https://doi.org/10.1089/ees.2017.0147 Ma, J., Addink, R., Yun, S., Cheng, J., Wang, W., Kannan, K., 2009. Polybrominated Dibenzo- p -dioxins/Dibenzofurans and Polybrominated Diphenyl Ethers in Soil, Vegetation, Workshop-Floor Dust, and Electronic Shredder Residue from an Electronic Waste Recycling Facility and in Soils from a Chemical Industrial Complex in Ea. Environ. Sci. Technol. 43, 7350–7356. https://doi.org/10.1021/es901713u MacIntosh, D.L., Minegishi, T., Fragala, M.A., Allen, J.G., Coghlan, K.M., Stewart, J.H., McCarthy, J.F., 2012. Mitigation of building-related polychlorinated biphenyls in indoor air of a school. Environ. Heal. A Glob. Access Sci. Source 11, 1–10. https://doi.org/10.1186/1476-069X-11-24 Mäkinen, M.S.E., Mäkinen, M.R.A., Koistinen, J.T.B., Pasanen, A.-L., Pasanen, P.O., Kalliokoski, P.J., Korpi, A.M., 2009. Respiratory and Dermal Exposure to Organophosphorus Flame Retardants and Tetrabromobisphenol A at Five Work Environments. Environ. Sci. Technol. 43, 941–947. https://doi.org/10.1021/es802593t Marek, R.F., Thorne, P.S., Herkert, N.J., Awad, A.M., Hornbuckle, K.C., 2017. Airborne PCBs and OH-PCBs Inside and Outside Urban and Rural U.S. Schools. Environ. Sci. Technol. 51, 7853–7860. https://doi.org/10.1021/acs.est.7b01910 Meeker, J.D., Cooper, E.M., Stapleton, H.M., Hauser, R., 2013. Exploratory analysis of urinary metabolites of phosphorus-containing flame retardants in relation to markers of male reproductive health. Endocr. Disruptors 1, e26306. https://doi.org/10.4161/endo.26306 Meeker, J.D., Stapleton, H.M., 2009. House Dust Concentrations of Organophosphate Flame Retardants in Relation to Hormone Levels and Semen Quality Parameters. Environ. Health Perspect. 118, 318–323. https://doi.org/10.1289/ehp.0901332 Meironyté, D., Norén, K., Bergman, Å., 1999. Analysis of polybrominated diphenyl ethers in swedish human milk. A time-related trend study, 1972–1997. J. Toxicol. Environ. Heal. - Part A 58, 329–341. https://doi.org/10.1080/009841099157197 Melymuk, L., Robson, M., Helm, P.A., Diamond, M.L., 2011. Evaluation of passive air sampler calibrations: Selection of sampling rates and implications for the measurement of persistent organic pollutants in air. Atmos. Environ. 45, 1867–1875. https://doi.org/10.1016/j.atmosenv.2011.01.011 Mendelsohn, E., Hagopian, A., Hoffman, K., Butt, C.M., Lorenzo, A., Congleton, J., Webster, T.F., Stapleton, H.M., 2016. Nail polish as a source of exposure to triphenyl phosphate. Environ. Int. 86, 45–51. https://doi.org/10.1016/j.envint.2015.10.005 Moeckel, C., Harner, T., Nizzetto, L., Strandberg, B., Lindroth, A., Jones, K.C., 2009. Use of depuration compounds in passive air samplers: Results from active sampling-supported field deployment, potential uses, and recommendations. Environ. Sci. Technol. 43, 3227–3232. https://doi.org/10.1021/es802897x Morrison, G.C., Weschler, C.J., Bekö, G., Koch, H.M., Salthammer, T., Schripp, T., Toftum, J., Clausen, G., 2016. Role of clothing in both accelerating and impeding dermal absorption of airborne SVOCs. J. Expo. Sci. Environ. Epidemiol. 26, 113–118. https://doi.org/10.1038/jes.2015.42 Muenhor, D., Harrad, S., Ali, N., Covaci, A., 2010. Brominated flame retardants (BFRs) in air and dust from electronic waste storage facilities in Thailand. Environ. Int. 36, 690– 698. https://doi.org/10.1016/j.envint.2010.05.002 Nalli, S., Horn, O.J., Grochowalski, A.R., Cooper, D.G., Nicell, J.A., 2006. Origin of 2-

166

ethylhexanol as a VOC. Environ. Pollut. 140, 181–185. https://doi.org/10.1016/j.envpol.2005.06.018 National Academies of Sciences Engineering and Medicine, 2017. Application of Systematic Review Methods in an Overall Strategy for Evaluating Low-Dose Toxicity from Endocrine Active Chemicals. The National Academies Press, Washington,DC. https://doi.org/10.17226/24758 Nguyen, L. V., Diamond, M.L., Venier, M., Stubbings, W.A., Romanak, K., Bajard, L., Melymuk, L., Jantunen, L.M., Arrandale, V.H., 2019. Exposure of Canadian electronic waste dismantlers to flame retardants. Environ. Int. 129, 95–104. https://doi.org/10.1016/j.envint.2019.04.056 Nguyen, L. V., Gravel, S., Labrèche, F., Bakhiyi, B., Verner, M.A., Zayed, J., Jantunen, L.M., Arrandale, V.H., Diamond, M.L., 2020. Can Silicone Passive Samplers be Used for Measuring Exposure of e-Waste Workers to Flame Retardants? Environ. Sci. Technol. 54, 15277–15286. https://doi.org/10.1021/acs.est.0c05240 North, M.L., Takaro, T.K., Diamond, M.L., Ellis, A.K., 2014. Effects of phthalates on the development and expression of allergic disease and asthma. Ann. Allergy, Asthma Immunol. 112, 496–502. https://doi.org/10.1016/j.anai.2014.03.013 NTP, 1991. Toxicology and Carcinogenesis Studies of TRIS(2- CHLOROETHYL)PHOSPHATE (CAS NO. 115-96-8) in F344 / N Rats. Natl. Toxicol. Program Tech. Rep. Ser. 409, 1–171. O’Connell, S.G., Kincl, L.D., Anderson, K.A., 2014. Silicone Wristbands as Personal Passive Samplers. Environ. Sci. Technol. 48, 3327–3335. https://doi.org/10.1021/es405022f Okeme, J.O., Nguyen, L. V., Lorenzo, M., Dhal, S., Pico, Y., Arrandale, V.H., Diamond, M.L., 2018a. Polydimethylsiloxane (silicone rubber) brooch as a personal passive air sampler for semi-volatile organic compounds. Chemosphere 208, 1002–1007. https://doi.org/10.1016/j.chemosphere.2018.05.196 Okeme, J.O., Nguyen, L. V., Lorenzo, M., Dhal, S., Pico, Y., Arrandale, V.H., Diamond, M.L., 2018b. Polydimethylsiloxane (silicone rubber) brooch as a personal passive air sampler for semi-volatile organic compounds. Chemosphere 208, 1002–1007. https://doi.org/10.1016/j.chemosphere.2018.05.196 Okeme, J.O., Parnis, J.M., Poole, J., Diamond, M.L., Jantunen, L.M., 2016a. Polydimethylsiloxane-air partition ratios for semi-volatile organic compounds by GC- based measurement and COSMO-RS estimation: Rapid measurements and accurate modelling. Chemosphere 156, 204–211. https://doi.org/10.1016/j.chemosphere.2016.04.094 Okeme, J.O., Rodgers, T.F.M., Jantunen, L.M., Diamond, M.L., 2018c. Examining the Gas- Particle Partitioning of Organophosphate Esters: How Reliable Are Air Measurements? Environ. Sci. Technol. 52, 13834–13844. https://doi.org/10.1021/acs.est.8b04588 Okeme, J.O., Saini, A., Yang, C., Zhu, J., Smedes, F., Klánová, J., Diamond, M.L., 2016b. Calibration of polydimethylsiloxane and XAD-Pocket passive air samplers (PAS) for measuring gas- and particle-phase SVOCs. Atmos. Environ. 143, 202–208. https://doi.org/10.1016/j.atmosenv.2016.08.023 Okeme, J.O., Yang, C., Abdollahi, A., Dhal, S., Harris, S.A., Jantunen, L.M., Tsirlin, D., Diamond, M.L., 2018d. Passive air sampling of flame retardants and plasticizers in Canadian homes using PDMS, XAD-coated PDMS and PUF samplers. Environ. Pollut. 239, 109–117. https://doi.org/10.1016/j.envpol.2018.03.103 Okonski, K., Degrendele, C., Melymuk, L., Landlová, L., Kukučka, P., Vojta, Š., Kohoutek, J., Čupr, P., Klánová, J., 2014. Particle Size Distribution of Halogenated Flame Retardants and Implications for Atmospheric Deposition and Transport. Environ. Sci.

167

Technol. 48, 14426–14434. https://doi.org/10.1021/es5044547 Ospina, M., Jayatilaka, N.K., Wong, L.-Y., Restrepo, P., Calafat, A.M., 2018. Exposure to organophosphate flame retardant chemicals in the U.S. general population: Data from the 2013–2014 National Health and Nutrition Examination Survey. Environ. Int. 110, 32–41. https://doi.org/10.1016/j.envint.2017.10.001 Park, S.A., Gwak, S., Choi, S., 2014. Assessment of occupational symptoms and chemical exposures for nail salon technicians in Daegu City, Korea. J. Prev. Med. Public Heal. 47, 169–176. https://doi.org/10.3961/jpmph.2014.47.3.169 Pawar, G., 2017. Exploring the utility of 3-D skin models to evaluate trans-dermal uptake of flame retardants from indoor dust and consumer product. University of Birmingham. Pelucchi, C., Negri, E., Gallus, S., Boffetta, P., Tramacere, I., La Vecchia, C., 2009. Long- term particulate matter exposure and mortality: a review of European epidemiological studies. BMC Public Health 9, 453. https://doi.org/10.1186/1471-2458-9-453 Percy, Z., Vuong, A.M., Ospina, M., Calafat, A.M., La Guardia, M.J., Xu, Y., Hale, R.C., Dietrich, K.N., Xie, C., Lanphear, B.P., Braun, J.M., Cecil, K.M., Yolton, K., Chen, A., 2020. Organophosphate esters in a cohort of pregnant women: Variability and predictors of exposure. Environ. Res. 184, 109255. https://doi.org/10.1016/j.envres.2020.109255 Pettersson-Julander, A., van Bavel, B., Engwall, M., Westberg, H., 2004. Personal air sampling and analysis of polybrominated diphenyl ethers and other bromine containing compounds at an electronic recycling facility in Sweden. J. Environ. Monit. 6, 874. https://doi.org/10.1039/b408381d Philippat, C., Bennett, D., Calafat, A.M., Picciotto, I.H., Xu, F., Giovanoulis, G., Van Waes, S., Padilla-Sanchez, J.A., Papadopoulou, E., Magnér, J., Haug, L.S., Neels, H., Covaci, A., 2016. Exposure to select phthalates and phenols through use of personal care products among Californian adults and their children. Environ. Res. 50, 7752–7760. https://doi.org/10.1021/acs.est.6b00246 Pinson, A., Bourguignon, J.P., Parent, A.S., 2016. Exposure to endocrine disrupting chemicals and neurodevelopmental alterations. Andrology 4, 706–722. https://doi.org/10.1111/andr.12211 Pope III, C.A., 2002. Lung Cancer, Cardiopulmonary Mortality, and Long-term Exposure to Fine Particulate Air Pollution. JAMA 287, 1132. https://doi.org/10.1001/jama.287.9.1132 Quach, T., Gunier, R., Tran, A., Von Behren, J., Doan-Billings, P.-A., Nguyen, K.-D., Okahara, L., Lui, B.Y.-B., Nguyen, M., Huynh, J., Reynolds, P., 2011. Characterizing Workplace Exposures in Vietnamese Women Working in California Nail Salons. Am. J. Public Health 101, S271–S276. https://doi.org/10.2105/AJPH.2010.300099 Radke, E.G., Braun, J.M., Meeker, J.D., Cooper, G.S., Agency, U.S.E.P., States, U., 2018. Phthalate exposure and male reproductive outcomes : A systematic review of the human epidemiological evidence. Environ. Int. 121, 764–793. https://doi.org/10.1016/j.envint.2018.07.029 Rakkestad, K.E., Dye, C.J., Yttri, K.E., Holme, J.A., Hongslo, J.K., Schwarze, P.E., Becher, R., 2007. Phthalate levels in Norwegian indoor air related to particle size fraction. J. Environ. Monit. 9, 1419. https://doi.org/10.1039/b709947a Rengasamy, S., Eimer, B., Shaffer, R.E., 2010. Simple respiratory protection - Evaluation of the filtration performance of cloth masks and common fabric materials against 20-1000 nm size particles. Ann. Occup. Hyg. 54, 789–798. https://doi.org/10.1093/annhyg/meq044 Richman, K.E., Butt, C.M., Young, C.J., 2018. Size-resolved particle measurements of polybrominated diphenyl ethers indoors: Implications for sources and human exposure.

168

Environ. Toxicol. Chem. 37, 481–490. https://doi.org/10.1002/etc.3981 Robinson, B.H., 2009. E-waste: An assessment of global production and environmental impacts. Sci. Total Environ. 408, 183–191. https://doi.org/10.1016/j.scitotenv.2009.09.044 Rodes, C.E., Kamens, R.M., Wiener, R.W., 1991. The Significance and Characteristics of the Personal Activity Cloud on Exposure Assessment Measurements for Indoor Contaminants. Indoor Air 1, 123–145. https://doi.org/10.1111/j.1600-0668.1991.03- 12.x Romanak, K.A., Wang, S., Stubbings, W.A., Hendryx, M., Venier, M., Salamova, A., 2019. Analysis of brominated and chlorinated flame retardants, organophosphate esters, and polycyclic aromatic hydrocarbons in silicone wristbands used as personal passive samplers. J. Chromatogr. A 1588, 41–47. https://doi.org/10.1016/j.chroma.2018.12.041 Romero-Franco, M., Hernández-Ramírez, R.U., Calafat, A.M., Cebrián, M.E., Needham, L.L., Teitelbaum, S., Wolff, M.S., López-Carrillo, L., 2011. Personal care product use and urinary levels of phthalate metabolites in Mexican women. Environ. Int. 37, 867– 871. https://doi.org/10.1016/j.envint.2011.02.014 Rosenberg, C., Hämeilä, M., Tornaeus, J., Säkkinen, K., Puttonen, K., Korpi, A., Kiilunen, M., Linnainmaa, M., Hesso, A., 2011. Exposure to Flame Retardants in Electronics Recycling Sites. Ann. Occup. Hyg. 55, 658–665. https://doi.org/10.1093/annhyg/mer033 Saini, A., Okeme, J.O., Goosey, E., Diamond, M.L., 2015. Calibration of two passive air samplers for monitoring phthalates and brominated flame-retardants in indoor air. Chemosphere 137, 166–173. https://doi.org/10.1016/j.chemosphere.2015.06.099 Saini, A., Okeme, J.O., Mark Parnis, J., McQueen, R.H., Diamond, M.L., 2016. From air to clothing: characterizing the accumulation of semi-volatile organic compounds to fabrics in indoor environments. Indoor Air. https://doi.org/10.1111/ina.12328 SCHETTLER, T., 2006. Human exposure to phthalates via consumer products. Int. J. Androl. 29, 134–139. https://doi.org/10.1111/j.1365-2605.2005.00567.x Schreder, E.D., Uding, N., La Guardia, M.J., 2016. Inhalation a significant exposure route for chlorinated organophosphate flame retardants. Chemosphere 150, 499–504. https://doi.org/10.1016/j.chemosphere.2015.11.084 Schwartz, J., Neas, L.M., 2000. Fine particles are more strongly associated than coarse particleswithacute respiratoryhealtheffectsinschoolchildren. Epidemiology 11, 6–10. Shi, T., Chen, S.-J., Luo, X.-J., Zhang, X.-L., Tang, C.-M., Luo, Y., Ma, Y.-J., Wu, J.-P., Peng, X.-Z., Mai, B.-X., 2009. Occurrence of brominated flame retardants other than polybrominated diphenyl ethers in environmental and biota samples from southern China. Chemosphere 74, 910–916. https://doi.org/10.1016/j.chemosphere.2008.10.047 Shoeib, M., Harner, T., 2002. Characterization and Comparison of Three Passive Air Samplers for Persistent Organic Pollutants. Environ. Sci. Technol. 36, 4142–4151. https://doi.org/10.1021/es020635t Sindiku, O., Babayemi, J., Osibanjo, O., Schlummer, M., Schluep, M., Watson, A., Weber, R., 2015. Polybrominated diphenyl ethers listed as Stockholm Convention POPs, other brominated flame retardants and heavy metals in e-waste polymers in Nigeria. Environ. Sci. Pollut. Res. 22, 14489–14501. https://doi.org/10.1007/s11356-014-3266-0 Singh, M., Thind, P.S., John, S., 2018. Health risk assessment of the workers exposed to the heavy metals in e-waste recycling sites of Chandigarh and Ludhiana, Punjab, India. Chemosphere 203, 426–433. https://doi.org/10.1016/j.chemosphere.2018.03.138 Sjödin, A., Carlsson, H., Thuresson, K., Sjölin, S., Bergman, Å., Östman, C., 2001. Flame Retardants in Indoor Air at an Electronics Recycling Plant and at Other Work Environments. Environ. Sci. Technol. 35, 448–454. https://doi.org/10.1021/es000077n

169

Slotkin, T.A., Skavicus, S., Stapleton, H.M., Seidler, F.J., 2017. Brominated and organophosphate flame retardants target different neurodevelopmental stages, characterized with embryonic neural stem cells and neuronotypic PC12 cells. Toxicology 390, 32–42. https://doi.org/10.1016/j.tox.2017.08.009 Smil, V., 2017. PLANET OF THE COWS. IEEE Spectr. 54, 24. Snedeker, S.M., 2014. Toxicants in Food Packaging and Household Plastics, Molecular and Integrative Toxicology. Springer London, London. https://doi.org/10.1007/978-1-4471- 6500-2 Staaf, T., Ostman, C., 2005. Organophosphate triesters in indoor environments. J. Environ. Monit. 7, 883–887. https://doi.org/10.1039/b506631j Stapleton, H.M., Allen, J.G., Kelly, S.M., Konstantinov, A., Klosterhaus, S., Watkins, D., McClean, M.D., Webster, T.F., 2008a. Alternate and New Brominated Flame Retardants Detected in U.S. House Dust. Environ. Sci. Technol. 42, 6910–6916. https://doi.org/10.1021/es801070p Stapleton, H.M., Kelly, S.M., Allen, J.G., McClean, M.D., Webster, T.F., Stapleton, M.H., Kelly, S.M., Allen, J.G., McClean, M.D., Webster, T.F., Stapleton, H.M., Kelly, S.M., Allen, J.G., McClean, M.D., Webster, T.F., 2008b. Measurement of Polybrominated Diphenyl Ethers on Hand Wipes: Estimating Exposure from Hand-to-Mouth Contact. Environ. Sci. Technol. 42, 3329–3334. https://doi.org/10.1021/es7029625 Statistics Canada, 2016. EnviroStats Trash talking: Dealing with Canadian household e- waste. [WWW Document]. URL http://www.statcan.gc.ca/pub/16-002- x/2016001/article/14570-eng.htm (accessed 7.15.18). Stubbings, W.A., Nguyen, L. V., Romanak, K., Jantunen, L., Melymuk, L., Arrandale, V., Diamond, M.L., Venier, M., 2019a. Flame retardants and plasticizers in a Canadian waste electrical and electronic equipment (WEEE) dismantling facility. Sci. Total Environ. 675, 594–603. https://doi.org/10.1016/j.scitotenv.2019.04.265 Stubbings, W.A., Nguyen, L. V., Romanak, K., Jantunen, L., Melymuk, L., Arrandale, V., Diamond, M.L., Venier, M., 2019b. Flame retardants and plasticizers in a Canadian waste electrical and electronic equipment (WEEE)dismantling facility. Sci. Total Environ. 675, 594–603. https://doi.org/10.1016/j.scitotenv.2019.04.265 Suzuki, G., Tue, N.M., Malarvannan, G., Sudaryanto, A., Takahashi, S., Tanabe, S., Sakai, S., Brouwer, A., Uramaru, N., Kitamura, S., Takigami, H., 2013. Similarities in the Endocrine-Disrupting Potencies of Indoor Dust and Flame Retardants by Using Human Osteosarcoma (U2OS) Cell-Based Reporter Gene Assays. Environ. Sci. Technol. 47, 2898–2908. https://doi.org/10.1021/es304691a Swedish Chemicals Inspectorate, 2003. Brominated flame retardants – Prospects of a national ban. KemI Report 4/03. Takigami, H., Suzuki, G., Hirai, Y., Sakai, S., 2008. Transfer of brominated flame retardants from components into dust inside television cabinets. Chemosphere 73, 161–169. https://doi.org/10.1016/j.chemosphere.2008.06.032 Tansel, B., 2017. From electronic consumer products to e-wastes: Global outlook, waste quantities, recycling challenges. Environ. Int. 98, 35–45. https://doi.org/10.1016/j.envint.2016.10.002 Thuresson, K., Höglund, P., Hagmar, L., Sjödin, A., Bergman, Å., Jakobsson, K., 2006. Apparent Half-Lives of Hepta- to Decabrominated Diphenyl Ethers in Human Serum as Determined in Occupationally Exposed Workers. Environ. Health Perspect. 114, 176– 181. https://doi.org/10.1289/ehp.8350 Tran, T.M., Kannan, K., 2015. Occurrence of Phthalate Diesters in Particulate and Vapor Phases in Indoor Air and Implications for Human Exposure in Albany, New York, USA. Arch. Environ. Contam. Toxicol. 68, 489–499. https://doi.org/10.1007/s00244-

170

015-0140-0 Tran, T.M., Le, H.T., Minh, T.B., Kannan, K., 2017. Occurrence of phthalate diesters in indoor air from several Northern cities in Vietnam, and its implication for human exposure. Sci. Total Environ. 601–602, 1695–1701. https://doi.org/10.1016/j.scitotenv.2017.06.016 Traore, I.T., Gravel, S., Diamond, M.L., Jantunen, L., Nguyen, L.V., Yang, C., Bernstein, S., Zayed, J., Labrèche, F., Verner, M.-A., 2018. Urinary Metabolites of Organophosphate Esters (OPEs) in Electronic Waste Recycling Workers from the Province of Quebec, Canada. ISEE Conf. Abstr. 2018, isesisee.2018.P01.3100. https://doi.org/10.1289/isesisee.2018.P01.3100 Tromp, P.C., Beeltje, H., Okeme, J.O., Vermeulen, R., Pronk, A., Diamond, M.L., 2019. Calibration of polydimethylsiloxane and polyurethane foam passive air samplers for measuring semi volatile organic compounds using a novel exposure chamber design. Chemosphere 227, 435–443. https://doi.org/10.1016/j.chemosphere.2019.04.043 Tue, N.M., Takahashi, S., Suzuki, G., Isobe, T., Viet, P.H., Kobara, Y., Seike, N., Zhang, G., Sudaryanto, A., Tanabe, S., 2013. Contamination of indoor dust and air by polychlorinated biphenyls and brominated flame retardants and relevance of non-dietary exposure in Vietnamese informal e-waste recycling sites. Environ. Int. 51, 160–167. https://doi.org/10.1016/j.envint.2012.11.006 U.S.Bureau of Labor, 2020. Occupational Outlook Handbook [WWW Document]. UCLA Labor Center, 2018. Nail Files: A study of nail salon workers and industry in United States. UNEP, 2019. A New Circular Vision for Electronics Time for a Global Reboot 24. UNEP, 2016. GEO-6 North America Regional Assessment [WWW Document]. URL http://wedocs.unep.org/bitstream/handle/20.500.11822/7611/GEO_North_America_201 611.pdf?sequence=1&isAllowed=y (accessed 6.27.18). UNEP, 2010. Technical review of the implications of recycling commercial pentabromodiphenyl ether and commercial octabromodi- phenyl ether. UNEP, 2008. Report of the Persistent Organic Pollutants Review Committee on the work of its fourth meeting. United States Department of Labor, 2017. Occupational Employment and Wages, May 2017 [WWW Document]. URL https://www.bls.gov/oes/current/oes395092.htm#st US EPA, 2018a. IRIS Assessments [WWW Document]. URL https://cfpub.epa.gov/ncea/iris2/atoz.cfm (accessed 6.27.18). US EPA, 2018b. Chemistry Dashboard [WWW Document]. URL https://comptox.epa.gov/dashboard (accessed 6.27.18). US EPA, 2018c. 2,2’,4,4’,5-Pentabromodiphenyl ether (BDE-99) [WWW Document]. URL https://cfpub.epa.gov/ncea/iris2/chemicalLanding.cfm?substance_nmbr=1008 (accessed 6.27.18). US EPA, 2011. September 2011 EXPOSURE FACTORS HANDBOOK : 2011 EDITION National Center for Environmental Assessment Office of Research and Development U . S . Environmental Protection Agency Washington , DC 20460 Exposure Factors Handbook. Exposure. USEPA, 2020. CHEMICALS KNOWN TO THE STATE TO CAUSE CANCER OR REPRODUCTIVE TOXICITY January 3, 2020. Veen, I. Van Der, Boer, J. De, 2012. Chemosphere Phosphorus flame retardants : Properties , production , environmental occurrence , toxicity and analysis. Chemosphere 88, 1119– 1153. https://doi.org/10.1016/j.chemosphere.2012.03.067 Venier, M., Ma, Y., Hites, R.A., 2012. Brominated flame retardants in the Great Lakes atmosphere. Environ. Sci. Technol. 46, 8653–8660.

171

172

Wei, W., Bonvallot, N., Gustafsson, Å., Raffy, G., Glorennec, P., Krais, A., Ramalho, O., Le Bot, B., Mandin, C., 2018. Bioaccessibility and bioavailability of environmental semi- volatile organic compounds via inhalation: A review of methods and models. Environ. Int. 113, 202–213. https://doi.org/10.1016/j.envint.2018.01.024 Wei, W., Mandin, C., Ramalho, O., 2017. Reactivity of Semivolatile Organic Compounds with Hydroxyl Radicals, Nitrate Radicals, and Ozone in Indoor Air. Int. J. Chem. Kinet. 49, 506–521. https://doi.org/10.1002/kin.21093 Weschler, C.J., Nazaroff, W.W., 2014. Dermal Uptake of Organic Vapors Commonly Found in Indoor Air. Environ. Sci. Technol. 48, 1230–1237. https://doi.org/10.1021/es405490a Weschler, C.J., Nazaroff, W.W., 2012. SVOC exposure indoors: Fresh look at dermal pathways. Indoor Air. https://doi.org/10.1111/j.1600-0668.2012.00772.x Weschler, C.J., Nazaroff, W.W., 2010. SVOC partitioning between the gas phase and settled dust indoors. Atmos. Environ. 44, 3609–3620. https://doi.org/10.1016/j.atmosenv.2010.06.029 Weschler, C.J., Nazaroff, W.W., 2008. Semivolatile organic compounds in indoor environments. Atmos. Environ. 42, 9018–9040. https://doi.org/10.1016/j.atmosenv.2008.09.052 Whitman, W.G., 1962. The two film theory of gas absorption. Int. J. Heat Mass Transf. 5, 429–433. https://doi.org/10.1016/0017-9310(62)90032-7 Wielsøe, M., Kern, P., Bonefeld-Jørgensen, E.C., 2017. Serum levels of environmental pollutants is a risk factor for breast cancer in Inuit: a case control study. Environ. Heal. 16, 56. https://doi.org/10.1186/s12940-017-0269-6 Wong, C.S.C., Duzgoren-Aydin, N.S., Aydin, A., Wong, M.H., 2007. Evidence of excessive releases of metals from primitive e-waste processing in Guiyu, China. Environ. Pollut. 148, 62–72. https://doi.org/10.1016/j.envpol.2006.11.006 Wu, C.-C., Bao, L.-J., Tao, S., Zeng, E.Y., 2016. Dermal Uptake from Airborne Organics as an Important Route of Human Exposure to E-Waste Combustion Fumes. Environ. Sci. Technol. 50, 6599–6605. https://doi.org/10.1021/acs.est.5b05952 Xu, F., Zhang, G., Wang, J., Zhang, W., Liu, L., Lin, K., 2015. Polybrominated diphenyl ethers in air and fallouts from an e-waste polluted region in southeast China: insight into levels, compositional profiles, and seasonal variation. Environ. Sci. Pollut. Res. 22, 19676–19686. https://doi.org/10.1007/s11356-015-5168-1 Xu, Y., Cohen Hubal, E.A., Clausen, P.A., Little, J.C., 2009. Predicting Residential Exposure to Phthalate Plasticizer Emitted from Vinyl Flooring: A Mechanistic Analysis. Environ. Sci. Technol. 43, 2374–2380. https://doi.org/10.1021/es801354f Xu, Y., Cohen Hubal, E.A., Little, J.C., 2010. Predicting residential exposure to phthalate plasticizer emitted from vinyl flooring: Sensitivity, uncertainty, and implications for biomonitoring. Environ. Health Perspect. 118, 253–258. https://doi.org/10.1289/ehp.0900559 Yang, C., Harris, S.A., Jantunen, L.M., Kvasnicka, J., Nguyen, L. V., Diamond, M.L., 2020a. Phthalates: Relationships between Air, Dust, Electronic Devices, and Hands with Implications for Exposure. Environ. Sci. Technol. 54, acs.est.0c00229. https://doi.org/10.1021/acs.est.0c00229 Yang, C., Harris, S.A., Jantunen, L.M., Siddique, S., Kubwabo, C., Tsirlin, D., Latifovic, L., Fraser, B., St-Jean, M., De La Campa, R., You, H., Kulka, R., Diamond, M.L., 2018. Are cell phones an indicator of personal exposure to organophosphate flame retardants and plasticizers? Environ. Int. in press, 1–13. https://doi.org/10.1016/j.envint.2018.10.021 Yang, C., Jílková, S.R., Melymuk, L., Harris, S.A., Jantunen, L.M., Pertili, J., Winn, L., Diamond, M.L., 2020b. Are We Exposed to Halogenated Flame Retardants from both

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Primary and Secondary Sources? Environ. Sci. Technol. Lett. 7, 585–593. https://doi.org/10.1021/acs.estlett.0c00268 Young, A.S., Allen, J.G., Kim, U.-J.J., Seller, S., Webster, T.F., Kannan, K., Ceballos, D.M., 2018. Phthalate and Organophosphate Plasticizers in Nail Polish: Evaluation of Labels and Ingredients. Environ. Sci. Technol. 52, acs.est.8b04495. https://doi.org/10.1021/acs.est.8b04495 Zabiegała, B., Zygmunt, B., Przyk, E., Namieśnik, J., 2000. Applicability of silicone membrane passive samplers for monitoring of indoor air quality. Anal. Lett. 33, 1361– 1372. https://doi.org/10.1080/00032710008543127 Zeng, X., Yang, C., Chiang, J.F., Li, J., 2017. Innovating e-waste management: From macroscopic to microscopic scales. Sci. Total Environ. 575, 1–5. https://doi.org/10.1016/j.scitotenv.2016.09.078 Zhang, H., Yolton, K., Webster, G.M., Sjödin, A., Calafat, A.M., Dietrich, K.N., Xu, Y., Xie, C., Braun, J.M., Lanphear, B.P., Chen, A., 2016. Prenatal PBDE and PCB Exposures and Reading, Cognition, and Externalizing Behavior in Children. Environ. Health Perspect. 125, 7–16. https://doi.org/10.1289/EHP478 Zhang, X., Diamond, M.L., Robson, M., Harrad, S., 2011. Sources, emissions, and fate of polybrominated diphenyl ethers and polychlorinated biphenyls indoors in Toronto, Canada. Environ. Sci. Technol. 45, 3268–3274. https://doi.org/10.1021/es102767g Zhang, Z., Sun, Z.-Z., Xiao, X., Zhou, S., Wang, X.X.-C., Gu, J., Qiu, L.-L., Zhang, X.-H., Xu, Q., Zhen, B., Wang, X.X.-C., Wang, S.-L., 2013a. Mechanism of BDE209-induced impaired glucose homeostasis based on gene microarray analysis of adult rat liver. Arch. Toxicol. 87, 1557–1567. https://doi.org/10.1007/s00204-013-1059-8 Zhang, Z., Zhang, X., Sun, Z., Dong, H., Qiu, L., Gu, J., Zhou, J., Wang, X., Wang, S.L., 2013b. Cytochrome P450 3A1 Mediates 2,2′,4,4′-Tetrabromodiphenyl Ether-Induced Reduction of Spermatogenesis in Adult Rats. PLoS One 8. https://doi.org/10.1371/journal.pone.0066301 Zheng, X., Xu, F., Chen, K., Zeng, Y., Luo, X., Chen, S., Mai, B., Covaci, A., 2015. Flame retardants and organochlorines in indoor dust from several e-waste recycling sites in South China: Composition variations and implications for human exposure. Environ. Int. 78, 1–7. https://doi.org/10.1016/j.envint.2015.02.006 Zota, A.R., Rudel, R.A., Morello-Frosch, R.A., Brody, J.G., 2008. Elevated House Dust and Serum Concentrations of PBDEs in California: Unintended Consequences of Furniture Flammability Standards? Environ. Sci. Technol. 42, 8158–8164. https://doi.org/10.1021/es801792z

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Chapter 5 - Conclusions

5.1 Summary of contributions

Humans are exposed to a complex mixture of natural and anthropogenic contaminants including FRs and plasticizers through both occupational exposure and interactions with the ambient environment. Environmental exposures to some FRs and plasticizers, which occur at relatively low levels, have been associated with human health effects including neurodevelopmental effects arising from fetal exposure and reduced reproductive success among individuals of child-bearing years (Carignan et al., 2018; Glazer et al., 2018; Lam et al.,

2017; Meeker and Stapleton, 2009). However, less well investigated are exposures and potential adverse effects to these contaminants among occupational groups who could be exposed to higher levels. One challenge to studying the effects of contaminants in the workplace is the ability to monitor exposures. Here, passive samplers could be useful for measuring occupational exposure to FRs and plasticizers.

With the goal of addressing these concerns, this thesis reports on the development and evaluation of the passive measurement methods for improving occupational exposure monitoring and assessment. The thesis also provides new data on air and dust exposure of e- waste recycling workers to 37 FRs, as well as on air exposure of nail salon workers to 29 FRs and plasticizers (including phthalates and OPEs).

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5.2 Detailed discussion of contributions to environmental and exposure science

5.2.1 Documenting current exposure levels of FRs in e-waste facilities

Before this thesis, there was little information about current exposure levels of FRs in e-waste facilities in high-income countries. Most studies of e-waste facilities in high-income countries had been done over a decade ago (Pettersson-Julander et al., 2004; Rosenberg et al.,

2011; Sjödin et al., 2001). Chapters 2 and 3 reported current exposure levels of over 37 FRs collected by various measurement methods (e.g., active air sampling, passive stationary air sampling, personal passive samplers, and dust collection) in four e-waste recycling facilities in

Canada (one in Ontario and three in Quebec). The thesis adds more data to the existing scant literature on both stationary (Chapter 2) and personal (chapter 2 and 3) concentrations of a wide range of FRs in e-waste recycling facilities.

Results from chapter 2 showed unexpectedly high exposures in a formal Ontario e- waste facility that exceeded for both now “banned” FRs (e.g., PBDEs) and their replacements

(e.g., NHFRs and OPEs) compared to several previous e-waste studies of formal and informal facilities located in other countries. Chapter 3 reported that total levels of PBDEs in silicone wristbands worn by Quebec e-waste workers were 14 times higher than wristbands with similar size and design worn by Bangladeshi e-waste workers (Wang et al., 2020). Not surprisingly, higher detection frequencies were found for FRs in silicone samplers worn by e-waste workers

(especially e-waste dismantlers) in Quebec facilities (Chapter 3) compared to previous studies in office (Okeme et al., 2018a) and home environments (Wang et al., 2019). Most PBDEs in silicone brooches in Chapter 3 were detected in > 80% of samples deployed for 6-10 hours while no PBDEs were detected in silicone brooches deployed for 24 hours in the office environments. The higher detection frequency here compared to other indoor environments is

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presumably due to the higher air concentrations of FRs in e-waste environment. The thesis documented a wide range of PBDEs in silicone brooches for the first time.

5.2.2 Documenting current exposure levels of plasticizers in nail salons

Only two studies, those of Estill et al. (2020) and Craig et al. (2019), have reported personal exposure levels of nail salon workers to plasticizers (including phthalates and OPEs).

Among OPEs, Estill et al. (2020) only analyzed TPhP and found that levels in hand wipes of nail salon workers (n = 12) were at least 2 times higher than those of workers in other industries such as electronic scrap, carpet installation, spray polyurethane industries. However, personal air levels of TPhP in nail salon were less than a half of those levels in other industries (Estill et al., 2020). A pilot study of Craig et al. (2019) found that nail salon workers (n = 10) were exposed to phthalate and OPEs during their single work shift where higher concentrations of phthalate and OPE urinary metabolites were found in post-shift samples compared to pre-shift samples. Additionally, post-shift urinary concentrations for DEHTP, TCEP and TPhP reported by Craig et al. (2019) were higher than concentrations from US females reported in the National

Health and Nutrition Examination Survey (NHANES). However, both of these nail salon studies had small sample sizes (≤12 participants) and analyzed less than 5 OPEs.

Before this thesis, no study had reported on exposures to phthalates and OPEs among

Canadian nail salon workers. To fill this knowledge gap, Chapter 4 contributed new data on personal exposure levels to over 29 phthalates and OPEs among 45 nail salon workers in

Toronto. This study used conventional personal active air samplers and also novel personal silicone passive samplers.

Results from Chapter 4 confirmed high exposure levels of TPhP in nail salons found in previous studies. Median air levels of most phthalates found in this thesis were at least 2 times

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higher than those found in office environment (Okeme et al., 2018a). In comparison to the pilot study of Craig et al. (2019) in US nail salons, median levels of individual phthalates and OPEs found in wristbands here were at least 1.5 and 51 times higher for phthalate and OPEs, respectively. Additionally, the thesis reported unexpectedly high detection frequencies (>98%) and elevated exposures to TCEP and TCIPP via air among nail salon workers. In particular,

TCEP has been associated with papillary thyroid cancer (Hoffman et al., 2017b) but there are no occupational exposure limits for TCEP and other OPEs (except from TPhP) in Canada.

I hypothesized that the types of services and numbers of services workers performed by each nail salon worker on the sampling day were related to the personal air concentrations of plasticizers in nail salons. However, results in Chapter 4 did not support this hypothesis.

5.2.3 Advancing our understanding of the use of silicone passive samplers as a promising measurement tool in occupational exposure monitoring and assessment.

Several studies have used silicone passive samplers as stationary air samplers and personal integrative samplers for measuring SVOC exposure over relatively long periods of time (3 - 50 days) to allow sufficient time for the samplers to accumulate SVOCs given the low concentrations in non-occupational indoor environments (e.g., homes, schools, offices, etc.)

(Hammel et al., 2016, 2018; Okeme et al., 2018d, 2016b). Only two studies with small sample sizes (n < 10) co-deployed active air and silicone brooches to characterize the silicone brooch as personal passive air sampler in offices (Okeme et al., 2018b) and homes (Wang et al., 2019).

Further, the use of wristbands for measuring personal exposure to SVOCs over a relative short deployment time (8 – 24 hours) has only been reported in two indoor occupational environments, specifically nail salons (Craig et al., 2019) and e-waste recycling workshops

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(Wang et al., 2020). The sample size of Craig et al. (2019) and Wang et al. (2020) were also relatively small (n < 15). Before this thesis, the usefulness of silicone passive samplers for measuring personal exposure levels of SVOCs in occupational settings over shorter deployment (~ 8 working hours, or a standard work day) was not well-studied.

The thesis (Chapter 3 and 4) advanced our knowledge of the usefulness of passive samplers as a qualitative measurement tool for SVOC exposure. Results of Chapter 3 and 4 suggested that silicone samplers can accumulate detectable amounts of a wide range of FRs and plasticizers during a single work shift (~8 hours) in occupational settings where these

SVOCs are expected. Future occupational studies can use silicone samplers as a reliable, easy- to-deploy and relatively cheap measurement tools for assessing SVOC exposure where qualitative information on exposure is desirable.

Prior to this thesis, only one small (n = 10) non-occupational study from Wang et al.

(2019) compared silicone samplers (brooches and wristbands) with the “gold standard” active air samplers for measuring SVOCs in air. Wang et al. (2019) concluded that silicone brooches are promising alternative to active air samplers for measuring OPEs and NHFRs based on strong correlations for these chemicals between silicone brooches and active air samplers. They also found poor correlations for PBDEs and PAHs. No study has further investigated the relationship between silicone samplers and active air samplers. As a contribution towards addressing this research gap, the thesis is the first study which used active air samplers to calibrate the silicone samplers as personal passive air samplers in occupational indoor environments. Chapters 3 and 4 compared personal passive silicone samplers and personal active air samplers for measuring occupational exposure to FRs and plasticizers in e-waste and nail salon workplaces. Results from Chapter 3 suggested that levels accumulated by silicone brooches compared to armbands and wristbands were better correlated with levels from active air samplers for a wide range of FRs (including PBDEs, NHFRs and OPEs) in e-waste recycling

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environment. Results from Chapter 4 support these findings in Chapter 3, but weaker correlations between brooches and active air samplers were observed in nail salons (Chapter

4). As discussed below in section 5.3, this difference may be due to multiple factors. The findings of this thesis were consistent with results in the non-occupational study of Wang et al.

(2019) which found stronger correlations between active air samplers and silicone brooches compared to active air samplers and silicone wristbands. To sum up, the inconsistency from results in Chapter 3 and 4 indicated that silicone brooches and wristbands are not necessarily reliable quantitative measurement tools for assessing inhalation exposure to FRs and plasticizers and other exposures related to air concentrations in occupational settings. However, silicone brooch and wristbands can offer a valuable screening tool in indoor and occupational settings since these samplers provide reasonable estimates of both SVOC concentrations and profiles which are indicative of ambient concentrations and likely sources.

The use of personal passive samplers can have several purposes. One is to quantify exposure from a specific pathway, for example inhalation. Another purpose is for use to indicate internal contaminant burden. For example, much of the literature on the deployment of wristbands in residential settings has related contaminant levels in those wristbands with either parent or metabolite levels from biomonitoring (Hammel et al., 2016, 2018). Results from Chapter 3 showed that both silicone brooches and wristbands can be useful in an occupational setting for assessing internal exposure to compounds with relatively long biological half-lives (e.g., BDE-209 in blood; half-life of 15 days). However, their application for assessing exposure to contaminants with relatively short half-lives (e.g., OPE metaobiltes in urine) is uncertain. The lack of correlation between silicone samplers and urinary metabolites may result from the limitation that our study was able to collect only urinary samples spot samples where urinary OPE metabolites could fluctuate due to the relatively short metabolic half-lives (Percy et al., 2020).

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5.2.4 Updating the sampling rates of silicone samplers for assessing SVOC exposure in indoor environments

The choice of a sampling rate that reflects the sampling environment is critical for reporting reliable and comparable air concentration data. Because of the impracticality of calibrating passive air samplers at each sampling site, generic sampling rates measured at one location are commonly used to interpret passive sampler results obtained at different locations

(e.g., Gevao et al., 2006; Zhang et al., 2011). Generic sampling rates of silicone samplers in this thesis and other studies in Table 5.1 (Okeme et al., 2018, 2016; Okeme and Yang et al.,

2018) were obtained by taking the average of compound-specific rates.

Before this thesis, only three studies (Okeme et al., 2018a, 2016; Okeme and Yang et al.,2018) provided the generic sampling rates of stationary and personal silicone samplers for

SVOCs in homes and offices (see Table 5.1). The thesis substantially added to the literature on the sampling rates of silicone brooches for measuring FRs from occupational environment such as e-waste facilities (Chapter 3) (see Table 5.1). Since correlations were not strong between silicone brooches and active air samplers deployed in nail salons (Chapter 4), the thesis did not report estimated sampling rates of brooch for phthalates and OPEs in this environment.

Table 5.1. Summary of generic sampling rates (m3 day -1 dm-2) of silicone passive samplers used for measuring SVOCs exposure via air in various indoor environments.

Sampling locations, Generic sampling Group of compounds References sampler types (number of rates (mean ± SD) samples, n) (m3 day-1 dm-2) E-waste facilities, 19 ± 11 PBDEs, NHFRs, This thesis, Chapter 3 personal silicone brooches OPEs (n = 45) Canadian offices, personal 0.9 ± 0.3 Phthalates and OPEs Okeme et al. (2018) silicone brooches (n = 5) Canadian homes, 1.5± 1.1 Phthalates, NHFRs, Okeme and Yang et al. stationary silicone PBDEs and OPEs (2018) Canadiansamplers (noffices, = 51) 0.8± 1.1 Phthalates, NHFRs, Okeme et al. (2016) stationary silicone PBDEs samplers (n = 10)

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Higher generic sampling rates of silicone samplers estimated in e-waste facilities compared to those values in the home and office studies may be explained by several factors noted in the following section 5.3.

5.3 Proposed main factors influencing personal exposure measurements of passive samplers

The accumulation of SVOCs in passive samplers is related to three main parameters including the air-side mass transfer coefficient, exposed surface area of the passive sampler, and the air concentration of that chemical. Based on results from this thesis, and previous studies (Allen et al., 2007; Pernilla Bohlin et al., 2014; Okeme et al., 2018b; Shoeib and Harner,

2002), four main factors are proposed to affect these parameters and hence influence exposure measurements: sampler characteristics, personal characteristics, chemical emission sources and indoor environment characteristics. These factors are summarized in a conceptual model shown in Figure 5.1. This model can guide the interpretation of results obtained from deployment of personal passive samplers.

Figure 5.1. Main factors proposed to influence the exposure measurements collected using personal passive samplers.

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5.3.1 Sampler characteristics

The sampler type, position (or location) of deployment and sampler materials may influence the amount of chemicals collected by passive samplers (Bohlin et al., 2010b; Okeme et al., 2018d, 2016b; Saini et al., 2015). Previous studies in both occupational and non- occupational environments have reported higher exposure levels in personal samplers compared to stationary samplers from the same environment (Allen et al., 2007; Bohlin et al.,

2010a; Mäkinen et al., 2009). Personal samplers better reflect personal exposure to chemicals compared to stationary samplers. Results presented in Chapters 3 and 4 indicated that a sampler’s deployment position can influence the mass of chemical accumulated. For example, silicone wristbands and armbands likely capture chemicals on contaminated surfaces by direct contact while silicone brooches are unlikely to efficiently collect from surfaces.

Passive samplers consisting of materials other than silicone were not tested in this thesis, but sampling materials with rougher surface morphology such as polyurethane foam

(PUF) and XAD better capture particles than silicone rubber, which has a smoother surface

(Okeme and Yang et al., 2018). However, in occupational environments that involve intensive physical activities (e.g., e-waste facilities, construction site) PUF without enclosed housing

(Bohlin et al., 2010a) may be impractical as it is more fragile than silicone rubber and can be ripped off when performing tasks such as holding and lifting heavy objects.

5.3.2 Chemical emission sources

The characteristics of emission sources, such as whether emissions are constant or intermittent, point or area emissions, can contribute to the variability of contaminant concentrations and variability of contaminant levels collected by passive samplers. For example, a passive sampler with a slow uptake rate is likely to miss sporadic high emission

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events, compared to a faster uptake active air sampler. Further, emissions of phthalates and

OPEs in a workplace such as a nail salon (Chapter 4) may be higher at specific times when the nail products (e.g., nail polishes or solvents) are used and specific locations where services are performed. The variability in emission sources may also contribute to the variability of personal exposure to those chemicals. For example, higher levels of BDE-209 found in brooches of e- waste dismantlers who handling television and larger electronic devices compared to those handling smaller devices (Chapter 3) is consistent with the higher levels of BDE-209 in used in television casing compared to smaller devices (e.g., personal computers, audio/video devices, etc.) (Abbasi et al., 2016). Finally, the phase in which the chemical is emitted can influence the uptake efficiency of the sampler. Silicone rubber efficiently accumulates gas- phase compounds but its efficiency for particle-phase compounds is lower and not well characterized (Okeme et al., 2018b, 2018d).

5.3.3 Personal characteristics

The physical movement of workers can create a personal cloud of contaminants in the close proximity of their body, leading to increase personal exposure to those contaminants

(Allen et al., 2007; Rodes et al., 1991; Wallace, 2000). The personal cloud effect would be stronger when the air is more stagnant and poorly mixed with ambient air. For example, having emission sources (e.g., nail polishes or solvents in nail salons) close to workers who do not move much in an enclosed environment, like nail salons where the air may be poorly mixed with outdoor air, could result in high gas-phase concentrations in their personal cloud.

Variability of activities including job tasks or personal habits also can lead to variability in contaminant exposure. For an example, in e-waste recycling settings (Chapter 3), lower

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levels of FRs were found in brooches worn by workers who handled smaller electronics compared to those worn by workers who dismantled larger electronics.

5.3.4 Indoor environment characteristics

Indoor environment characteristics (ventilation, temperature, indoor chemistry, etc.) can also influence the variability of exposure measurements collected by passive samplers. For an example, higher air levels of FRs in the formal e-waste facility (Chapter 2) compared to those in Vietnamese informal e-waste facilities (Tue et al., 2013) could be partly due to the fact that the air in the informal e-waste facilities was more likely diluted by the outdoor air via natural ventilation.

Temperature can also influence the variability of SVOC concentrations in indoor environments (Bi et al., 2015; Gaspar et al., 2014; MacIntosh et al., 2012). For example, in US school environment, the indoor temperature accounted for 79% of the variability of polychlorinatedbiphenyls (PCBs) air concentrations over the period of 2 days (MacIntosh et al., 2012). Furthermore, the air concentrations of DEHP and BzBP in a test house at 30℃ were higher than those at 21℃ by a factor of 3 (Bi et al., 2015). However, the influence of temperature on SVOC indoor concentrations are inconsistent in literature. For example, in the study at Canadian residential buildings, Wan et al. (2020) found that there were weak correlations between air concentrations of phthalates and room temperatures. No correlations were found between temperature and the air concentrations of phthalates and OPEs in the multi- location indoor study of Bergh et al. (2011).

Previous studies showed that relative humidity was not correlated to concentrations of

SVOCs (Bergh et al., 2011; Okeme and Yang et al., 2018). In the study at Canadian homes,

Okeme and Yang et al. (2018) found that air concentrations of numerous SVOCs including

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phthalates, PBDEs, NHFRs and OPEs, were not systematically correlated with relative humidity (22 - 67%). Bergh et al. (2011) in the study of muli-location indoor study also found no correlation between relative humidity (16 - 35%) and air concentrations of phthalates and

OPEs.

Variability of indoor SVOCs concentrations may also be influenced by indoor transformation reactions such as hydrolysis of phthalates (Ekelund et al., 2010; Nalli et al.,

2006) and reactivity of SVOCs with indoor oxidants (e.g, ozone, hydroxyl radical (OH) and nitrate radicals (NO3) (Wei et al., 2017). Further, in the study of reactivity of SVOCs with indoor oxidants, Wei et al. (2017) concluded that reaction of some SVOCs such as PAHs and biocides in indoor air has an impact on the SVOC concentrations.

5.4 Overall strengths and limitations

5.4.1 Strengths

• The thesis provides first reports on occupation exposures of a wide range of FRs and

plasticizers in Canadian e-waste recycling and nail salon industry to advance our

knowledge of occupational exposure in those two industries in Canada.

o The findings in the formal e-waste facilities studied here showed the surprisingly

higher levels of various FRs compared to those in the informal e-waste facilities.

Results suggest that having a “formal” facility does not necessarily reduce

exposures to FRs for e-waste workers.

o The thesis reported unexpected exposures to some OPEs (e.g., TCEP and TCIPP),

which are known more as FRs than plasticizers, in personal exposure

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measurements among nail salon workers studied; levels were substantially higher

than previous studies.

• The thesis advanced the understanding of the use of personal silicone passive samplers

with a relatively short-term deployment in occupational settings (e.g. e-waste recycling

facilities and nail salons).

• The deployment of passive samplers in two different occupational environments

provided data allowing the comparison of passive samplers and between passive and

active air samplers and biomarkers. These results can help to guide future study designs

for measuring exposure to SVOCs in other indoor environments.

5.4.2 Limitations

• For this research we accessed 4 e-waste recycling facilities and 18 nail salons in total.

Hence, the thesis reflects a subset of e-waste recycling and nail salon industry in

Canada.

• Various assumptions about exposure factors were made in order to estimate exposure

via non-dietary pathways (Chapter 2). The exposure factors used to estimate exposures

were obtained from U.S. Environmental Protection Agency (US EPA, 2011) mainly

based on general population data intended for long-term exposure. It may lead to over

or underestimate exposure to FRs by occupational workers.

• Biological measures of exposure represent exposure from all sources and routes of

exposures (e.g., diet, environmental exposures outside of the workplace) for which we

did not collect information.

• A single spot urine sample, as used in Chapter 3, may not be representative of the

exposure captured by personal passive and active air sampler, particularly for relatively

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short half-lives compounds like OPEs. Spot urine levels are not necessarily

representative of the whole sampling period and may be affected by the choices of

collection time.

• Silicone rubber more efficiently accumulates SVOCs in the gas than particle phase,

which could be the problematic when assessing exposure in dusty environments such as

e-waste facilities.

5.5 Overall conclusions

The thesis contributed knowledge on occupational exposures to FRs and plasticizers in formal e-waste facilities and nail salons in Canada. Exposures in a formal Ontario e-waste facility were higher, and more FRs were detected, compared to previous studies in formal and informal facilities in other countries. A wide range of FRs and plasticizers were found at elevated concentrations in nail salons. Surprisingly, some chlorinated OPEs which are known for their use as FRs and not for their use in personal care products, were found at relatively high concentrations. Hence, the thesis suggests that e-waste and nail salon workers have been exposed to high levels of FRs and plasticizers which are, largely, not addressed by occupational exposure limits.

This thesis also advanced the understanding of the uses of silicone passive samplers for personal exposure monitoring and assessment. All silicone samplers accumulated detectable amounts of FRs and plasticizers within relative short deployment time (average of ~8 hours).

Silicone brooches and wristbands deployed in a single work shift (~8 hours) can be useful for indicating internal burdens to compounds at relatively high concentrations in air and/or particles, and with relatively long-biological half-lives like BDE-209 in blood. However, their uses for compounds with relatively short half-lives like OPEs has not been established. Among three types of silicone samplers, the silicone brooch was the best alternative to active air

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samplers. The correlations between passive and active air samplers varied between occupational environments. In general, strong correlations were not found between FRs and plasticizer levels in passive samplers worn at different positions on the body. These variations could be due to many factors including the extent of air mixing around the worker and site- specific characteristics. Hence, silicone samplers are recommended for use in future occupational studies as a convenient screening tool for personal exposure monitoring and assessment, but not yet as a reliable quantitative measurement tool.

5.6 Recommendations for future work

The thesis has provided important insights into the occupational exposure to FRs and plasticizers at e-waste recycling sites and nail salons and the use of silicone passive samplers in occupational settings for measuring SVOCs. However, some limitations can be more fully investigated in future work in order to improve our understanding of occupational exposure to

SVOCs and advance the science of silicone samplers for exposure monitoring:

• High levels of FRs and phthalates found in both e-waste and nail salon environments

indicate a need for more studies of exposure interventions to reduce occupational

exposures to FRs and plasticizers. For example, future research should investigate

emissions of phthalates and OPEs from personal care products (e.g., nail polishes,

shellac, lotions, etc.) and other consumer products (e.g., cleaning products, air

fresheners, etc.) used in nail salons in order to identify and eliminate sources of those

contaminants. Future studies should also investigate the effectiveness of engineering

controls (e.g., local exhaust ventilation, local fans, etc.) and personal protective

equipment (e.g, face masks, gloves, protective suits, etc.) to reduce exposures to FRs

and plasticizers at e-waste facilities and nail salons. High levels of FRs and plasticizers

189

found in air and dust at e-waste workers and nail salons also call for more studies on

health effects from exposures to those compounds.

• The lack of strong correlation between silicone wristbands and active air samplers in

the studies presented here suggests that future studies should investigate the factors that

influence exposure levels and exposure measurement methods. Information on many

factors that can influence exposure (e.g., products used, ventilation rates) was not

collected in the studies that make up this thesis. Future studies should investigate such

factors. Future occupational studies should also investigate relationships between

silicone wristbands and other routes of exposure (e.g., dust ingestion, hand-to-mouth,

dermal absorption) in order to better understanding the data obtained from wristbands.

• Both active and passive air samplers represent an integrated exposure across the whole

sampling period, while spot urine levels are not integrated over the sampling period and

may be affected by the choices of collection time. More studies should further assess

the relationship between silicone samplers and biomonitoring measurements. For

instance, future work could test the correlation between silicone samplers and changes

in biomarkers (e.g., from urine) collected at various time points (e.g., pre- and post-

work shift) to better assess the relationship between silicone samplers and urine during

a single work shift.

References

Abbasi, G., Buser, A.M., Soehl, A., Murray, M.W., Diamond, M.L., 2015. Stocks and flows

of PBDEs in products from use to waste in the U.S. and canada from 1970 to 2020.

Environ. Sci. Technol. 49, 1521–1528. https://doi.org/10.1021/es504007v

Abbasi, G., Saini, A., Goosey, E., Diamond, M.L., 2016. Product screening for sources of

halogenated flame retardants in Canadian house and office dust. Sci. Total Environ.

545–546, 299–307. https://doi.org/10.1016/j.scitotenv.2015.12.028

190

Abdallah, M.A.-E., Pawar, G., Harrad, S., 2015a. Evaluation of 3D-human skin equivalents

for assessment of human dermal absorption of some brominated flame retardants.

Environ. Int. 84, 64–70. https://doi.org/10.1016/j.envint.2015.07.015

Abdallah, M.A.-E., Pawar, G., Harrad, S., 2015b. Effect of Bromine Substitution on Human

Dermal Absorption of Polybrominated Diphenyl Ethers. Environ. Sci. Technol. 49,

10976–10983. https://doi.org/10.1021/acs.est.5b03904

Abou-Elwafa Abdallah, M., Pawar, G., Harrad, S., 2016. Human dermal absorption of

chlorinated organophosphate flame retardants; implications for human exposure.

Toxicol. Appl. Pharmacol. 291, 28–37. https://doi.org/10.1016/j.taap.2015.12.004

ACGIH, 2018. TLVs ® and BEIs ® : Threshold limit values for chemical substances and

physical agents biological exposure indices. American Conference of Governmental

Industrial Hygienists, Cincinnati, OH, OH.

ACGIH, 2001. Documentation of threshold limit values for substances in work environment.

American Conference of Governmental Industrial Hygienists, Cincinnati, OH, OH.

Ait, Y., Araki, A., Kawai, T., Tsuboi, T., Saito, I., Yoshioka, E., Kanazawa, A., 2014.

Science of the Total Environment Associations of phthalate concentrations in fl oor dust

and multi-surface dust with the interior materials in Japanese dwellings. Sci. Total

Environ. 468–469, 147–157. https://doi.org/10.1016/j.scitotenv.2013.07.107

Akormedi, M., Asampong, E., Fobil, J.N., 2013. Working conditions and environmental

exposures among electronic waste workers in Ghana. Int. J. Occup. Environ. Health 19,

278–286. https://doi.org/10.1179/2049396713Y.0000000034

Allen, J.G., McClean, M.D., Stapleton, H.M., Nelson, J.W., Webster, T.F., 2007. Personal

Exposure to Polybrominated Diphenyl Ethers (PBDEs) in Residential Indoor Air.

Environ. Sci. Technol. 41, 4574–4579. https://doi.org/10.1021/es0703170

Allen, J.O., Dookeran, N.M., Smith, K.A., Sarofim, A.F., Taghizadeh, K., Lafleur, A.L.,

191

1996. Measurement of polycyclic aromatic hydrocarbons associated with size-

segregated atmospheric aerosols in Massachusetts. Environ. Sci. Technol. 30, 1023–

1031. https://doi.org/10.1021/es950517o

Andersen, C., Krais, A.M., Eriksson, A.C., Jakobsson, J., Löndahl, J., Nielsen, J., Lindh,

C.H., Pagels, J., Gudmundsson, A., Wierzbicka, A., 2018. Inhalation and Dermal Uptake

of Particle and Gas-Phase Phthalates—A Human Exposure Study. Environ. Sci.

Technol. 52, 12792–12800. https://doi.org/10.1021/acs.est.8b03761

Asante, K.A., Agusa, T., Biney, C.A., Agyekum, W.A., Bello, M., Otsuka, M., Itai, T.,

Takahashi, S., Tanabe, S., 2012. Multi-trace element levels and arsenic speciation in

urine of e-waste recycling workers from Agbogbloshie, Accra in Ghana. Sci. Total

Environ. 424, 63–73. https://doi.org/10.1016/j.scitotenv.2012.02.072

ATSDR, 2012. Toxicological Profile for Phosphate Ester Flame Retardants.

ATSDR, 2005. Public Health Assessment Guidance Manual (2005 Update). Atlanta, Georgia.

ATSDR, 2004. Toxicological profile for polybrominated biphenyl and polybrominated

diphenyl ethers 1–599.

Awasthi, A.K., Wang, M., Wang, Z., Awasthi, M.K., Li, J., 2018. E-waste management in

India: A mini-review. Waste Manag. Res. 36, 408–414.

https://doi.org/10.1177/0734242X18767038

Bakhiyi, B., Gravel, S., Ceballos, D., Flynn, M.A., Zayed, J., 2018. Has the question of e-

waste opened a Pandora’s box? An overview of unpredictable issues and challenges.

Environ. Int. 110, 173–192. https://doi.org/https://doi.org/10.1016/j.envint.2017.10.021

Balde, C.P., Forti, V., Gray, V., Kuehr, R., Stegmann, P., 2017. The global e-waste monitor

2017, United Nations University. https://doi.org/10.1016/j.proci.2014.05.148

Baldé, C.P., Wang, F., Kuehr, R., Huisman, J., 2015. The Global E-waste Monitor 2014:

Quantitites, flows and resources. Bonn, Germany. https://doi.org/ISBN 978-92-808-

192

4556-3

Bartkow, M.E., Booij, K., Kennedy, K.E., Müller, J.F., Hawker, D.W., 2005. Passive air

sampling theory for semivolatile organic compounds. Chemosphere 60, 170–176.

https://doi.org/10.1016/j.chemosphere.2004.12.033

Basel Convention, 2011. Electrical and electronic equipment when becoming waste (e-waste)

such as personal computers, printers, televisions, mobile phones, refrigerators and air-

conditioning units is one of the fastest growing waste streams in the world today.

[WWW Document]. URL

http://www.basel.int/Implementation/Ewaste/Overview/tabid/4063/Default.aspx

(accessed 3.8.20).

Beaucham, C.C., Ceballos, D., Page, E.H., Mueller, C., Calafat, A.M., Sjodin, A., Ospina,

M., Guardia, M. La, Glassford, E., 2018. Evaluation of Exposure to Metals , Flame

Retardants , and Nanomaterials at an Electronics Recycling Company 1–80.

Behl, M., Hsieh, J.H., Shafer, T.J., Mundy, W.R., Rice, J.R., Boyd, W.A., Freedman, J.H.,

Hunter, E.S., Jarema, K.A., Padilla, S., Tice, R.R., 2015. Use of alternative assays to

identify and prioritize organophosphorus flame retardants for potential developmental

and neurotoxicity. Neurotoxicol. Teratol. 52, 181–193.

https://doi.org/10.1016/j.ntt.2015.09.003

Behl, M., Rice, J.R., Smith, M. V., Co, C.A., Bridge, M.F., Hsieh, J.-H., Freedman, J.H.,

Boyd, W.A., 2016. Editor’s Highlight: Comparative Toxicity of Organophosphate Flame

Retardants and Polybrominated Diphenyl Ethers to Caenorhabditis elegans. Toxicol.

Sci. 154, 241–252. https://doi.org/10.1093/toxsci/kfw162

Bergh, C., Torgrip, R., Emenius, G., Östman, C., 2011. Organophosphate and phthalate esters

in air and settled dust - a multi-location indoor study. Indoor Air 21, 67–76.

https://doi.org/10.1111/j.1600-0668.2010.00684.x

193

Betts, K.S., 2002. Rapidly rising PBDE levels in North America. Environ. Sci. Technol. 36,

50A-52A. https://doi.org/10.1021/es022197w

Bi, C., Liang, Y., Xu, Y., 2015. Fate and Transport of Phthalates in Indoor Environments and

the Influence of Temperature: A Case Study in a Test House. Environ. Sci. Technol. 49,

9674–9681. https://doi.org/10.1021/acs.est.5b02787

Bidleman, T.F., 1988. Atmospheric processes. Environ. Sci. Technol. 22, 361–367.

https://doi.org/10.1021/es00169a002

Blum, A., Behl, M., Birnbaum, L.S., Diamond, M.L., Phillips, A., Singla, V., Sipes, N.S.,

Stapleton, H.M., Venier, M., 2019. Organophosphate Ester Flame Retardants: Are They

a Regrettable Substitution for Polybrominated Diphenyl Ethers? Environ. Sci. Technol.

Lett. 6, 638–649. https://doi.org/10.1021/acs.estlett.9b00582

Bohlin, P., Audy, O., Škrdlíková, L., Kukučka, P., Přibylová, P., Prokeš, R., Vojta, Š.,

Klánová, J., 2014. Outdoor passive air monitoring of semi volatile organic compounds

(SVOCs): a critical evaluation of performance and limitations of polyurethane foam

(PUF) disks. Environ. Sci. Process. Impacts 16, 433–444.

https://doi.org/10.1039/C3EM00644A

Bohlin, Pernilla, Audy, O., Škrdlíková, L., Kukučka, P., Vojta, Š., Přibylová, P., Prokeš, R.,

Čupr, P., Klánová, J., 2014. Evaluation and guidelines for using polyurethane foam

(PUF) passive air samplers in double-dome chambers to assess semi-volatile organic

compounds (SVOCs) in non-industrial indoor environments. Environ. Sci. Process.

Impacts 16, 2617–2626. https://doi.org/10.1039/C4EM00305E

Bohlin, P., Jones, K.C., Levin, J.-O., Lindahl, R., Strandberg, B., 2010a. Field evaluation of a

passive personal air sampler for screening of PAH exposure in workplaces. J. Environ.

Monit. 12, 1437. https://doi.org/10.1039/c0em00018c

Bohlin, P., Jones, K.C., Strandberg, B., 2010b. Field evaluation of polyurethane foam passive

194

air samplers to assess airborne PAHs in occupational environments. Environ. Sci.

Technol. 44, 749–754. https://doi.org/10.1021/es902318g

Bohlin, P., Jones, K.C., Strandberg, B., 2007. Occupational and indoor air exposure to

persistent organic pollutants: A review of passive sampling techniques and needs. J.

Environ. Monit. 9, 501. https://doi.org/10.1039/b700627f

Bornehag, C.G., Nanberg, E., 2010. Phthalate exposure and asthma in children 33, 333–345.

https://doi.org/10.1111/j.1365-2605.2009.01023.x

Braun, J.M., Kalkbrenner, A.E., Just, A.C., Yolton, K., Calafat, A.M., Sjödin, A., Hauser, R.,

Webster, G.M., Chen, A., Lanphear, B.P., 2014. Gestational Exposure to Endocrine-

Disrupting Chemicals and Reciprocal Social, Repetitive, and Stereotypic Behaviors in 4-

and 5-Year-Old Children: The HOME Study. Environ. Health Perspect. 122, 513–520.

https://doi.org/10.1289/ehp.1307261

Breul, S., Van Landuyt, K.L., Reichl, F.X., Högg, C., Hoet, P., Godderis, L., Van Meerbeek,

B., Cokic, S.M., 2020. Filtration efficiency of surgical and FFP3 masks against

composite dust. Eur. J. Oral Sci. 128, 233–240. https://doi.org/10.1111/eos.12697

Brown, J., Gordon, T., Price, O., Asgharian, B., 2013. Thoracic and respirable particle

deinitions for human health risk assessment. Part. Fibre Toxicol. 10, 1–12.

Cahill, T.M., Groskova, D., Charles, M.J., Sanborn, J.R., Denison, M.S., Baker, L., 2007.

Atmospheric concentrations of polybrominated diphenyl ethers at near-source sites.

Environ. Sci. Technol. 41, 6370–6377. https://doi.org/10.1021/es070844j

Callesen, M., Bekö, G., Weschler, C.J., Langer, S., Brive, L., Clausen, G., Toftum, J.,

Sigsgaard, T., Høst, A., Kold, T., 2014. International Journal of Hygiene and Phthalate

metabolites in urine and asthma , allergic rhinoconjunctivitis and atopic dermatitis in

preschool children. Int. J. Hyg. Environ. Health 217, 645–652.

https://doi.org/10.1016/j.ijheh.2013.12.001

195

Cao, Z., Xu, F., Covaci, A., Wu, M., Wang, H., Yu, G., Wang, B., Deng, S., Huang, J.,

Wang, X., 2014. Distribution patterns of brominated, chlorinated, and phosphorus flame

retardants with particle size in indoor and outdoor dust and implications for human

exposure. Environ. Sci. Technol. 48, 8839–8846. https://doi.org/10.1021/es501224b

Carignan, C.C., Mínguez-Alarcón, L., Butt, C.M., Williams, P.L., Meeker, J.D., Stapleton,

H.M., Toth, T.L., Ford, J.B., Hauser, R., 2017. Urinary Concentrations of

Organophosphate Flame Retardant Metabolites and Pregnancy Outcomes among

Women Undergoing in Vitro Fertilization. Environ. Health Perspect. 125, 087018.

https://doi.org/10.1289/EHP1021

Carignan, C.C., Mínguez-Alarcón, L., Williams, P.L., Meeker, J.D., Stapleton, H.M., Butt,

C.M., Toth, T.L., Ford, J.B., Hauser, R., 2018. Paternal urinary concentrations of

organophosphate flame retardant metabolites, fertility measures, and pregnancy

outcomes among couples undergoing in vitro fertilization. Environ. Int. 111, 232–238.

https://doi.org/10.1016/j.envint.2017.12.005

Castorina, R., Bradman, A., Stapleton, H.M., Butt, C., Avery, D., Harley, K.G., Gunier, R.B.,

Holland, N., Eskenazi, B., 2017. Current-use flame retardants: Maternal exposure and

neurodevelopment in children of the CHAMACOS cohort. Chemosphere 189, 574–580.

https://doi.org/10.1016/j.chemosphere.2017.09.037

Ceballos, D.M., Côté, D., Bakhiyi, B., Flynn, M.A., Zayed, J., Gravel, S., Herrick, R.F.,

Labrèche, F., 2020. Overlapping vulnerabilities in workers of the electronics recycling

industry formal sector: A commentary. Am. J. Ind. Med. 63, 955–962.

https://doi.org/10.1002/ajim.23173

Ceballos, D.M., Dong, Z., 2016. The formal electronic recycling industry: Challenges and

opportunities in occupational and environmental health research. Environ. Int. 95, 157–

166. https://doi.org/10.1016/j.envint.2016.07.010

196

CEPA, 1999. Canadian Environmental Protection Act.

Cequier, E., Sakhi, A.K., Marcé, R.M., Becher, G., Thomsen, C., 2015. Human exposure

pathways to organophosphate triesters — A biomonitoring study of mother–child pairs.

Environ. Int. 75, 159–165. https://doi.org/10.1016/j.envint.2014.11.009

Chan, J.K.Y., Wong, M.H., 2013. A review of environmental fate, body burdens, and human

health risk assessment of PCDD/Fs at two typical electronic waste recycling sites in

China. Sci. Total Environ. 463–464, 1111–1123.

https://doi.org/10.1016/j.scitotenv.2012.07.098

Cherrie, J.W., 2003. CommentaryThe Beginning of the Science Underpinning

Occupational Hygiene. Ann. Occup. Hyg. 47, 179–185.

https://doi.org/10.1093/annhyg/meg030

City of Toronto, 2019. Search for an Establishment Monitored by BodySafe [WWW

Document]. URL https://www.toronto.ca/community-people/health-wellness-

care/health-programs-advice/bodysafe/search-for-an-establishment-space-holder-for-

map/ (accessed 7.18.19).

Consumer Product Safety Commission, 2008. Consumer Product Safety Improvement Act of

2008.

Craig, J.A., Ceballos, D.M., Fruh, V., Petropoulos, Z.E., Allen, J.G., Calafat, A.M., Ospina,

M., Stapleton, H.M., Hammel, S., Gray, R., Webster, T.F., 2019. Exposure of Nail Salon

Workers to Phthalates, Di(2-ethylhexyl) Terephthalate, and Organophosphate Esters: A

Pilot Study. Environ. Sci. Technol. 53, 14630–14637.

https://doi.org/10.1021/acs.est.9b02474 de Winter-Sorkina, R., Bakker, M.., Wolterink, G., Zielmaker, M.J., 2006. Brominated flame

retardants: occurrence, dietary intake and risk assessment [WWW Document]. URL

https://www.rivm.nl/bibliotheek/rapporten/320100002.pdf (accessed 6.7.18).

197

Delgado-Saborit, J.M., Stark, C., Harrison, R.M., 2014. Use of a versatile high efficiency

multiparallel denuder for the sampling of PAHs in ambient air: Gas and particle phase

concentrations, particle size distribution and artifact formation. Environ. Sci. Technol.

48, 499–507. https://doi.org/10.1021/es402937d

Dixon, H.M., Scott, R.P., Holmes, D., Calero, L., Kincl, L.D., Waters, K.M., Camann, D.E.,

Calafat, A.M., Herbstman, J.B., Anderson, K.A., 2018. Silicone wristbands compared

with traditional polycyclic aromatic hydrocarbon exposure assessment methods. Anal.

Bioanal. Chem. 410, 3059–3071. https://doi.org/10.1007/s00216-018-0992-z

Eakin, J.M., Champoux, D., MacEachen, E., 2017. Health and safety in small workplaces:

refocusing upstream. Can. J. Public Health 101 Suppl, S29-33.

EC, 2018. Waste Electrical & Electronic Equipment (WEEE) [WWW Document]. Eur.

Comm. https://doi.org/10.1016/j.geb.2005.03.002

Ekelund, M., Azhdar, B., Gedde, U.W., 2010. Evaporative loss kinetics of di(2-

ethylhexyl)phthalate (DEHP) from pristine DEHP and plasticized PVC. Polym. Degrad.

Stab. 95, 1789–1793. https://doi.org/10.1016/j.polymdegradstab.2010.05.007

Eriksson, P., Jakobsson, E., Fredriksson, A., 2001. Brominated flame retardants: a novel class

of developmental toxicants in our environment? Environ. Health Perspect. 109, 903–

908. https://doi.org/10.1289/ehp.01109903

Estill, C.F., Slone, J., Mayer, A., Chen, I.-C., La Guardia, M.J., 2020. Worker exposure to

flame retardants in manufacturing, construction and service industries. Environ. Int. 135,

105349. https://doi.org/10.1016/j.envint.2019.105349

European Commission, 2014. COMMUNICATION FROM THE COMMISSION on the

finalisation of the restriction process on the four phthalates (DEHP, DBP, BBP and

DIBP) under Regulation (EC) No 1907/2006 of the European Parliament and of the

Council concerning Registration, Evaluation, Authori. Off. J. Eur. Union 73, 1–4.

198

ExpoStats, 2015. NDExpo – Treatment of non-detects in industrial hygiene samples [WWW

Document]. URL http://www.expostats.ca/site/app-local/NDExpo/ (accessed 2.20.20).

Factor-Litvak, P., Insel, B., Calafat, A.M., Liu, X., Perera, F., Rauh, V.A., Whyatt, R.M.,

2014. Persistent Associations between Maternal Prenatal Exposure to Phthalates on

Child IQ at Age 7 Years. PLoS One 9, e114003.

https://doi.org/10.1371/journal.pone.0114003

Federman, M.N., Harrington, D.E., Krynski, K.J., 2006. Vietnamese Manicurists: Are

Immigrants Displacing Natives or Finding New Nails to Polish? ILR Rev. 59, 302–318.

https://doi.org/10.1177/001979390605900207

Fisher, M., Arbuckle, T.E., MacPherson, S., Braun, J.M., Feeley, M., Gaudreau, É., 2019.

Phthalate and BPA Exposure in Women and Newborns through Personal Care Product

Use and Food Packaging. Environ. Sci. Technol. 53, 10813–10826.

https://doi.org/10.1021/acs.est.9b02372

Flanagan, M.E., Seixas, N., Majar, M., Camp, J., Morgan, M., 2003. Silica Dust Exposures

During Selected Construction Activities. AIHA J. 64, 319–328.

https://doi.org/10.1080/15428110308984823

Fortia, V., Balde, C.P., Kuehr, R., Bel, G., 2020. The Global E-waste Monitor 2020:

Quantitites, flows and circular economy potential [WWW Document]. URL

https://collections.unu.edu/view/UNU:7737 (accessed 10.13.20).

Fraser, A.J., Webster, T.F., McClean, M.D., 2009. Diet Contributes Significantly to the Body

Burden of PBDEs in the General U.S. Population. Environ. Health Perspect. 117, 1520–

1525. https://doi.org/10.1289/ehp.0900817

Frazzoli, C., Orisakwe, O.E., Dragone, R., Mantovani, A., 2010. Diagnostic health risk

assessment of electronic waste on the general population in developing countries’

scenarios. Environ. Impact Assess. Rev. 30, 388–399.

199

https://doi.org/10.1016/j.eiar.2009.12.004

Frederiksen, M., Stapleton, H.M., Vorkamp, K., Webster, T.F., Jensen, N.M., Sørensen, J.A.,

Nielsen, F., Knudsen, L.E., Sørensen, L.S., Clausen, P.A., Nielsen, J.B., 2018. Dermal

uptake and percutaneous penetration of organophosphate esters in a human skin ex vivo

model. Chemosphere 197, 185–192. https://doi.org/10.1016/j.chemosphere.2018.01.032

Fromme, H., Becher, G., Hilger, B., Völkel, W., 2016. Brominated flame retardants -

Exposure and risk assessment for the general population. Int. J. Hyg. Environ. Health

219, 1–23. https://doi.org/10.1016/j.ijheh.2015.08.004

Gaspar, F.W., Castorina, R., Maddalena, R.L., Nishioka, M.G., McKone, T.E., Bradman, A.,

2014. Phthalate exposure and risk assessment in California child care facilities. Environ.

Sci. Technol. 48, 7593–7601. https://doi.org/10.1021/es501189t

Gevao, B., Al-Bahloul, M., Al-Ghadban, A.N., Ali, L., Al-Omair, A., Helaleh, M., Al-

Matrouk, K., Zafar, J., 2006. Polybrominated diphenyl ethers in indoor air in Kuwait:

Implications for human exposure. Atmos. Environ. 40, 1419–1426.

https://doi.org/10.1016/j.atmosenv.2005.10.053

Gioia, R., Steinnes, E., Thomas, G.O., Mejier, S.N., Jones, K.C., 2006. Persistent organic

pollutants in European background air: derivation of temporal and latitudinal trends. J.

Environ. Monit. 8, 700. https://doi.org/10.1039/b604821h

Giovanoulis, G., Bui, T., Xu, F., Papadopoulou, E., Padilla-Sanchez, J.A., Covaci, A., Haug,

L.S., Cousins, A.P., Magnér, J., Cousins, I.T., de Wit, C.A., 2018. Multi-pathway human

exposure assessment of phthalate esters and DINCH. Environ. Int. 112, 115–126.

https://doi.org/10.1016/j.envint.2017.12.016

Glazer, L., Hawkey, A.B., Wells, C.N., Drastal, M., Odamah, K.-A., Behl, M., Levin, E.D.,

2018. Developmental Exposure to Low Concentrations of Organophosphate Flame

Retardants Causes Life-Long Behavioral Alterations in Zebrafish. Toxicol. Sci. 165,

200

487–498. https://doi.org/10.1093/toxsci/kfy173

Godwin, A.D., 2017. Plasticizers, in: Applied Plastics Engineering Handbook. Elsevier, pp.

533–553.

Godwin, A.D., 2010. Uses of Phthalates and Other Plasticizers [WWW Document]. URL

https://www.cpsc.gov/s3fs-public/godwin.pdf (accessed 10.21.20).

Gong, M., Weschler, C.J., Zhang, Y., 2016. Impact of Clothing on Dermal Exposure to

Phthalates: Observations and Insights from Sampling Both Skin and Clothing. Environ.

Sci. Technol. 50, 4350–4357. https://doi.org/10.1021/acs.est.6b00113

Goodyer, C.G., Poon, S., Aleksa, K., Hou, L., Atehortua, V., Carnevale, A., Jednak, R., Emil,

S., Bagli, D., Dave, S., Hales, B.F., Chevrier, J., 2017. A case-control study of maternal

polybrominated diphenyl ether (PBDE) exposure and cryptorchidism in Canadian

populations. Environ. Health Perspect. 125, 1–9. https://doi.org/10.1289/EHP522

Gouin, T., Harner, T., Blanchard, P., Mackay, D., 2005. Passive and Active Air Samplers as

Complementary Methods for Investigating Persistent Organic Pollutants in the Great

Lakes Basin. Environ. Sci. Technol. 39, 9115–9122. https://doi.org/10.1021/es051397f

Goverment of Canada, 2017. Phthalates Regulations Règlement sur les phtalates 21–23.

Government of Canada, 2019. Cosmetic Ingredient Hotlist [WWW Document]. URL

https://www.canada.ca/en/health-canada/services/consumer-product-

safety/cosmetics/cosmetic-ingredient-hotlist-prohibited-restricted-

ingredients/hotlist.html#tbl1 (accessed 5.4.20).

Government of Canada, 2016. Toxic substances list: PBDEs [WWW Document].

Government of Canada, 2012. Regulations Amending the Prohibition of Certain Toxic

Substances Regulations, 2012 [WWW Document]. Canada Gaz. Part II. URL

http://www.gazette.gc.ca/rp-pr/p2/2016/2016-10-05/pdf/g2-15020.pdf (accessed

2.18.21).

201

Government of Ontario, 2018. Waste management [WWW Document]. URL

https://www.ontario.ca/page/waste-management (accessed 12.9.18).

Graham, P.R., 1973. Phthalate ester plasticizers—why and how they are used. Environ.

Health Perspect. 3, 3–12. https://doi.org/10.1289/ehp.73033

Grant, K., Goldizen, F.C., Sly, P.D., Brune, M.-N., Neira, M., van den Berg, M., Norman,

R.E., 2013. Health consequences of exposure to e-waste: a systematic review. Lancet

Glob. Heal. 1, e350–e361. https://doi.org/10.1016/S2214-109X(13)70101-3

Gravel, S., Bakhiyi, B., Lavoué, J., Verner, M.-A., Zayed, J., Labreche, F., 2019a. Electronic

waste recycling exposure and hormone levels in workers., in: 27th EPICOH

International Symposium on Epidemiology in Occupational Health. Wellington,

NewZealand.

Gravel, S., Diamond, M.L., Jantunen, L.M., Verner, M.-A., Zayed, J., Labrèche, F., 2019b. Is

airborne concentration of BDE209 associated with serum concentration in recycling

workers?, in: 9th International Symposium on Flame Retardants BFR 2019. Montreal,

Canada.

Gravel, S., Lavoué, J., Bakhiyi, B., Diamond, M.L., Jantunen, L.M., Lavoie, J., Roberge, B.,

Verner, M.-A., Zayed, J., Labrèche, F., 2019c. Halogenated flame retardants and

organophosphate esters in the air of electronic waste recycling facilities: Evidence of

high concentrations and multiple exposures. Environ. Int. 128, 244–253.

https://doi.org/10.1016/j.envint.2019.04.027

Gravel, S., Lavoué, J., Bakhiyi, B., Lavoie, J., Roberge, B., Patry, L., Bouchard, M.F.,

Verner, M., Zayed, J., Labrèche, F., 2020. Multi-exposures to suspected endocrine

disruptors in electronic waste recycling workers: Associations with thyroid and

reproductive hormones. Int. J. Hyg. Environ. Health 225, 113445.

https://doi.org/10.1016/j.ijheh.2019.113445

202

Guo, J., Lin, K., Deng, J., Fu, X., Xu, Z., 2015. Polybrominated diphenyl ethers in indoor air

during waste TV recycling process. J. Hazard. Mater. 283, 439–446.

https://doi.org/10.1016/j.jhazmat.2014.09.044

Guo, Y., Kannan, K., 2013. A survey of phthalates and parabens in personal care products

from the United States and its implications for human exposure. Environ. Sci. Technol.

47, 14442–14449. https://doi.org/10.1021/es4042034

Guo, Y., Kannan, K., 2011. Comparative Assessment of Human Exposure to Phthalate Esters

from House Dust in China and the United States. Environ. Sci. Technol. 45, 3788–3794.

https://doi.org/10.1021/es2002106

Hammel, S., Hoffman, K., Webster, T.F., Anderson, K.A., Stapleton, H.M., 2016. Measuring

Personal Exposure to Organophosphate Flame Retardants using Silicone Wristbands and

Hand Wipes. Environ. Sci. Technol. acs.est.6b00030.

https://doi.org/10.1021/acs.est.6b00030

Hammel, S.C., Phillips, A.L., Hoffman, K., Stapleton, H.M., 2018. Evaluating the Use of

Silicone Wristbands To Measure Personal Exposure to Brominated Flame Retardants.

Environ. Sci. Technol. 52, acs.est.8b03755. https://doi.org/10.1021/acs.est.8b03755

Harley, K.G., Marks, A.R., Chevrier, J., Bradman, A., Sjödin, A., Eskenazi, B., 2010. PBDE

Concentrations in Women’s Serum and Fecundability. Environ. Health Perspect. 118,

699–704. https://doi.org/10.1289/ehp.0901450

Harner, T., Bartkow, M., Holoubek, I., Klanova, J., Wania, F., Gioia, R., Moeckel, C.,

Sweetman, A.J., Jones, K.C., 2006. Passive air sampling for persistent organic

pollutants: Introductory remarks to the special issue. Environ. Pollut. 144, 361–364.

https://doi.org/10.1016/j.envpol.2005.12.044

Hartmann, P.C., Burgi, D., Giger, W., 2004. Organophosphate flame retardants and

plasticizers in indoor air. Chemosphere 57, 781–787.

203

https://doi.org/10.1016/j.chemosphere.2004.08.051

Hays, S.M., Kirman, C.R., 2017. Risk assessment and Biomonitoring Equivalent for 2-

ethylhexyl-2,3,4,5 tetrabromobenzoate (TBB) and tetrabromobenzoic acid (TBBA).

Regul. Toxicol. Pharmacol. 89, 186–192. https://doi.org/10.1016/j.yrtph.2017.07.022

Hazrati, S., Harrad, S., 2006. Causes of Variability in Concentrations of Polychlorinated

Biphenyls and Polybrominated Diphenyl Ethers in Indoor air. Environ. Sci. Technol. 40,

7584–7589. https://doi.org/10.1021/es0617082

Heacock, M., Kelly, C.B., Asante, K.A., Birnbaum, L.S., Bergman, Å.L., Bruné, M.-N.,

Buka, I., Carpenter, D.O., Chen, A., Huo, X., Kamel, M., Landrigan, P.J., Magalini, F.,

Diaz-Barriga, F., Neira, M., Omar, M., Pascale, A., Ruchirawat, M., Sly, L., Sly, P.D.,

Van den Berg, M., Suk, W.A., 2015. E-Waste and Harm to Vulnerable Populations: A

Growing Global Problem. Environ. Health Perspect. 124, 550–555.

https://doi.org/10.1289/ehp.1509699

Heudorf, U., Mersch-Sundermann, V., Angerer, J., 2007. Phthalates: Toxicology and

exposure. Int. J. Hyg. Environ. Health 210, 623–634.

https://doi.org/10.1016/j.ijheh.2007.07.011

Hill, K.L., Hamers, T., Kamstra, J.H., Willmore, W.G., Letcher, R.J., 2018. Organophosphate

triesters and selected metabolites enhance binding of thyroxine to human transthyretin in

vitro. Toxicol. Lett. 285, 87–93. https://doi.org/10.1016/j.toxlet.2017.12.030

Hites, R.A., 2004. Polybrominated Diphenyl Ethers in the Environment and in People: A

Meta-Analysis of Concentrations. Environ. Sci. Technol. 38, 945–956.

https://doi.org/10.1021/es035082g

Hoffman, K., Butt, C.M., Webster, T.F., Preston, E. V., Hammel, S.C., Makey, C., Lorenzo,

A.M., Cooper, E.M., Carignan, C., Meeker, J.D., Hauser, R., Soubry, A., Murphy, S.K.,

Price, T.M., Hoyo, C., Mendelsohn, E., Congleton, J., Daniels, J.L., Stapleton, H.M.,

204

2017a. Temporal Trends in Exposure to Organophosphate Flame Retardants in the

United States. Environ. Sci. Technol. Lett. 4, 112–118.

https://doi.org/10.1021/acs.estlett.6b00475

Hoffman, K., Lorenzo, A., Butt, C.M., Hammel, S.C., Henderson, B.B., Roman, S.A., Scheri,

R.P., Stapleton, H.M., Sosa, J.A., 2017b. Exposure to flame retardant chemicals and

occurrence and severity of papillary thyroid cancer: A case-control study. Environ. Int.

107, 235–242. https://doi.org/10.1016/j.envint.2017.06.021

Holmes, A.K., Koller, K.R., Kieszak, S.M., Sjodin, A., Calafat, A.M., Sacco, F.D., Varner,

D.W., Lanier, A.P., Rubin, C.H., 2014. Case–control study of breast cancer and

exposure to synthetic environmental chemicals among Alaska Native women. Int. J.

Circumpolar Health 73, 25760. https://doi.org/10.3402/ijch.v73.25760

Hou, R., Xu, Y., Wang, Z., 2016. Review of OPFRs in animals and humans: Absorption,

bioaccumulation, metabolism, and internal exposure research. Chemosphere 153, 78–90.

https://doi.org/10.1016/j.chemosphere.2016.03.003

Hubinger, J.C., Havery, D.C., 2006. Analysis of consumer cosmetic products for phthalate

esters. J. Cosmet. Sci. 57, 127–37.

Hutter, H.-P., Haluza, D., Piegler, K., Hohenblum, P., Fröhlich, M., Scharf, S., Uhl, M.,

Damberger, B., Tappler, P., Kundi, M., Wallner, P., Moshammer, H., 2013. Semivolatile

compounds in schools and their influence on cognitive performance of children. Int. J.

Occup. Med. Environ. Health 26, 628–635. https://doi.org/10.2478/s13382-013-0125-z

IARC Working Group on the Evaluation of Carcinogenic Risks to Humans, 2013. Some

chemicals present in industrial and consumer products, food and drinking-water. IARC

Monogr. Eval. Carcinog. Risks Hum. 101, 9–549.

Igharo, O.G., Anetor, J.I., Osibanjo, O., Osadolor, H.B., Odazie, E.C., Uche, Z.C., 2018.

Endocrine disrupting metals lead to alteration in the gonadal hormone levels in Nigerian

205

e-waste workers. Universa Med. 37, 65. https://doi.org/10.18051/UnivMed.2018.v37.65-

Iqbal, M., Syed, J.H., Breivik, K., Chaudhry, M.J.I., Li, J., Zhang, G., Malik, R.N., 2017. E-

Waste Driven Pollution in Pakistan: The First Evidence of Environmental and Human

Exposure to Flame Retardants (FRs) in Karachi City. Environ. Sci. Technol. 51, 13895–

13905. https://doi.org/10.1021/acs.est.7b03159

Jacobson, M.H., Barr, D.B., Marcus, M., Muir, A.B., Lyles, R.H., Howards, P.P., Pardo, L.,

Darrow, L.A., 2016. Serum polybrominated diphenyl ether concentrations and thyroid

function in young children. Environ. Res. 149, 222–230.

https://doi.org/10.1016/j.envres.2016.05.022

Jarema, K.A., Hunter, D.L., Shaffer, R.M., Behl, M., Padilla, S., 2015. Acute and

developmental behavioral effects of flame retardants and related chemicals in zebrafish.

Neurotoxicol. Teratol. 52, 194–209. https://doi.org/10.1016/j.ntt.2015.08.010

Julander, A., Westberg, H., Engwall, M., van Bavel, B., 2005. Distribution of brominated

flame retardants in different dust fractions in air from an electronics recycling facility.

Sci. Total Environ. 350, 151–160. https://doi.org/10.1016/j.scitotenv.2005.01.015

Kahhat, R., Williams, E., 2012. Materials flow analysis of e-waste: Domestic flows and

exports of used computers from the United States. Resour. Conserv. Recycl. 67, 67–74.

https://doi.org/10.1016/j.resconrec.2012.07.008

Kammerer, F., 2017. Safe Drinking Water and Toxic Enforcement Act of 1986. Environ.

Heal. 1–22.

Kile, M.L., Scott, R.P., O’Connell, S.G., Lipscomb, S., MacDonald, M., McClelland, M.,

Anderson, K.A., Gibson, E.A., Stapleton, H.M., Calero, L., Holmes, D., Burke, K.,

Martinez, R., Cortes, B., Nematollahi, A., Evans, D., Anderson, K.A., Herbstman, J.B.,

Fisher, M., Arbuckle, T.E., MacPherson, S., Braun, J.M., Feeley, M., Gaudreau, É.,

206

Dixon, H.M., Scott, R.P., Holmes, D., Calero, L., Kincl, L.D., Waters, K.M., Camann,

D.E., Calafat, A.M., Herbstman, J.B., Anderson, K.A., Bohlin, P., Jones, K.C., Levin,

J.O., Lindahl, R., Strandberg, B., 2019. Using silicone wristbands to evaluate preschool

children’s exposure to flame retardants. Chemosphere 219, 567–573.

https://doi.org/10.1007/s00216-018-0992-z

Kim, E.-H., Jeon, B.-H., Kim, J., Kim, Y.-M., Han, Y., Ahn, K., Cheong, H.-K., 2017.

Exposure to phthalates and bisphenol A are associated with atopic dermatitis symptoms

in children: a time-series analysis. Environ. Heal. 16, 24.

https://doi.org/10.1186/s12940-017-0225-5

Kim, Y.H., Wyrzykowska-Ceradini, B., Touati, A., Krantz, Q.T., Dye, J.A., Linak, W.P.,

Gullett, B., Gilmour, M.I., 2015. Characterization of Size-Fractionated Airborne

Particles Inside an Electronic Waste Recycling Facility and Acute Toxicity Testing in

Mice. Environ. Sci. Technol. 49, 11543–11550. https://doi.org/10.1021/acs.est.5b03263

Koniecki, D., Wang, R., Moody, R.P., Zhu, J., 2011. Phthalates in cosmetic and personal care

products: Concentrations and possible dermal exposure. Environ. Res. 111, 329–336.

https://doi.org/10.1016/j.envres.2011.01.013

Kuo, L., Cade, S.E., Cullinan, V., Schultz, I.R., 2019. Polybrominated diphenyl ethers

(PBDEs) in plasma from E-waste recyclers, outdoor and indoor workers in the Puget

Sound, WA region. Chemosphere 219, 209–216.

https://doi.org/10.1016/j.chemosphere.2018.12.006

Kuriyama, S.N., Talsness, C.E., Grote, K., Chahoud, I., 2005. Developmental exposure to

low-dose PBDE-99: Effects on male fertility and neurobehavior in rat offspring.

Environ. Health Perspect. 113, 149–154. https://doi.org/10.1289/ehp.7421

La Guardia, M.J., Hale, R.C., Harvey, E., 2006. Detailed Polybrominated Diphenyl Ether

(PBDE) Congener Composition of the Widely Used Penta-, Octa-, and Deca-PBDE

207

Technical Flame-retardant Mixtures. Environ. Sci. Technol. 40, 6247–6254.

https://doi.org/10.1021/es060630m

Labunska, I., Harrad, S., Wang, M., Santillo, D., Johnston, P., 2014. Human Dietary

Exposure to PBDEs Around E-Waste Recycling Sites in Eastern China. Environ. Sci.

Technol. 48, 5555–5564. https://doi.org/10.1021/es500241m

Lam, J., Lanphear, B.P., Bellinger, D., Axelrad, D.A., McPartland, J., Sutton, P., Davidson,

L., Daniels, N., Sen, S., Woodruff, T.J., 2017. Developmental PBDE Exposure and

IQ/ADHD in Childhood: A Systematic Review and Meta-analysis. Environ. Health

Perspect. 125. https://doi.org/10.1289/EHP1632

Lenters, V., Portengen, L., Rignell-Hydbom, A., Jönsson, B.A.G., Lindh, C.H., Piersma,

A.H., Toft, G., Bonde, J.P., Heederik, D., Rylander, L., Vermeulen, R., 2016. Prenatal

Phthalate, Perfluoroalkyl Acid, and Organochlorine Exposures and Term Birth Weight

in Three Birth Cohorts: Multi-Pollutant Models Based on Elastic Net Regression.

Environ. Health Perspect. 124, 365–372. https://doi.org/10.1289/ehp.1408933

Li, F., Xie, Q., Li, X., Li, N., Chi, P., Chen, J., Wang, Z., Hao, C., 2010. Hormone Activity of

Hydroxylated Polybrominated Diphenyl Ethers on Human Thyroid Receptor-β: In Vitro

and In Silico Investigations. Environ. Health Perspect. 118, 602–606.

https://doi.org/10.1289/ehp.0901457

Lilienthal, H., Hack, A., Roth-Härer, A., Grande, S.W., Talsness, C.E., 2006. Effects of

developmental exposure to 2,2′,4,4′, 5-pentabromodiphenyl ether (PBDE-99) on sex

steroids, sexual development, and sexually dimorphic behavior in rats. Environ. Health

Perspect. 114, 194–201. https://doi.org/10.1289/ehp.8391

Lippmann, M., 1998. The 1997 US EPA Standards for Particulate Matter and Ozone, in: Air

Pollution and Health. pp. 75–100. https://doi.org/10.1039/9781847550095-00075

Little, J.C., Weschler, C.J., Nazaroff, W.W., Liu, Z., Cohen Hubal, E.A., 2012. Rapid

208

Methods to Estimate Potential Exposure to Semivolatile Organic Compounds in the

Indoor Environment. Environ. Sci. Technol. 46, 11171–11178.

https://doi.org/10.1021/es301088a

Liu, C., Zhang, Y., Weschler, C.J., 2017. Exposure to SVOCs from Inhaled Particles: Impact

of Desorption. Environ. Sci. Technol. 51, 6220–6228.

https://doi.org/10.1021/acs.est.6b05864

Lu, S.Y., Li, Y.X., Zhang, T., Cai, D., Ruan, J.J., Huang, M.Z., Wang, L., Zhang, J.Q., Qiu,

R.L., 2017. Effect of E-waste Recycling on Urinary Metabolites of Organophosphate

Flame Retardants and Plasticizers and Their Association with Oxidative Stress. Environ.

Sci. Technol. 51, 2427–2437. https://doi.org/10.1021/acs.est.6b05462

Lucas, D., Petty, S.M., Keen, O., Luedeka, B., Schlummer, M., Weber, R., Barlaz, M.,

Yazdani, R., Riise, B., Rhodes, J., Nightingale, D., Diamond, M.L., Vijgen, J.,

Lindeman, A., Blum, A., Koshland, C.P., 2017. Methods of Responsibly Managing End-

of-Life Foams and Plastics Containing Flame Retardants: Part I. Environ. Eng. Sci.

https://doi.org/10.1089/ees.2017.0147

Ma, J., Addink, R., Yun, S., Cheng, J., Wang, W., Kannan, K., 2009. Polybrominated

Dibenzo- p -dioxins/Dibenzofurans and Polybrominated Diphenyl Ethers in Soil,

Vegetation, Workshop-Floor Dust, and Electronic Shredder Residue from an Electronic

Waste Recycling Facility and in Soils from a Chemical Industrial Complex in Ea.

Environ. Sci. Technol. 43, 7350–7356. https://doi.org/10.1021/es901713u

MacIntosh, D.L., Minegishi, T., Fragala, M.A., Allen, J.G., Coghlan, K.M., Stewart, J.H.,

McCarthy, J.F., 2012. Mitigation of building-related polychlorinated biphenyls in indoor

air of a school. Environ. Heal. A Glob. Access Sci. Source 11, 1–10.

https://doi.org/10.1186/1476-069X-11-24

Mäkinen, M.S.E., Mäkinen, M.R.A., Koistinen, J.T.B., Pasanen, A.-L., Pasanen, P.O.,

209

Kalliokoski, P.J., Korpi, A.M., 2009. Respiratory and Dermal Exposure to

Organophosphorus Flame Retardants and Tetrabromobisphenol A at Five Work

Environments. Environ. Sci. Technol. 43, 941–947. https://doi.org/10.1021/es802593t

Marek, R.F., Thorne, P.S., Herkert, N.J., Awad, A.M., Hornbuckle, K.C., 2017. Airborne

PCBs and OH-PCBs Inside and Outside Urban and Rural U.S. Schools. Environ. Sci.

Technol. 51, 7853–7860. https://doi.org/10.1021/acs.est.7b01910

Meeker, J.D., Cooper, E.M., Stapleton, H.M., Hauser, R., 2013. Exploratory analysis of

urinary metabolites of phosphorus-containing flame retardants in relation to markers of

male reproductive health. Endocr. Disruptors 1, e26306.

https://doi.org/10.4161/endo.26306

Meeker, J.D., Stapleton, H.M., 2009. House Dust Concentrations of Organophosphate Flame

Retardants in Relation to Hormone Levels and Semen Quality Parameters. Environ.

Health Perspect. 118, 318–323. https://doi.org/10.1289/ehp.0901332

Meironyté, D., Norén, K., Bergman, Å., 1999. Analysis of polybrominated diphenyl ethers in

swedish human milk. A time-related trend study, 1972–1997. J. Toxicol. Environ. Heal.

- Part A 58, 329–341. https://doi.org/10.1080/009841099157197

Melymuk, L., Robson, M., Helm, P.A., Diamond, M.L., 2011. Evaluation of passive air

sampler calibrations: Selection of sampling rates and implications for the measurement

of persistent organic pollutants in air. Atmos. Environ. 45, 1867–1875.

https://doi.org/10.1016/j.atmosenv.2011.01.011

Mendelsohn, E., Hagopian, A., Hoffman, K., Butt, C.M., Lorenzo, A., Congleton, J.,

Webster, T.F., Stapleton, H.M., 2016. Nail polish as a source of exposure to triphenyl

phosphate. Environ. Int. 86, 45–51. https://doi.org/10.1016/j.envint.2015.10.005

Moeckel, C., Harner, T., Nizzetto, L., Strandberg, B., Lindroth, A., Jones, K.C., 2009. Use of

depuration compounds in passive air samplers: Results from active sampling-supported

210

field deployment, potential uses, and recommendations. Environ. Sci. Technol. 43,

3227–3232. https://doi.org/10.1021/es802897x

Morrison, G.C., Weschler, C.J., Bekö, G., Koch, H.M., Salthammer, T., Schripp, T., Toftum,

J., Clausen, G., 2016. Role of clothing in both accelerating and impeding dermal

absorption of airborne SVOCs. J. Expo. Sci. Environ. Epidemiol. 26, 113–118.

https://doi.org/10.1038/jes.2015.42

Muenhor, D., Harrad, S., Ali, N., Covaci, A., 2010. Brominated flame retardants (BFRs) in

air and dust from electronic waste storage facilities in Thailand. Environ. Int. 36, 690–

698. https://doi.org/10.1016/j.envint.2010.05.002

Nalli, S., Horn, O.J., Grochowalski, A.R., Cooper, D.G., Nicell, J.A., 2006. Origin of 2-

ethylhexanol as a VOC. Environ. Pollut. 140, 181–185.

https://doi.org/10.1016/j.envpol.2005.06.018

National Academies of Sciences Engineering and Medicine, 2017. Application of Systematic

Review Methods in an Overall Strategy for Evaluating Low-Dose Toxicity from

Endocrine Active Chemicals. The National Academies Press, Washington,DC.

https://doi.org/10.17226/24758

Nguyen, L. V., Diamond, M.L., Venier, M., Stubbings, W.A., Romanak, K., Bajard, L.,

Melymuk, L., Jantunen, L.M., Arrandale, V.H., 2019. Exposure of Canadian electronic

waste dismantlers to flame retardants. Environ. Int. 129, 95–104.

https://doi.org/10.1016/j.envint.2019.04.056

Nguyen, L. V., Gravel, S., Labrèche, F., Bakhiyi, B., Verner, M.A., Zayed, J., Jantunen,

L.M., Arrandale, V.H., Diamond, M.L., 2020. Can Silicone Passive Samplers be Used

for Measuring Exposure of e-Waste Workers to Flame Retardants? Environ. Sci.

Technol. 54, 15277–15286. https://doi.org/10.1021/acs.est.0c05240

North, M.L., Takaro, T.K., Diamond, M.L., Ellis, A.K., 2014. Effects of phthalates on the

211

development and expression of allergic disease and asthma. Ann. Allergy, Asthma

Immunol. 112, 496–502. https://doi.org/10.1016/j.anai.2014.03.013

NTP, 1991. Toxicology and Carcinogenesis Studies of TRIS(2-

CHLOROETHYL)PHOSPHATE (CAS NO. 115-96-8) in F344 / N Rats. Natl. Toxicol.

Program Tech. Rep. Ser. 409, 1–171.

O’Connell, S.G., Kincl, L.D., Anderson, K.A., 2014. Silicone Wristbands as Personal Passive

Samplers. Environ. Sci. Technol. 48, 3327–3335. https://doi.org/10.1021/es405022f

Okeme, J.O., Nguyen, L. V., Lorenzo, M., Dhal, S., Pico, Y., Arrandale, V.H., Diamond,

M.L., 2018a. Polydimethylsiloxane (silicone rubber) brooch as a personal passive air

sampler for semi-volatile organic compounds. Chemosphere 208, 1002–1007.

https://doi.org/10.1016/j.chemosphere.2018.05.196

Okeme, J.O., Nguyen, L. V., Lorenzo, M., Dhal, S., Pico, Y., Arrandale, V.H., Diamond,

M.L., 2018b. Polydimethylsiloxane (silicone rubber) brooch as a personal passive air

sampler for semi-volatile organic compounds. Chemosphere 208, 1002–1007.

https://doi.org/10.1016/j.chemosphere.2018.05.196

Okeme, J.O., Parnis, J.M., Poole, J., Diamond, M.L., Jantunen, L.M., 2016a.

Polydimethylsiloxane-air partition ratios for semi-volatile organic compounds by GC-

based measurement and COSMO-RS estimation: Rapid measurements and accurate

modelling. Chemosphere 156, 204–211.

https://doi.org/10.1016/j.chemosphere.2016.04.094

Okeme, J.O., Rodgers, T.F.M., Jantunen, L.M., Diamond, M.L., 2018c. Examining the Gas-

Particle Partitioning of Organophosphate Esters: How Reliable Are Air Measurements?

Environ. Sci. Technol. 52, 13834–13844. https://doi.org/10.1021/acs.est.8b04588

Okeme, J.O., Saini, A., Yang, C., Zhu, J., Smedes, F., Klánová, J., Diamond, M.L., 2016b.

Calibration of polydimethylsiloxane and XAD-Pocket passive air samplers (PAS) for

212

measuring gas- and particle-phase SVOCs. Atmos. Environ. 143, 202–208.

https://doi.org/10.1016/j.atmosenv.2016.08.023

Okeme, J.O., Yang, C., Abdollahi, A., Dhal, S., Harris, S.A., Jantunen, L.M., Tsirlin, D.,

Diamond, M.L., 2018d. Passive air sampling of flame retardants and plasticizers in

Canadian homes using PDMS, XAD-coated PDMS and PUF samplers. Environ. Pollut.

239, 109–117. https://doi.org/10.1016/j.envpol.2018.03.103

Okonski, K., Degrendele, C., Melymuk, L., Landlová, L., Kukučka, P., Vojta, Š., Kohoutek,

J., Čupr, P., Klánová, J., 2014. Particle Size Distribution of Halogenated Flame

Retardants and Implications for Atmospheric Deposition and Transport. Environ. Sci.

Technol. 48, 14426–14434. https://doi.org/10.1021/es5044547

Ospina, M., Jayatilaka, N.K., Wong, L.-Y., Restrepo, P., Calafat, A.M., 2018. Exposure to

organophosphate flame retardant chemicals in the U.S. general population: Data from

the 2013–2014 National Health and Nutrition Examination Survey. Environ. Int. 110,

32–41. https://doi.org/10.1016/j.envint.2017.10.001

Park, S.A., Gwak, S., Choi, S., 2014. Assessment of occupational symptoms and chemical

exposures for nail salon technicians in Daegu City, Korea. J. Prev. Med. Public Heal. 47,

169–176. https://doi.org/10.3961/jpmph.2014.47.3.169

Pawar, G., 2017. Exploring the utility of 3-D skin models to evaluate trans-dermal uptake of

flame retardants from indoor dust and consumer product. University of Birmingham.

Pelucchi, C., Negri, E., Gallus, S., Boffetta, P., Tramacere, I., La Vecchia, C., 2009. Long-

term particulate matter exposure and mortality: a review of European epidemiological

studies. BMC Public Health 9, 453. https://doi.org/10.1186/1471-2458-9-453

Percy, Z., Vuong, A.M., Ospina, M., Calafat, A.M., La Guardia, M.J., Xu, Y., Hale, R.C.,

Dietrich, K.N., Xie, C., Lanphear, B.P., Braun, J.M., Cecil, K.M., Yolton, K., Chen, A.,

2020. Organophosphate esters in a cohort of pregnant women: Variability and predictors

213

of exposure. Environ. Res. 184, 109255. https://doi.org/10.1016/j.envres.2020.109255

Pettersson-Julander, A., van Bavel, B., Engwall, M., Westberg, H., 2004. Personal air

sampling and analysis of polybrominated diphenyl ethers and other bromine containing

compounds at an electronic recycling facility in Sweden. J. Environ. Monit. 6, 874.

https://doi.org/10.1039/b408381d

Philippat, C., Bennett, D., Calafat, A.M., Picciotto, I.H., Xu, F., Giovanoulis, G., Van Waes,

S., Padilla-Sanchez, J.A., Papadopoulou, E., Magnér, J., Haug, L.S., Neels, H., Covaci,

A., 2016. Exposure to select phthalates and phenols through use of personal care

products among Californian adults and their children. Environ. Res. 50, 7752–7760.

https://doi.org/10.1021/acs.est.6b00246

Pinson, A., Bourguignon, J.P., Parent, A.S., 2016. Exposure to endocrine disrupting

chemicals and neurodevelopmental alterations. Andrology 4, 706–722.

https://doi.org/10.1111/andr.12211

Pope III, C.A., 2002. Lung Cancer, Cardiopulmonary Mortality, and Long-term Exposure to

Fine Particulate Air Pollution. JAMA 287, 1132.

https://doi.org/10.1001/jama.287.9.1132

Quach, T., Gunier, R., Tran, A., Von Behren, J., Doan-Billings, P.-A., Nguyen, K.-D.,

Okahara, L., Lui, B.Y.-B., Nguyen, M., Huynh, J., Reynolds, P., 2011. Characterizing

Workplace Exposures in Vietnamese Women Working in California Nail Salons. Am. J.

Public Health 101, S271–S276. https://doi.org/10.2105/AJPH.2010.300099

Radke, E.G., Braun, J.M., Meeker, J.D., Cooper, G.S., Agency, U.S.E.P., States, U., 2018.

Phthalate exposure and male reproductive outcomes : A systematic review of the human

epidemiological evidence. Environ. Int. 121, 764–793.

https://doi.org/10.1016/j.envint.2018.07.029

Rakkestad, K.E., Dye, C.J., Yttri, K.E., Holme, J.A., Hongslo, J.K., Schwarze, P.E., Becher,

214

R., 2007. Phthalate levels in Norwegian indoor air related to particle size fraction. J.

Environ. Monit. 9, 1419. https://doi.org/10.1039/b709947a

Rengasamy, S., Eimer, B., Shaffer, R.E., 2010. Simple respiratory protection - Evaluation of

the filtration performance of cloth masks and common fabric materials against 20-1000

nm size particles. Ann. Occup. Hyg. 54, 789–798.

https://doi.org/10.1093/annhyg/meq044

Richman, K.E., Butt, C.M., Young, C.J., 2018. Size-resolved particle measurements of

polybrominated diphenyl ethers indoors: Implications for sources and human exposure.

Environ. Toxicol. Chem. 37, 481–490. https://doi.org/10.1002/etc.3981

Robinson, B.H., 2009. E-waste: An assessment of global production and environmental

impacts. Sci. Total Environ. 408, 183–191.

https://doi.org/10.1016/j.scitotenv.2009.09.044

Rodes, C.E., Kamens, R.M., Wiener, R.W., 1991. The Significance and Characteristics of the

Personal Activity Cloud on Exposure Assessment Measurements for Indoor

Contaminants. Indoor Air 1, 123–145. https://doi.org/10.1111/j.1600-0668.1991.03-12.x

Romanak, K.A., Wang, S., Stubbings, W.A., Hendryx, M., Venier, M., Salamova, A., 2019.

Analysis of brominated and chlorinated flame retardants, organophosphate esters, and

polycyclic aromatic hydrocarbons in silicone wristbands used as personal passive

samplers. J. Chromatogr. A 1588, 41–47. https://doi.org/10.1016/j.chroma.2018.12.041

Romero-Franco, M., Hernández-Ramírez, R.U., Calafat, A.M., Cebrián, M.E., Needham,

L.L., Teitelbaum, S., Wolff, M.S., López-Carrillo, L., 2011. Personal care product use

and urinary levels of phthalate metabolites in Mexican women. Environ. Int. 37, 867–

871. https://doi.org/10.1016/j.envint.2011.02.014

Rosenberg, C., Hämeilä, M., Tornaeus, J., Säkkinen, K., Puttonen, K., Korpi, A., Kiilunen,

M., Linnainmaa, M., Hesso, A., 2011. Exposure to Flame Retardants in Electronics

215

Recycling Sites. Ann. Occup. Hyg. 55, 658–665. https://doi.org/10.1093/annhyg/mer033

Saini, A., Okeme, J.O., Goosey, E., Diamond, M.L., 2015. Calibration of two passive air

samplers for monitoring phthalates and brominated flame-retardants in indoor air.

Chemosphere 137, 166–173. https://doi.org/10.1016/j.chemosphere.2015.06.099

Saini, A., Okeme, J.O., Mark Parnis, J., McQueen, R.H., Diamond, M.L., 2016. From air to

clothing: characterizing the accumulation of semi-volatile organic compounds to fabrics

in indoor environments. Indoor Air. https://doi.org/10.1111/ina.12328

SCHETTLER, T., 2006. Human exposure to phthalates via consumer products. Int. J. Androl.

29, 134–139. https://doi.org/10.1111/j.1365-2605.2005.00567.x

Schreder, E.D., Uding, N., La Guardia, M.J., 2016. Inhalation a significant exposure route for

chlorinated organophosphate flame retardants. Chemosphere 150, 499–504.

https://doi.org/10.1016/j.chemosphere.2015.11.084

Schwartz, J., Neas, L.M., 2000. Fine particles are more strongly associated than coarse

particleswithacute respiratoryhealtheffectsinschoolchildren. Epidemiology 11, 6–10.

Shi, T., Chen, S.-J., Luo, X.-J., Zhang, X.-L., Tang, C.-M., Luo, Y., Ma, Y.-J., Wu, J.-P.,

Peng, X.-Z., Mai, B.-X., 2009. Occurrence of brominated flame retardants other than

polybrominated diphenyl ethers in environmental and biota samples from southern

China. Chemosphere 74, 910–916. https://doi.org/10.1016/j.chemosphere.2008.10.047

Shoeib, M., Harner, T., 2002. Characterization and Comparison of Three Passive Air

Samplers for Persistent Organic Pollutants. Environ. Sci. Technol. 36, 4142–4151.

https://doi.org/10.1021/es020635t

Sindiku, O., Babayemi, J., Osibanjo, O., Schlummer, M., Schluep, M., Watson, A., Weber,

R., 2015. Polybrominated diphenyl ethers listed as Stockholm Convention POPs, other

brominated flame retardants and heavy metals in e-waste polymers in Nigeria. Environ.

Sci. Pollut. Res. 22, 14489–14501. https://doi.org/10.1007/s11356-014-3266-0

216

Singh, M., Thind, P.S., John, S., 2018. Health risk assessment of the workers exposed to the

heavy metals in e-waste recycling sites of Chandigarh and Ludhiana, Punjab, India.

Chemosphere 203, 426–433. https://doi.org/10.1016/j.chemosphere.2018.03.138

Sjödin, A., Carlsson, H., Thuresson, K., Sjölin, S., Bergman, Å., Östman, C., 2001. Flame

Retardants in Indoor Air at an Electronics Recycling Plant and at Other Work

Environments. Environ. Sci. Technol. 35, 448–454. https://doi.org/10.1021/es000077n

Slotkin, T.A., Skavicus, S., Stapleton, H.M., Seidler, F.J., 2017. Brominated and

organophosphate flame retardants target different neurodevelopmental stages,

characterized with embryonic neural stem cells and neuronotypic PC12 cells.

Toxicology 390, 32–42. https://doi.org/10.1016/j.tox.2017.08.009

Smil, V., 2017. PLANET OF THE COWS. IEEE Spectr. 54, 24.

Snedeker, S.M., 2014. Toxicants in Food Packaging and Household Plastics, Molecular and

Integrative Toxicology. Springer London, London. https://doi.org/10.1007/978-1-4471-

6500-2

Staaf, T., Ostman, C., 2005. Organophosphate triesters in indoor environments. J. Environ.

Monit. 7, 883–887. https://doi.org/10.1039/b506631j

Stapleton, H.M., Allen, J.G., Kelly, S.M., Konstantinov, A., Klosterhaus, S., Watkins, D.,

McClean, M.D., Webster, T.F., 2008a. Alternate and New Brominated Flame Retardants

Detected in U.S. House Dust. Environ. Sci. Technol. 42, 6910–6916.

https://doi.org/10.1021/es801070p

Stapleton, H.M., Kelly, S.M., Allen, J.G., McClean, M.D., Webster, T.F., Stapleton, M.H.,

Kelly, S.M., Allen, J.G., McClean, M.D., Webster, T.F., Stapleton, H.M., Kelly, S.M.,

Allen, J.G., McClean, M.D., Webster, T.F., 2008b. Measurement of Polybrominated

Diphenyl Ethers on Hand Wipes: Estimating Exposure from Hand-to-Mouth Contact.

Environ. Sci. Technol. 42, 3329–3334. https://doi.org/10.1021/es7029625

217

Statistics Canada, 2016. EnviroStats Trash talking: Dealing with Canadian household e-

waste. [WWW Document]. URL http://www.statcan.gc.ca/pub/16-002-

x/2016001/article/14570-eng.htm (accessed 7.15.18).

Stubbings, W.A., Nguyen, L. V., Romanak, K., Jantunen, L., Melymuk, L., Arrandale, V.,

Diamond, M.L., Venier, M., 2019a. Flame retardants and plasticizers in a Canadian

waste electrical and electronic equipment (WEEE) dismantling facility. Sci. Total

Environ. 675, 594–603. https://doi.org/10.1016/j.scitotenv.2019.04.265

Stubbings, W.A., Nguyen, L. V., Romanak, K., Jantunen, L., Melymuk, L., Arrandale, V.,

Diamond, M.L., Venier, M., 2019b. Flame retardants and plasticizers in a Canadian

waste electrical and electronic equipment (WEEE)dismantling facility. Sci. Total

Environ. 675, 594–603. https://doi.org/10.1016/j.scitotenv.2019.04.265

Suzuki, G., Tue, N.M., Malarvannan, G., Sudaryanto, A., Takahashi, S., Tanabe, S., Sakai,

S., Brouwer, A., Uramaru, N., Kitamura, S., Takigami, H., 2013. Similarities in the

Endocrine-Disrupting Potencies of Indoor Dust and Flame Retardants by Using Human

Osteosarcoma (U2OS) Cell-Based Reporter Gene Assays. Environ. Sci. Technol. 47,

2898–2908. https://doi.org/10.1021/es304691a

Swedish Chemicals Inspectorate, 2003. Brominated flame retardants – Prospects of a national

ban. KemI Report 4/03.

Takigami, H., Suzuki, G., Hirai, Y., Sakai, S., 2008. Transfer of brominated flame retardants

from components into dust inside television cabinets. Chemosphere 73, 161–169.

https://doi.org/10.1016/j.chemosphere.2008.06.032

Tansel, B., 2017. From electronic consumer products to e-wastes: Global outlook, waste

quantities, recycling challenges. Environ. Int. 98, 35–45.

https://doi.org/10.1016/j.envint.2016.10.002

Thuresson, K., Höglund, P., Hagmar, L., Sjödin, A., Bergman, Å., Jakobsson, K., 2006.

218

Apparent Half-Lives of Hepta- to Decabrominated Diphenyl Ethers in Human Serum as

Determined in Occupationally Exposed Workers. Environ. Health Perspect. 114, 176–

181. https://doi.org/10.1289/ehp.8350

Tran, T.M., Kannan, K., 2015. Occurrence of Phthalate Diesters in Particulate and Vapor

Phases in Indoor Air and Implications for Human Exposure in Albany, New York, USA.

Arch. Environ. Contam. Toxicol. 68, 489–499. https://doi.org/10.1007/s00244-015-

0140-0

Tran, T.M., Le, H.T., Minh, T.B., Kannan, K., 2017. Occurrence of phthalate diesters in

indoor air from several Northern cities in Vietnam, and its implication for human

exposure. Sci. Total Environ. 601–602, 1695–1701.

https://doi.org/10.1016/j.scitotenv.2017.06.016

Traore, I.T., Gravel, S., Diamond, M.L., Jantunen, L., Nguyen, L.V., Yang, C., Bernstein, S.,

Zayed, J., Labrèche, F., Verner, M.-A., 2018. Urinary Metabolites of Organophosphate

Esters (OPEs) in Electronic Waste Recycling Workers from the Province of Quebec,

Canada. ISEE Conf. Abstr. 2018, isesisee.2018.P01.3100.

https://doi.org/10.1289/isesisee.2018.P01.3100

Tromp, P.C., Beeltje, H., Okeme, J.O., Vermeulen, R., Pronk, A., Diamond, M.L., 2019.

Calibration of polydimethylsiloxane and polyurethane foam passive air samplers for

measuring semi volatile organic compounds using a novel exposure chamber design.

Chemosphere 227, 435–443. https://doi.org/10.1016/j.chemosphere.2019.04.043

Tue, N.M., Takahashi, S., Suzuki, G., Isobe, T., Viet, P.H., Kobara, Y., Seike, N., Zhang, G.,

Sudaryanto, A., Tanabe, S., 2013. Contamination of indoor dust and air by

polychlorinated biphenyls and brominated flame retardants and relevance of non-dietary

exposure in Vietnamese informal e-waste recycling sites. Environ. Int. 51, 160–167.

https://doi.org/10.1016/j.envint.2012.11.006

219

U.S.Bureau of Labor, 2020. Occupational Outlook Handbook [WWW Document].

UCLA Labor Center, 2018. Nail Files: A study of nail salon workers and industry in United

States.

UNEP, 2019. A New Circular Vision for Electronics Time for a Global Reboot 24.

UNEP, 2016. GEO-6 North America Regional Assessment [WWW Document]. URL

http://wedocs.unep.org/bitstream/handle/20.500.11822/7611/GEO_North_America_201

611.pdf?sequence=1&isAllowed=y (accessed 6.27.18).

UNEP, 2010. Technical review of the implications of recycling commercial

pentabromodiphenyl ether and commercial octabromodi- phenyl ether.

UNEP, 2008. Report of the Persistent Organic Pollutants Review Committee on the work of

its fourth meeting.

United States Department of Labor, 2017. Occupational Employment and Wages, May 2017

[WWW Document]. URL https://www.bls.gov/oes/current/oes395092.htm#st

US EPA, 2018a. IRIS Assessments [WWW Document]. URL

https://cfpub.epa.gov/ncea/iris2/atoz.cfm (accessed 6.27.18).

US EPA, 2018b. Chemistry Dashboard [WWW Document]. URL

https://comptox.epa.gov/dashboard (accessed 6.27.18).

US EPA, 2018c. 2,2’,4,4’,5-Pentabromodiphenyl ether (BDE-99) [WWW Document]. URL

https://cfpub.epa.gov/ncea/iris2/chemicalLanding.cfm?substance_nmbr=1008 (accessed

6.27.18).

US EPA, 2011. September 2011 EXPOSURE FACTORS HANDBOOK : 2011 EDITION

National Center for Environmental Assessment Office of Research and Development U .

S . Environmental Protection Agency Washington , DC 20460 Exposure Factors

Handbook. Exposure.

220

USEPA, 2020. CHEMICALS KNOWN TO THE STATE TO CAUSE CANCER OR

REPRODUCTIVE TOXICITY January 3, 2020.

Veen, I. Van Der, Boer, J. De, 2012. Chemosphere Phosphorus flame retardants : Properties ,

production , environmental occurrence , toxicity and analysis. Chemosphere 88, 1119–

1153. https://doi.org/10.1016/j.chemosphere.2012.03.067

Venier, M., Ma, Y., Hites, R.A., 2012. Brominated flame retardants in the Great Lakes

atmosphere. Environ. Sci. Technol. 46, 8653–8660.

https://doi.org/dx.doi.org/10.1021/es3015919

Viberg, H., Fredriksson, A., Eriksson, P., 2004. Investigations of strain and/or gender

differences in developmental neurotoxic effects of polybrominated diphenyl ethers in

mice. Toxicol. Sci. 81, 344–353. https://doi.org/10.1093/toxsci/kfh215

Viberg, H., Fredriksson, A., Jakobsson, E., Orn, U., Erikson, P., 2003. Neurobehavioral

derangements in adult mice receiving decabrominated diphenyl ether (PBDE 209)

during a defined period of neonatal brain development. Toxicol. Sci. 76, 112–120.

https://doi.org/10.1093/toxsci/kfg210

Vojta, Š., Bečanová, J., Melymuk, L., Komprdová, K., Kohoutek, J., Kukučka, P., Klánová,

J., 2017. Screening for halogenated flame retardants in European consumer products,

building materials and wastes. Chemosphere 168, 457–466.

https://doi.org/10.1016/j.chemosphere.2016.11.032

Vuong, A.M., Braun, J.M., Webster, G.M., Thomas Zoeller, R., Hoofnagle, A.N., Sjödin, A.,

Yolton, K., Lanphear, B.P., Chen, A., 2018. Polybrominated diphenyl ether (PBDE)

exposures and thyroid hormones in children at age 3 years. Environ. Int. 117, 339–347.

https://doi.org/10.1016/j.envint.2018.05.019

Vuong, A.M., Yolton, K., Xie, C., Webster, G.M., Sjödin, A., Braun, J.M., Dietrich, K.N.,

Lanphear, B.P., Chen, A., 2017. Childhood polybrominated diphenyl ether (PBDE)

221

exposure and neurobehavior in children at 8 years. Environ. Res. 158, 677–684.

https://doi.org/10.1016/j.envres.2017.07.028

Vykoukalová, M., Venier, M., Vojta, Š., Melymuk, L., Bečanová, J., Romanak, K., Prokeš,

R., Okeme, J.O., Saini, A., Diamond, M.L., Klánová, J., 2017. Organophosphate esters

flame retardants in the indoor environment. Environ. Int. 106, 97–104.

https://doi.org/10.1016/j.envint.2017.05.020

Wallace, L., 2000. Correlations of personal exposure to particles with outdoor air

measurements: A review of recent studies. Aerosol Sci. Technol. 32, 15–25.

https://doi.org/10.1080/027868200303894

Wallner, P., Kundi, M., Hohenblum, P., Scharf, S., Hutter, H., 2016. Phthalate Metabolites,

Consumer Habits and Health Effects. Int. J. Environ. Res. Public Health 13, 717.

https://doi.org/10.3390/ijerph13070717

Wan, Y., Diamond, M.L., Siegel, J.A., 2020. Elevated Concentrations of Semivolatile

Organic Compounds in Social Housing Multiunit Residential Building Apartments.

Environ. Sci. Technol. Lett. 7, 191–197. https://doi.org/10.1021/acs.estlett.0c00068

Wang, D.G., Alaee, M., Byer, J.D., Brimble, S., Pacepavicius, G., 2013. Human health risk

assessment of occupational and residential exposures to dechlorane plus in the

manufacturing facility area in China and comparison with e-waste recycling site. Sci.

Total Environ. 445–446, 329–336. https://doi.org/10.1016/j.scitotenv.2012.12.059

Wang, S., Romanak, K.A., Stubbings, W.A., Arrandale, V.H., Hendryx, M., Diamond, M.L.,

Salamova, A., Venier, M., 2019. Silicone wristbands integrate dermal and inhalation

exposures to semi-volatile organic compounds (SVOCs). Environ. Int. 132, 105104.

https://doi.org/10.1016/j.envint.2019.105104

Wang, Y., Peris, A., Rifat, M.R., Ahmed, S.I., Aich, N., Nguyen, L. V., Urík, J., Eljarrat, E.,

Vrana, B., Jantunen, L.M., Diamond, M.L., 2020. Measuring exposure of e-waste

222

dismantlers in Dhaka Bangladesh to organophosphate esters and halogenated flame

retardants using silicone wristbands and T-shirts. Sci. Total Environ. 720, 137480.

https://doi.org/10.1016/j.scitotenv.2020.137480

Wei, G.-L., Li, D.-Q., Zhuo, M.-N., Liao, Y.-S., Xie, Z.-Y., Guo, T.-L., Li, J.-J., Zhang, S.-

Y., Liang, Z.-Q., 2015. Organophosphorus flame retardants and plasticizers: Sources,

occurrence, toxicity and human exposure. Environ. Pollut. 196, 29–46.

https://doi.org/10.1016/j.envpol.2014.09.012

Wei, W., Bonvallot, N., Gustafsson, Å., Raffy, G., Glorennec, P., Krais, A., Ramalho, O., Le

Bot, B., Mandin, C., 2018. Bioaccessibility and bioavailability of environmental semi-

volatile organic compounds via inhalation: A review of methods and models. Environ.

Int. 113, 202–213. https://doi.org/10.1016/j.envint.2018.01.024

Wei, W., Mandin, C., Ramalho, O., 2017. Reactivity of Semivolatile Organic Compounds

with Hydroxyl Radicals, Nitrate Radicals, and Ozone in Indoor Air. Int. J. Chem. Kinet.

49, 506–521. https://doi.org/10.1002/kin.21093

Weschler, C.J., Nazaroff, W.W., 2014. Dermal Uptake of Organic Vapors Commonly Found

in Indoor Air. Environ. Sci. Technol. 48, 1230–1237. https://doi.org/10.1021/es405490a

Weschler, C.J., Nazaroff, W.W., 2012. SVOC exposure indoors: Fresh look at dermal

pathways. Indoor Air. https://doi.org/10.1111/j.1600-0668.2012.00772.x

Weschler, C.J., Nazaroff, W.W., 2010. SVOC partitioning between the gas phase and settled

dust indoors. Atmos. Environ. 44, 3609–3620.

https://doi.org/10.1016/j.atmosenv.2010.06.029

Weschler, C.J., Nazaroff, W.W., 2008. Semivolatile organic compounds in indoor

environments. Atmos. Environ. 42, 9018–9040.

https://doi.org/10.1016/j.atmosenv.2008.09.052

Whitman, W.G., 1962. The two film theory of gas absorption. Int. J. Heat Mass Transf. 5,

223

429–433. https://doi.org/10.1016/0017-9310(62)90032-7

Wielsøe, M., Kern, P., Bonefeld-Jørgensen, E.C., 2017. Serum levels of environmental

pollutants is a risk factor for breast cancer in Inuit: a case control study. Environ. Heal.

16, 56. https://doi.org/10.1186/s12940-017-0269-6

Wong, C.S.C., Duzgoren-Aydin, N.S., Aydin, A., Wong, M.H., 2007. Evidence of excessive

releases of metals from primitive e-waste processing in Guiyu, China. Environ. Pollut.

148, 62–72. https://doi.org/10.1016/j.envpol.2006.11.006

Wu, C.-C., Bao, L.-J., Tao, S., Zeng, E.Y., 2016. Dermal Uptake from Airborne Organics as

an Important Route of Human Exposure to E-Waste Combustion Fumes. Environ. Sci.

Technol. 50, 6599–6605. https://doi.org/10.1021/acs.est.5b05952

Xu, F., Zhang, G., Wang, J., Zhang, W., Liu, L., Lin, K., 2015. Polybrominated diphenyl

ethers in air and fallouts from an e-waste polluted region in southeast China: insight into

levels, compositional profiles, and seasonal variation. Environ. Sci. Pollut. Res. 22,

19676–19686. https://doi.org/10.1007/s11356-015-5168-1

Xu, Y., Cohen Hubal, E.A., Clausen, P.A., Little, J.C., 2009. Predicting Residential Exposure

to Phthalate Plasticizer Emitted from Vinyl Flooring: A Mechanistic Analysis. Environ.

Sci. Technol. 43, 2374–2380. https://doi.org/10.1021/es801354f

Xu, Y., Cohen Hubal, E.A., Little, J.C., 2010. Predicting residential exposure to phthalate

plasticizer emitted from vinyl flooring: Sensitivity, uncertainty, and implications for

biomonitoring. Environ. Health Perspect. 118, 253–258.

https://doi.org/10.1289/ehp.0900559

Yang, C., Harris, S.A., Jantunen, L.M., Kvasnicka, J., Nguyen, L. V., Diamond, M.L., 2020a.

Phthalates: Relationships between Air, Dust, Electronic Devices, and Hands with

Implications for Exposure. Environ. Sci. Technol. 54, acs.est.0c00229.

https://doi.org/10.1021/acs.est.0c00229

224

Yang, C., Harris, S.A., Jantunen, L.M., Siddique, S., Kubwabo, C., Tsirlin, D., Latifovic, L.,

Fraser, B., St-Jean, M., De La Campa, R., You, H., Kulka, R., Diamond, M.L., 2018.

Are cell phones an indicator of personal exposure to organophosphate flame retardants

and plasticizers? Environ. Int. in press, 1–13.

https://doi.org/10.1016/j.envint.2018.10.021

Yang, C., Jílková, S.R., Melymuk, L., Harris, S.A., Jantunen, L.M., Pertili, J., Winn, L.,

Diamond, M.L., 2020b. Are We Exposed to Halogenated Flame Retardants from both

Primary and Secondary Sources? Environ. Sci. Technol. Lett. 7, 585–593.

https://doi.org/10.1021/acs.estlett.0c00268

Young, A.S., Allen, J.G., Kim, U.-J.J., Seller, S., Webster, T.F., Kannan, K., Ceballos, D.M.,

2018. Phthalate and Organophosphate Plasticizers in Nail Polish: Evaluation of Labels

and Ingredients. Environ. Sci. Technol. 52, acs.est.8b04495.

https://doi.org/10.1021/acs.est.8b04495

Zabiegała, B., Zygmunt, B., Przyk, E., Namieśnik, J., 2000. Applicability of silicone

membrane passive samplers for monitoring of indoor air quality. Anal. Lett. 33, 1361–

1372. https://doi.org/10.1080/00032710008543127

Zeng, X., Yang, C., Chiang, J.F., Li, J., 2017. Innovating e-waste management: From

macroscopic to microscopic scales. Sci. Total Environ. 575, 1–5.

https://doi.org/10.1016/j.scitotenv.2016.09.078

Zhang, H., Yolton, K., Webster, G.M., Sjödin, A., Calafat, A.M., Dietrich, K.N., Xu, Y., Xie,

C., Braun, J.M., Lanphear, B.P., Chen, A., 2016. Prenatal PBDE and PCB Exposures

and Reading, Cognition, and Externalizing Behavior in Children. Environ. Health

Perspect. 125, 7–16. https://doi.org/10.1289/EHP478

Zhang, X., Diamond, M.L., Robson, M., Harrad, S., 2011. Sources, emissions, and fate of

polybrominated diphenyl ethers and polychlorinated biphenyls indoors in Toronto,

225

Canada. Environ. Sci. Technol. 45, 3268–3274. https://doi.org/10.1021/es102767g

Zhang, Z., Sun, Z.-Z., Xiao, X., Zhou, S., Wang, X.X.-C., Gu, J., Qiu, L.-L., Zhang, X.-H.,

Xu, Q., Zhen, B., Wang, X.X.-C., Wang, S.-L., 2013a. Mechanism of BDE209-induced

impaired glucose homeostasis based on gene microarray analysis of adult rat liver. Arch.

Toxicol. 87, 1557–1567. https://doi.org/10.1007/s00204-013-1059-8

Zhang, Z., Zhang, X., Sun, Z., Dong, H., Qiu, L., Gu, J., Zhou, J., Wang, X., Wang, S.L.,

2013b. Cytochrome P450 3A1 Mediates 2,2′,4,4′-Tetrabromodiphenyl Ether-Induced

Reduction of Spermatogenesis in Adult Rats. PLoS One 8.

https://doi.org/10.1371/journal.pone.0066301

Zheng, X., Xu, F., Chen, K., Zeng, Y., Luo, X., Chen, S., Mai, B., Covaci, A., 2015. Flame

retardants and organochlorines in indoor dust from several e-waste recycling sites in

South China: Composition variations and implications for human exposure. Environ. Int.

78, 1–7. https://doi.org/10.1016/j.envint.2015.02.006

Zota, A.R., Rudel, R.A., Morello-Frosch, R.A., Brody, J.G., 2008. Elevated House Dust and

Serum Concentrations of PBDEs in California: Unintended Consequences of Furniture

Flammability Standards? Environ. Sci. Technol. 42, 8158–8164.

https://doi.org/10.1021/es801792z

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Appendices

Appendix 1: Supporting Information for Chapter 2

Table A2.1. Full names, CAS numbers, and molecular weights (g mol-1) of target compounds in Chapter 2. Family and CAS Molecular Full name acronym number weight Novel-brominated flame retardants (N-BFRs) EHTBB 2-Ethylhexyl-tetrabromobenzoate 183658-27-7 549.9 BEHTBP Bis(2-ethlyhexyl) tetrabromophthalate 26040-51-7 706.1 s-DP Dechlorane Plus (syn isomer) 13560-89-9 654 a-DP Dechlorane Plus (anti isomer) 13560-89-9 654 Polybrominated diphenyl ethers (PBDEs) BDE-47 2,2',4,4'-Tetrabromodiphenyl ether 5436-43-1 486 BDE-99 2,2',4,4',5-Pentabromodiphenyl ether 60348-60-9 565 2,2',3,4,4',5',6-Heptabromodiphenyl BDE-183 207122-16-5 722 ether BDE-209 Decabromodiphenyl ether 1163-19-5 959 Organophosphate esters (OPEs) TCEP Tris(2-chloroethyl) phosphate 115-96-8 285.49 TCIPP Tris(2-chloroisopropyl) phosphate 13674-84-5 327.57 TDClPP Tris(1,3-dichloro-2-propyl) phosphate 13674-87-8 430.90 TPhP Triphenyl phosphate 115-86-6 326.28 EHDPP 2-Ethylhexyl diphenyl phosphate 1241-94-7 362.40

A2.1 – Sample preparation

All glass fiber filters (GFFs) used in active air samplers and MOUDI were baked at

450 °C for 12 hours, wrapped in aluminum foil and kept in air-tight jars before deployment.

All ORBO cartridges and OVS were pre-cleaned by Soxhlet extraction for 24 hours with n-hexane : acetone : dichloromethane (1:1:1, v/v), dried with chromatography grade nitrogen, wrapped in aluminium foil and stored in air-tight jars before deployment.

Nylon vacuum socks were pre-cleaned by accelerated solvent extraction (ASE;

Dionex, Sunnyvale, CA, USA) with n-hexane at 90 °C for 4 cycles, dried and wrapped in aluminium foil before deployment.

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A2.2 - Details of extraction and analysis

Before extraction, all samples were spiked with surrogate standards (BDE-77, BDE-

13 13 166, and C12-BDE-209, d12-TCEP, and C-TPhP). GFFs from the active air sampling train

(GFF-AA), MOUDI (MOUDI-GFF) and dust were extracted in 1:1 acetone in n-hexane via three 10-min cycles of ultra-sonication followed by vortexing. The OVS and ORBO cartridges were extracted via accelerated solvent extraction (ASE; Dionex, Sunnyvale, CA, USA) with acetone, dichloromethane and n-hexane (1:1:1 v:v:v) at 90 °C. Individual dust samples were emptied from nylon socks and sieved at 500 µm from which 50 mg was subsampled. All extracts were spiked with internal standards (BDE-118 and -181 for HFRs; d10-anthracene, d12-benz[a]-anthracene, and d12-perylene for OPEs).

Dust and air extracts (from ORBO cartridges, GFF-AAs and OVS samples) were evaporated to 2 mL via RapidVap (Labconco, Kansas City, MO, USA) with two solvent exchanges of 75 mL of n-hexane each. All extracts were then fractionated on a 3.5 g silica column topped 1.5 cm with sodium sulfate. The column was eluted with 25 mL of n-hexane,

25 mL of 1:1 (v/v) n-hexane in DCM, and 25 mL of 7:3 (v/v) acetone in DCM. Each fraction was evaporated under a gentle stream of nitrogen to ~1 mL and then solvent exchanged to n- hexane. Fractions 1 and 2 were further concentrated to 100 µL with a gentle stream of N2. The

MOUDI-GFFs were volume reduced using a gentle steam of N2 to ~0.5mL and no cleanup was performed.

HFRs were analysed on an Agilent 7890 series GC coupled to an Agilent 5975C mass spectrometer operating in the electron capture negative ionization (ECNI) mode with methane as the reagent gas. One µL sample was injected in the pulsed splitless mode. Inlet, ion source, and GC/MS interface temperatures were 240 °C, 200 °C, and 320 °C respectively.

Chromatographic resolution was achieved with an Rtx-1614 (15 m × 0.25 mm × 0.1 µm) fused silica capillary GC column (Restek, USA), using helium as the carrier gas with a constant flow

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of 1.5 mL/min. Four PBDE congeners and four alternative BFRs were analysed. The GC oven temperature program was as follows: 100 °C for 2 min, 25 °C/min to 250 °C, 3 °C/min to 270

°C, 25 °C/min to 320 °C and held for 9 min.

For OPEs, an Agilent 6890 series GC coupled to an Agilent 5973 MS was used for quantification. The MS was operated in the electron impact (EI) mode. The gas chromatography resolution was achieved with a RTX-OPPesticides2 (30 m, 250 μm i.d., and

0.25 μm film thickness) capillary column (Restek Corporation, Bellefonte, CA). One µL of the sample was injected in the pulsed splitless mode at 285 °C. The GC-MS interface was kept at 300 °C. Temperatures of the ion source and quadrupole were set at 230 °C and 150 °C, respectively. High purity helium (99.999%; Indiana Oxygen Co., Indianapolis) was used as the carrier gas. The GC oven temperature was held at 50 °C for 3 min, increased to 100 °C at

20 °C /min, then increased to 170 °C at 10 °C /min, held for 3 min, then S6 increased to 230

°C at 12 °C/min, held for 4 min, then increased to 260 °C at 5 °C/min, finally increased to 300

°C at 10 °C/min, and held for 14 min.

Details on monitored ions are reported in Table A2.2.

A2.3 - Quality Assurance and Quality Control

Six dust field blanks were taken, one per day of dust sampling. Each dust field blank consisted of pre-cleaned 1.0 g sodium sulfate (Sigma-Aldrich, USA, baked at 450 °C and wrapped in pre-cleaned aluminum foil). Ten air active sample field blanks were taken, one per day of sampling for each of the OVS and ORBO samplers. Additionally, one lab blank and one matrix spike were analyzed per batch of dust, OVS, ORBO and GFF samples (a total of five for each matrix). For the MOUDI, two GFF field blanks were taken, one for each sample.

The masses of the target compounds in each sample were compared to the mean mass in the field blanks on a matrix specific basis. Blank levels were treated as follows, as described by

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(Saini et al., 2015): no correction if the blank level was <10% of the measured level; blank level was subtracted from the measured level if the blank level was 10 - 35 % of the measured level; the sample was reported as “non-detect” if the blank level was >35 % of the measured level. No blanks were >35% in this study. One to two values in the field blanks were excluded if they were outliers. Instrument detection limits (IDLs) were calculated as the standard deviation from 10 replicate injections of a low concentration standard (Table A2.3). Surrogate standard recoveries and matrix spike recoveries were considered satisfactory if they were between 50 – 150 % and no recovery correction was applied. Surrogate recoveries were considered satisfactory when two out of three recoveries were within the range 50-150 %.

Figure A2.1. Schematic of floor layout of Ontario e-waste recycling facility.

D E

Area A - Workbenches for dismantling TVs and screens.

Area B – Workbenches for dismantling computers.

Area C – Bins storing printers, adaptors, phones, toys and miscellaneous items.

Area D – Storage bins for un-sorted e-waste products

Area E – Storage piles for sorted e-waste products

Dash-line area – First-floor office area.

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Figure A2.2. The setting of area and workbench air samples.

Table A.2.2. Monitored quantifier and qualifier ions for surrogate and native compounds. Compounds Compound type Quantifier ion Qualifier ion Polybrominated diphenyl ethers (PBDEs) and Novel-brominated flame retardants (N- BFRs) BDE-47 TC 79 81 BDE-99 TC 79 81 BDE-183 TC 79 81 BDE-209 TC 487 489 EHTBB TC 357 359 BEHTBP TC 462 464 s-DP TC 652 654 a-DP TC 652 654 BDE-77 SS 79 81 BDE-166 SS 79 81 13 C12-BDE-209 SS 495 497 BDE-118 IS 79 81 BDE-181 IS 79 81 Organophosphate esters (OPEs) TCEP TC 249 251 TCIPP TC 277 279 TDCIPP TC 381 383 TPhP TC 326 325 EHDPP TC 251 250 d12-TCEP SS 261 263 13C18-TPhP SS 343 344 d10-anthracene IS 188 184 d12-benz[a]-anthracene IS 240 236 d12-perylene IS 264 - TC: Target compound; SS: Surrogate standard; IS: Internal standard

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Table A2.3. Instrumental limit of detections (IDLs) and method detection limits (MDLs). IDL (ng) MDLs Compounds Dust OVS ORBO GFF (ng/g) (ng/m3) (ng/m3) (ng/m3) Novel-brominated flame retardants (N-BFRs) EHTBB 0.123 0.553 0.022 0.008 0.002 BEHTBP 0.203 0.489 0.016 0.003 0.005 s-DP 0.211 0.120 0.004 0.001 0.000 a-DP 0.136 0.117 0.006 0.001 0.001 Polybrominated diphenyl ethers (PBDEs) BDE-47 0.137 0.534 0.009 0.004 0.005 BDE-99 0.055 0.448 0.011 0.003 0.004 BDE-183 0.163 1.086 0.024 0.007 0.009 BDE-209 0.219 3.113 0.053 0.027 0.023 Organophosphate esters (OPEs) TCEP 4.393 18.813 0.361 0.072 0.066 TCIPP 5.241 10.556 0.423 0.085 0.037 TDCIPP 13.205 52.671 1.003 0.201 0.184 TPhP 2.787 6.941 0.293 0.059 0.024 EHDPP 8.587 5.009 0.144 0.029 0.018

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Table A2.4. Summary of exposure factors and calculations via air inhalation, dermal absorption, and dust ingestion.

Exposure factors Exposure calculations Exposure duration 8 hours or 0.33 days Fraction of time spent▲ 0.33 Air inhalation (pg kg-bw-1 day-1) = Air Body weight (US EPA, 73 kg (female) concentration (pg m-3) * inhalation rate 2011) 85 kg (male) (m3 day-1) * Fraction of time spent / Inhalation rate (US EPA, 18 m3 day-1 (male) body weight (kg). 2011) 14 m3 day-1 (female) Body surface area for Dermal absorption (pg kg-bw-1 day-1) = only head and hand 2430 cm2 (male) Dust concentration (pg g-1) * BSA (cm2) exposure (BSA)(US 2030 cm2 (female) * DAS (mg cm-2) * Fa (unitless) * EPA, 2011) exposure duration (day) / body weight Dust adhered to skin (kg). 0.01 mg cm-2 (DAS)(US EPA, 2011) Fractions of target Dust ingestion (pg kg-bw-1 day-1) = compound absorbed by In Table A2.5 Dust concentration (pg g-1) * dust skin (Fa)(US EPA, 2011) ingestion rate (g day-1) * Fraction of Dust ingestion rate (US time spent / body weight (kg). 0.06 g day-1 EPA, 2011) ▲ We assume that a worker exposed to targeted compounds during 8 hours over 24 hours per day. Hence, a fraction of time a worker spent in the facility assumed as 8 hours /24 hours = 0.33.

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Table A2.5. Fraction of contaminant absorbed by human skin are taken from Abdallah et al. (2015a, 2015b), Abdallah et al. (2016) and Pawar (2017) (Abdallah et al., 2015b, 2015a; Abou-Elwafa Abdallah et al., 2016; Pawar, 2017).

Fraction absorbed Novel-brominated flame retardants (N-BFRs) EHTBB 0.007 BEHTBP No information s-DP No information a-DP No information Polybrominated diphenyl ethers (PBDEs) BDE-47 0.0285 BDE-99 0.0196 BDE-183 0.0005 BDE-209 Not absorbed Organophosphate esters (OPEs) TCEP 0.283 TCIPP 0.247 TDCIPP 0.127 TPhP 0.18 EHDPP 0.102

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Table A2.6. Median concentrations (ng m-3) of air concentrations collected from 4 workbenches in 5 days. Comparisons between benches and days were completed using Kruskal-Wallis test. No comparisons reached statistical significance (p-value < 0.05).

Compounds BDE BDE BDE BDE EHTBB BEHTBP s-DP a-DP TCEP TCIPP TDCIPP TPhP EHDPP Variables 47 99 183 209 Bench 1 1.1 2.2 3.0 140 1.3 7.1 2.2 4.1 61 62 31 62 26 2 0.7 1.2 1.8 184 0.7 4.1 2.4 3.8 58 50 99 38 19 3 0.8 1.3 2.6 250 1.1 4.2 2.0 4.6 49 46 78 56 23 4 0.7 1.2 1.7 87 1.2 6.3 1.7 3.3 47 45 33 38 20 Kruskal-Wallis 0.26 0.26 0.26 0.26 0.26 0.26 0.26 0.26 0.26 0.26 0.26 0.26 0.26 test, p-value Day 1 1.1 2.1 2.4 168 1.6 6.8 2.2 3.6 61 54 31 47 21 2 1.5 4.1 2.2 191 4.9 31 2.2 4.0 87 82 103 122 76 3 0.6 1.0 2.2 217 0.5 2.8 1.8 3.5 42 50 68 46 16 4 1.1 1.4 1.9 182 1.1 5.3 2.2 4.2 54 47 416 39 23 5 0.6 1.1 2.4 79 0.9 3.5 2.3 5.0 44 37 20 36 18 Kruskal-Wallis 0.46 0.46 0.46 0.46 0.46 0.46 0.46 0.46 0.46 0.46 0.46 0.46 0.46 test, p-value

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Table A2.7. Spearman’s correlation (rho) between the air and dust concentrations of FRs and the amount of e-waste products (in tonnes) processed in Ontario, Canada e-waste recycling facility. Compounds Variables BDE BDE BDE BDE EHTBB BEHTBP s-DP a-DP TCEP TCIPP TDCIPP TPhP EHDPP 47 99 183 209 Workbench Air E-waste Concentration Processed 0.2 0.1 0.01 0.5* 0.1 0.2 0.04 0.2 0.2 0.5* 0.1 0.3 0.1 (tonnes) Workbench Dust E-waste Concentration Processed 0.5 0.1 0.6 0.3 0 0.3 0.1 0.3 0.02 0.2 0.3 0.1 0.4 (tonnes) *p-value < 0.05

Table A2.8. Bulk air concentrations (ng m-3) of different size fractions collected using a MOUDI. Compounds Stage BDE BDE 99 BDE 183 BDE 209 EH-TBB BEH-TBP s-DP a-DP TCEP TCIPP TDCIPP TPhP EHDPP ∑13 FRs 47 1▲ ND ND ND 0.07 ND ND ND ND ND ND ND 1.0 ND 1.1 2▲ ND ND ND 0.07 0.01 0.01 0.01 0.01 0.76 0.27 ND 1.3 ND 2.4 3▲ ND ND ND 0.35 0.01 0.01 0.01 0.01 0.81 0.28 ND 2.3 ND 3.8 4▲ ND ND ND 0.64 0.01 0.02 0.01 0.02 0.92 0.31 ND 2.2 ND 4.1 5▲ ND 0.02 0.02 2.7 0.03 0.04 0.02 0.04 1.0 0.45 ND 4.0 0.53 8.8 6▲ 0.02 0.04 0.07 8.7 0.02 0.02 0.06 0.11 1.1 0.77 ND 9.5 1.3 22 7▲ 0.08 0.15 0.24 41 0.04 0.19 0.20 0.36 2.1 1.5 1.8 24.4 3.1 75 8 0.13 0.25 0.38 65 0.08 0.29 0.32 0.58 2.8 2.0 2.9 39.0 4.8 119 9 0.11 0.20 0.32 55 0.07 0.28 0.31 0.49 2.4 1.9 2.2 34.7 3.7 102 10 0.07 0.12 0.18 34 0.04 0.17 0.17 0.32 2.2 1.9 1.4 25.4 2.3 68 Respirable 0.10 0.21 0.33 53 0.12 0.28 0.30 0.55 6.6 3.5 2.8 45 5.9 119 size particles Particle sizes of: stage 1 = 0.056 – 0.1 µm; stage 2 = 0.1 – 0.18 µm; stage 3 = 0.18 – 0.32 µm; stage 4 = 0.32 – 0.56 µm; stage 5 = 0.56 – 1 µm; stage 6 = 1 – 1.8 µm; stage 7 = 1.8 – 3.2 µm; stage 8 = 3.2 – 5.6 µm; stage 9 = 5.6 – 10 µm and stage 10 = 10 – 18 µm.▲Respirable particles; ND: non-detect

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Table A2.9. Comparison of exposure estimates (pg kg-bw-1 day-1) to flame retardants via air inhalation, dermal ingestion and dust ingestion reported for indoor e-waste handling facilities in various countries.

Compounds Statistical BDE BDE BDE EH- BEH- Location, population exposed BDE 209 s-DP a-DP TCEP TCIPP TDCIPP TPhP EHDPP parameter 47 99 183 TBB TBP Air inhalation Canada, this study, male Median 59 107 150 11,030 84 385 143 270 4,130 3,540 3,380 3,220 1,500 dismantlers Canada, this study, female Median 53 97 136 9,990 76 348 129 244 3,740 3,210 3,060 2,920 1,350 dismantlers Thailand, e-waste workers ∆ Median - 1.1 ------(Muenhor et al., 2010) USA, male e-waste workers with shredding activities ◼ (Cahill et Average 148 154 2,028 36,900 ------al., 2007) USA, male e-waste workers with shredding activities ◼ (Cahill et Average 141 147 1,940 35,230 ------al., 2007) China, e-waste workers  (Guo et Average 260 340 795 ------al., 2015) Dermal absorption Canada, this study, male Median 0.95 0.94 0.1 - 0.55 - - - 243 274 201 795 61 dismantlers Canada, this study, female Median 0.92 0.91 0.08 - 0.53 - - - 237 266 195 773 60 dismantlers China, e-waste workers ⧫ (Wu et Average 240 50 ------al., 2016) Dust ingestion Canada, this study, male Median 402 618 1,370 89,200 693 1,940 2,086 4,520 7,440 10,890 21,500 36,700 8,190 dismantlers Canada, this study, female Median 310 270 - 30,000 ------dismantlers Thailand, e-waste workers ∆ Median 160 380 1,700 20,000 ------(Muenhor et al., 2010) Guiyu, China, e-waste workers  Median 234 326 483 13,119 14 12 250 566 151 895 357 2,336 519 (Zheng et al., 2015)

∆ Exposure duration = 16 h, inhalation rate = 0.83 m3 h-1 or 19.9 m3 day-1, body weight = 68.9 kg. ; ◼ Exposure duration = 8 h, inhalation rate = 0.6 m3 h-1 or 14.4 m3 day-1, body weight = 78.1 kg.

 Exposure duration = 8 h, inhalation rate (high intensive activity) = 3 m3 h-1 or 72 m3 day-1, body weight = 70 kg.

 Dermal absorption = Bulk air concentration * Overall permeability from bulk air to dermal capillaries * Skin surface area * fraction of skin exposed * exposure duration / body weight.(Little et al., 2012) Exposure duration = 24 h, other exposure factors can be found in Table 2 of Little et al.(Little et al., 2012) and Tables 1 and 3 of Weschler et al.(2010) 237

Table A2.10. Comparison of estimated dust ingestion exposure and available reference doses for select PBDEs and OPEs

Compounds Estimated exposure Reference value** Source Comment via dust ingestion* (pg kg-bw-1 day-1) (pg kg-bw-1 day-1) Novel-brominated flame retardants (N-BFRs) Maternal body weight – oral EHTBB 396 8 x 107 other chronical (Hays and Kirman, 2017) BEHTBP 1,750 NA - - s-DP 1,370 NOAEL oral sub-chronic (Wang et 5 x 109 other a-DP 2,900 al., 2013) Polybrominated diphenyl ethers (PBDEs) U.S. EPA/IRIS Neurobehavioral effects of single 1 x 105 (US EPA, oral dose (Eriksson et al., 2001) 2018a) BDE-47 192 ATSDR Decreased testosterone – oral sub- 3,000 (ATSDR, chronic (Zhang et al., 2013b) 2004) U.S. EPA/IRIS Neurobehavioral effects of single 1 x 105 (US EPA, oral dose (Viberg et al., 2004) 2018a) BDE-99 288 RIVM (de Effects on sperm production of Winter- 260 single oral dose (Kuriyama et al., Sorkina et al., 2005). Different calculation method 2006) BDE-183 1,750 NA _ _ U.S. EPA/IRIS Neurobehavioral effects of single 7 x 106 (US EPA, oral dose (Viberg et al., 2003) 2018a) BDE-209 61,100 ATSDR Increased serum glucose – oral sub- 2 x 105 (ATSDR, chronic (Zhang et al., 2013a) 2004) Organophosphate esters (OPEs) U.S. EPA Increased liver and kidney weight Chemistry 7 x 106 after sub-chronic oral exposure dashboard (US (NTP, 1991) TCEP 3,100 EPA, 2018b) ATSDR Renal hyperplasia after chronical 2 x 108 (ATSDR, oral exposure in rats 2012) U.S. EPA Chemistry TCIPP 3,627 1 x 107 Not specified dashboard (US EPA, 2018b) ATSDR Renal hyperplasia after chronical TDCIPP 7,100 2 x 107 (ATSDR, oral exposure in rats 2012) TPhP 15,500 NA - - EHDPP 3,660 NA - - * 95th percentile (female e-waste workers)

** Oral chronical (or sub-chronical) reference values: RfD (US-EPA), MRL (ATSDR), maximal allowed daily intake (RIVM)

NA: Not available

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References Abbasi, G., Buser, A.M., Soehl, A., Murray, M.W., Diamond, M.L., 2015. Stocks and flows of PBDEs in products from use to waste in the U.S. and canada from 1970 to 2020. Environ. Sci. Technol. 49, 1521–1528. https://doi.org/10.1021/es504007v Abbasi, G., Saini, A., Goosey, E., Diamond, M.L., 2016. Product screening for sources of halogenated flame retardants in Canadian house and office dust. Sci. Total Environ. 545–546, 299–307. https://doi.org/10.1016/j.scitotenv.2015.12.028 Abdallah, M.A.-E., Pawar, G., Harrad, S., 2015a. Evaluation of 3D-human skin equivalents for assessment of human dermal absorption of some brominated flame retardants. Environ. Int. 84, 64–70. https://doi.org/10.1016/j.envint.2015.07.015 Abdallah, M.A.-E., Pawar, G., Harrad, S., 2015b. Effect of Bromine Substitution on Human Dermal Absorption of Polybrominated Diphenyl Ethers. Environ. Sci. Technol. 49, 10976–10983. https://doi.org/10.1021/acs.est.5b03904 Abou-Elwafa Abdallah, M., Pawar, G., Harrad, S., 2016. Human dermal absorption of chlorinated organophosphate flame retardants; implications for human exposure. Toxicol. Appl. Pharmacol. 291, 28–37. https://doi.org/10.1016/j.taap.2015.12.004 ACGIH, 2018. TLVs ® and BEIs ® : Threshold limit values for chemical substances and physical agents biological exposure indices. American Conference of Governmental Industrial Hygienists, Cincinnati, OH, OH. ACGIH, 2001. Documentation of threshold limit values for substances in work environment. American Conference of Governmental Industrial Hygienists, Cincinnati, OH, OH. Ait, Y., Araki, A., Kawai, T., Tsuboi, T., Saito, I., Yoshioka, E., Kanazawa, A., 2014. Science of the Total Environment Associations of phthalate concentrations in fl oor dust and multi-surface dust with the interior materials in Japanese dwellings. Sci. Total Environ. 468–469, 147–157. https://doi.org/10.1016/j.scitotenv.2013.07.107 Akormedi, M., Asampong, E., Fobil, J.N., 2013. Working conditions and environmental exposures among electronic waste workers in Ghana. Int. J. Occup. Environ. Health 19, 278–286. https://doi.org/10.1179/2049396713Y.0000000034 Allen, J.G., McClean, M.D., Stapleton, H.M., Nelson, J.W., Webster, T.F., 2007. Personal Exposure to Polybrominated Diphenyl Ethers (PBDEs) in Residential Indoor Air. Environ. Sci. Technol. 41, 4574–4579. https://doi.org/10.1021/es0703170 Allen, J.O., Dookeran, N.M., Smith, K.A., Sarofim, A.F., Taghizadeh, K., Lafleur, A.L., 1996. Measurement of polycyclic aromatic hydrocarbons associated with size- segregated atmospheric aerosols in Massachusetts. Environ. Sci. Technol. 30, 1023– 1031. https://doi.org/10.1021/es950517o Andersen, C., Krais, A.M., Eriksson, A.C., Jakobsson, J., Löndahl, J., Nielsen, J., Lindh, C.H., Pagels, J., Gudmundsson, A., Wierzbicka, A., 2018. Inhalation and Dermal Uptake of Particle and Gas-Phase Phthalates—A Human Exposure Study. Environ. Sci. Technol. 52, 12792–12800. https://doi.org/10.1021/acs.est.8b03761 Asante, K.A., Agusa, T., Biney, C.A., Agyekum, W.A., Bello, M., Otsuka, M., Itai, T., Takahashi, S., Tanabe, S., 2012. Multi-trace element levels and arsenic speciation in urine of e-waste recycling workers from Agbogbloshie, Accra in Ghana. Sci. Total

239

Environ. 424, 63–73. https://doi.org/10.1016/j.scitotenv.2012.02.072 ATSDR, 2012. Toxicological Profile for Phosphate Ester Flame Retardants. ATSDR, 2005. Public Health Assessment Guidance Manual (2005 Update). Atlanta, Georgia. ATSDR, 2004. Toxicological profile for polybrominated biphenyl and polybrominated diphenyl ethers 1–599. Awasthi, A.K., Wang, M., Wang, Z., Awasthi, M.K., Li, J., 2018. E-waste management in India: A mini-review. Waste Manag. Res. 36, 408–414. https://doi.org/10.1177/0734242X18767038 Bakhiyi, B., Gravel, S., Ceballos, D., Flynn, M.A., Zayed, J., 2018. Has the question of e- waste opened a Pandora’s box? An overview of unpredictable issues and challenges. Environ. Int. 110, 173–192. https://doi.org/https://doi.org/10.1016/j.envint.2017.10.021 Balde, C.P., Forti, V., Gray, V., Kuehr, R., Stegmann, P., 2017. The global e-waste monitor 2017, United Nations University. https://doi.org/10.1016/j.proci.2014.05.148 Baldé, C.P., Wang, F., Kuehr, R., Huisman, J., 2015. The Global E-waste Monitor 2014: Quantitites, flows and resources. Bonn, Germany. https://doi.org/ISBN 978-92-808- 4556-3 Bartkow, M.E., Booij, K., Kennedy, K.E., Müller, J.F., Hawker, D.W., 2005. Passive air sampling theory for semivolatile organic compounds. Chemosphere 60, 170–176. https://doi.org/10.1016/j.chemosphere.2004.12.033 Basel Convention, 2011. Electrical and electronic equipment when becoming waste (e- waste) such as personal computers, printers, televisions, mobile phones, refrigerators and air-conditioning units is one of the fastest growing waste streams in the world today. [WWW Document]. URL http://www.basel.int/Implementation/Ewaste/Overview/tabid/4063/Default.aspx (accessed 3.8.20). Beaucham, C.C., Ceballos, D., Page, E.H., Mueller, C., Calafat, A.M., Sjodin, A., Ospina, M., Guardia, M. La, Glassford, E., 2018. Evaluation of Exposure to Metals , Flame Retardants , and Nanomaterials at an Electronics Recycling Company 1–80. Behl, M., Hsieh, J.H., Shafer, T.J., Mundy, W.R., Rice, J.R., Boyd, W.A., Freedman, J.H., Hunter, E.S., Jarema, K.A., Padilla, S., Tice, R.R., 2015. Use of alternative assays to identify and prioritize organophosphorus flame retardants for potential developmental and neurotoxicity. Neurotoxicol. Teratol. 52, 181–193. https://doi.org/10.1016/j.ntt.2015.09.003 Behl, M., Rice, J.R., Smith, M. V., Co, C.A., Bridge, M.F., Hsieh, J.-H., Freedman, J.H., Boyd, W.A., 2016. Editor’s Highlight: Comparative Toxicity of Organophosphate Flame Retardants and Polybrominated Diphenyl Ethers to Caenorhabditis elegans. Toxicol. Sci. 154, 241–252. https://doi.org/10.1093/toxsci/kfw162 Bergh, C., Torgrip, R., Emenius, G., Östman, C., 2011. Organophosphate and phthalate esters in air and settled dust - a multi-location indoor study. Indoor Air 21, 67–76. https://doi.org/10.1111/j.1600-0668.2010.00684.x Betts, K.S., 2002. Rapidly rising PBDE levels in North America. Environ. Sci. Technol. 36,

240

50A-52A. https://doi.org/10.1021/es022197w Bi, C., Liang, Y., Xu, Y., 2015. Fate and Transport of Phthalates in Indoor Environments and the Influence of Temperature: A Case Study in a Test House. Environ. Sci. Technol. 49, 9674–9681. https://doi.org/10.1021/acs.est.5b02787 Bidleman, T.F., 1988. Atmospheric processes. Environ. Sci. Technol. 22, 361–367. https://doi.org/10.1021/es00169a002 Blum, A., Behl, M., Birnbaum, L.S., Diamond, M.L., Phillips, A., Singla, V., Sipes, N.S., Stapleton, H.M., Venier, M., 2019. Organophosphate Ester Flame Retardants: Are They a Regrettable Substitution for Polybrominated Diphenyl Ethers? Environ. Sci. Technol. Lett. 6, 638–649. https://doi.org/10.1021/acs.estlett.9b00582 Bohlin, P., Audy, O., Škrdlíková, L., Kukučka, P., Přibylová, P., Prokeš, R., Vojta, Š., Klánová, J., 2014. Outdoor passive air monitoring of semi volatile organic compounds (SVOCs): a critical evaluation of performance and limitations of polyurethane foam (PUF) disks. Environ. Sci. Process. Impacts 16, 433–444. https://doi.org/10.1039/C3EM00644A Bohlin, Pernilla, Audy, O., Škrdlíková, L., Kukučka, P., Vojta, Š., Přibylová, P., Prokeš, R., Čupr, P., Klánová, J., 2014. Evaluation and guidelines for using polyurethane foam (PUF) passive air samplers in double-dome chambers to assess semi-volatile organic compounds (SVOCs) in non-industrial indoor environments. Environ. Sci. Process. Impacts 16, 2617–2626. https://doi.org/10.1039/C4EM00305E Bohlin, P., Jones, K.C., Levin, J.-O., Lindahl, R., Strandberg, B., 2010a. Field evaluation of a passive personal air sampler for screening of PAH exposure in workplaces. J. Environ. Monit. 12, 1437. https://doi.org/10.1039/c0em00018c Bohlin, P., Jones, K.C., Strandberg, B., 2010b. Field evaluation of polyurethane foam passive air samplers to assess airborne PAHs in occupational environments. Environ. Sci. Technol. 44, 749–754. https://doi.org/10.1021/es902318g Bohlin, P., Jones, K.C., Strandberg, B., 2007. Occupational and indoor air exposure to persistent organic pollutants: A review of passive sampling techniques and needs. J. Environ. Monit. 9, 501. https://doi.org/10.1039/b700627f Bornehag, C.G., Nanberg, E., 2010. Phthalate exposure and asthma in children 33, 333–345. https://doi.org/10.1111/j.1365-2605.2009.01023.x Braun, J.M., Kalkbrenner, A.E., Just, A.C., Yolton, K., Calafat, A.M., Sjödin, A., Hauser, R., Webster, G.M., Chen, A., Lanphear, B.P., 2014. Gestational Exposure to Endocrine- Disrupting Chemicals and Reciprocal Social, Repetitive, and Stereotypic Behaviors in 4- and 5-Year-Old Children: The HOME Study. Environ. Health Perspect. 122, 513– 520. https://doi.org/10.1289/ehp.1307261 Breul, S., Van Landuyt, K.L., Reichl, F.X., Högg, C., Hoet, P., Godderis, L., Van Meerbeek, B., Cokic, S.M., 2020. Filtration efficiency of surgical and FFP3 masks against composite dust. Eur. J. Oral Sci. 128, 233–240. https://doi.org/10.1111/eos.12697 Brown, J., Gordon, T., Price, O., Asgharian, B., 2013. Thoracic and respirable particle deinitions for human health risk assessment. Part. Fibre Toxicol. 10, 1–12. Cahill, T.M., Groskova, D., Charles, M.J., Sanborn, J.R., Denison, M.S., Baker, L., 2007. Atmospheric concentrations of polybrominated diphenyl ethers at near-source sites. 241

Environ. Sci. Technol. 41, 6370–6377. https://doi.org/10.1021/es070844j Callesen, M., Bekö, G., Weschler, C.J., Langer, S., Brive, L., Clausen, G., Toftum, J., Sigsgaard, T., Høst, A., Kold, T., 2014. International Journal of Hygiene and Phthalate metabolites in urine and asthma , allergic rhinoconjunctivitis and atopic dermatitis in preschool children. Int. J. Hyg. Environ. Health 217, 645–652. https://doi.org/10.1016/j.ijheh.2013.12.001 Cao, Z., Xu, F., Covaci, A., Wu, M., Wang, H., Yu, G., Wang, B., Deng, S., Huang, J., Wang, X., 2014. Distribution patterns of brominated, chlorinated, and phosphorus flame retardants with particle size in indoor and outdoor dust and implications for human exposure. Environ. Sci. Technol. 48, 8839–8846. https://doi.org/10.1021/es501224b Carignan, C.C., Mínguez-Alarcón, L., Butt, C.M., Williams, P.L., Meeker, J.D., Stapleton, H.M., Toth, T.L., Ford, J.B., Hauser, R., 2017. Urinary Concentrations of Organophosphate Flame Retardant Metabolites and Pregnancy Outcomes among Women Undergoing in Vitro Fertilization. Environ. Health Perspect. 125, 087018. https://doi.org/10.1289/EHP1021 Carignan, C.C., Mínguez-Alarcón, L., Williams, P.L., Meeker, J.D., Stapleton, H.M., Butt, C.M., Toth, T.L., Ford, J.B., Hauser, R., 2018. Paternal urinary concentrations of organophosphate flame retardant metabolites, fertility measures, and pregnancy outcomes among couples undergoing in vitro fertilization. Environ. Int. 111, 232–238. https://doi.org/10.1016/j.envint.2017.12.005 Castorina, R., Bradman, A., Stapleton, H.M., Butt, C., Avery, D., Harley, K.G., Gunier, R.B., Holland, N., Eskenazi, B., 2017. Current-use flame retardants: Maternal exposure and neurodevelopment in children of the CHAMACOS cohort. Chemosphere 189, 574– 580. https://doi.org/10.1016/j.chemosphere.2017.09.037 Ceballos, D.M., Côté, D., Bakhiyi, B., Flynn, M.A., Zayed, J., Gravel, S., Herrick, R.F., Labrèche, F., 2020. Overlapping vulnerabilities in workers of the electronics recycling industry formal sector: A commentary. Am. J. Ind. Med. 63, 955–962. https://doi.org/10.1002/ajim.23173 Ceballos, D.M., Dong, Z., 2016. The formal electronic recycling industry: Challenges and opportunities in occupational and environmental health research. Environ. Int. 95, 157– 166. https://doi.org/10.1016/j.envint.2016.07.010 CEPA, 1999. Canadian Environmental Protection Act. Cequier, E., Sakhi, A.K., Marcé, R.M., Becher, G., Thomsen, C., 2015. Human exposure pathways to organophosphate triesters — A biomonitoring study of mother–child pairs. Environ. Int. 75, 159–165. https://doi.org/10.1016/j.envint.2014.11.009 Chan, J.K.Y., Wong, M.H., 2013. A review of environmental fate, body burdens, and human health risk assessment of PCDD/Fs at two typical electronic waste recycling sites in China. Sci. Total Environ. 463–464, 1111–1123. https://doi.org/10.1016/j.scitotenv.2012.07.098 Cherrie, J.W., 2003. CommentaryThe Beginning of the Science Underpinning Occupational Hygiene. Ann. Occup. Hyg. 47, 179–185. https://doi.org/10.1093/annhyg/meg030 City of Toronto, 2019. Search for an Establishment Monitored by BodySafe [WWW

242

Document]. URL https://www.toronto.ca/community-people/health-wellness- care/health-programs-advice/bodysafe/search-for-an-establishment-space-holder-for- map/ (accessed 7.18.19). Consumer Product Safety Commission, 2008. Consumer Product Safety Improvement Act of 2008. Craig, J.A., Ceballos, D.M., Fruh, V., Petropoulos, Z.E., Allen, J.G., Calafat, A.M., Ospina, M., Stapleton, H.M., Hammel, S., Gray, R., Webster, T.F., 2019. Exposure of Nail Salon Workers to Phthalates, Di(2-ethylhexyl) Terephthalate, and Organophosphate Esters: A Pilot Study. Environ. Sci. Technol. 53, 14630–14637. https://doi.org/10.1021/acs.est.9b02474 de Winter-Sorkina, R., Bakker, M.., Wolterink, G., Zielmaker, M.J., 2006. Brominated flame retardants: occurrence, dietary intake and risk assessment [WWW Document]. URL https://www.rivm.nl/bibliotheek/rapporten/320100002.pdf (accessed 6.7.18). Delgado-Saborit, J.M., Stark, C., Harrison, R.M., 2014. Use of a versatile high efficiency multiparallel denuder for the sampling of PAHs in ambient air: Gas and particle phase concentrations, particle size distribution and artifact formation. Environ. Sci. Technol. 48, 499–507. https://doi.org/10.1021/es402937d Dixon, H.M., Scott, R.P., Holmes, D., Calero, L., Kincl, L.D., Waters, K.M., Camann, D.E., Calafat, A.M., Herbstman, J.B., Anderson, K.A., 2018. Silicone wristbands compared with traditional polycyclic aromatic hydrocarbon exposure assessment methods. Anal. Bioanal. Chem. 410, 3059–3071. https://doi.org/10.1007/s00216-018-0992-z Eakin, J.M., Champoux, D., MacEachen, E., 2017. Health and safety in small workplaces: refocusing upstream. Can. J. Public Health 101 Suppl, S29-33. EC, 2018. Waste Electrical & Electronic Equipment (WEEE) [WWW Document]. Eur. Comm. https://doi.org/10.1016/j.geb.2005.03.002 Ekelund, M., Azhdar, B., Gedde, U.W., 2010. Evaporative loss kinetics of di(2- ethylhexyl)phthalate (DEHP) from pristine DEHP and plasticized PVC. Polym. Degrad. Stab. 95, 1789–1793. https://doi.org/10.1016/j.polymdegradstab.2010.05.007 Eriksson, P., Jakobsson, E., Fredriksson, A., 2001. Brominated flame retardants: a novel class of developmental toxicants in our environment? Environ. Health Perspect. 109, 903–908. https://doi.org/10.1289/ehp.01109903 Estill, C.F., Slone, J., Mayer, A., Chen, I.-C., La Guardia, M.J., 2020. Worker exposure to flame retardants in manufacturing, construction and service industries. Environ. Int. 135, 105349. https://doi.org/10.1016/j.envint.2019.105349 European Commission, 2014. COMMUNICATION FROM THE COMMISSION on the finalisation of the restriction process on the four phthalates (DEHP, DBP, BBP and DIBP) under Regulation (EC) No 1907/2006 of the European Parliament and of the Council concerning Registration, Evaluation, Authori. Off. J. Eur. Union 73, 1–4. ExpoStats, 2015. NDExpo – Treatment of non-detects in industrial hygiene samples [WWW Document]. URL http://www.expostats.ca/site/app-local/NDExpo/ (accessed 2.20.20). Factor-Litvak, P., Insel, B., Calafat, A.M., Liu, X., Perera, F., Rauh, V.A., Whyatt, R.M., 2014. Persistent Associations between Maternal Prenatal Exposure to Phthalates on Child IQ at Age 7 Years. PLoS One 9, e114003. 243

https://doi.org/10.1371/journal.pone.0114003 Federman, M.N., Harrington, D.E., Krynski, K.J., 2006. Vietnamese Manicurists: Are Immigrants Displacing Natives or Finding New Nails to Polish? ILR Rev. 59, 302–318. https://doi.org/10.1177/001979390605900207 Fisher, M., Arbuckle, T.E., MacPherson, S., Braun, J.M., Feeley, M., Gaudreau, É., 2019. Phthalate and BPA Exposure in Women and Newborns through Personal Care Product Use and Food Packaging. Environ. Sci. Technol. 53, 10813–10826. https://doi.org/10.1021/acs.est.9b02372 Flanagan, M.E., Seixas, N., Majar, M., Camp, J., Morgan, M., 2003. Silica Dust Exposures During Selected Construction Activities. AIHA J. 64, 319–328. https://doi.org/10.1080/15428110308984823 Fortia, V., Balde, C.P., Kuehr, R., Bel, G., 2020. The Global E-waste Monitor 2020: Quantitites, flows and circular economy potential [WWW Document]. URL https://collections.unu.edu/view/UNU:7737 (accessed 10.13.20). Fraser, A.J., Webster, T.F., McClean, M.D., 2009. Diet Contributes Significantly to the Body Burden of PBDEs in the General U.S. Population. Environ. Health Perspect. 117, 1520– 1525. https://doi.org/10.1289/ehp.0900817 Frazzoli, C., Orisakwe, O.E., Dragone, R., Mantovani, A., 2010. Diagnostic health risk assessment of electronic waste on the general population in developing countries’ scenarios. Environ. Impact Assess. Rev. 30, 388–399. https://doi.org/10.1016/j.eiar.2009.12.004 Frederiksen, M., Stapleton, H.M., Vorkamp, K., Webster, T.F., Jensen, N.M., Sørensen, J.A., Nielsen, F., Knudsen, L.E., Sørensen, L.S., Clausen, P.A., Nielsen, J.B., 2018. Dermal uptake and percutaneous penetration of organophosphate esters in a human skin ex vivo model. Chemosphere 197, 185–192. https://doi.org/10.1016/j.chemosphere.2018.01.032 Fromme, H., Becher, G., Hilger, B., Völkel, W., 2016. Brominated flame retardants - Exposure and risk assessment for the general population. Int. J. Hyg. Environ. Health 219, 1–23. https://doi.org/10.1016/j.ijheh.2015.08.004 Gaspar, F.W., Castorina, R., Maddalena, R.L., Nishioka, M.G., McKone, T.E., Bradman, A., 2014. Phthalate exposure and risk assessment in California child care facilities. Environ. Sci. Technol. 48, 7593–7601. https://doi.org/10.1021/es501189t Gevao, B., Al-Bahloul, M., Al-Ghadban, A.N., Ali, L., Al-Omair, A., Helaleh, M., Al- Matrouk, K., Zafar, J., 2006. Polybrominated diphenyl ethers in indoor air in Kuwait: Implications for human exposure. Atmos. Environ. 40, 1419–1426. https://doi.org/10.1016/j.atmosenv.2005.10.053 Gioia, R., Steinnes, E., Thomas, G.O., Mejier, S.N., Jones, K.C., 2006. Persistent organic pollutants in European background air: derivation of temporal and latitudinal trends. J. Environ. Monit. 8, 700. https://doi.org/10.1039/b604821h Giovanoulis, G., Bui, T., Xu, F., Papadopoulou, E., Padilla-Sanchez, J.A., Covaci, A., Haug, L.S., Cousins, A.P., Magnér, J., Cousins, I.T., de Wit, C.A., 2018. Multi-pathway human exposure assessment of phthalate esters and DINCH. Environ. Int. 112, 115– 126. https://doi.org/10.1016/j.envint.2017.12.016 Glazer, L., Hawkey, A.B., Wells, C.N., Drastal, M., Odamah, K.-A., Behl, M., Levin, E.D., 244

2018. Developmental Exposure to Low Concentrations of Organophosphate Flame Retardants Causes Life-Long Behavioral Alterations in Zebrafish. Toxicol. Sci. 165, 487–498. https://doi.org/10.1093/toxsci/kfy173 Godwin, A.D., 2017. Plasticizers, in: Applied Plastics Engineering Handbook. Elsevier, pp. 533–553. Godwin, A.D., 2010. Uses of Phthalates and Other Plasticizers [WWW Document]. URL https://www.cpsc.gov/s3fs-public/godwin.pdf (accessed 10.21.20). Gong, M., Weschler, C.J., Zhang, Y., 2016. Impact of Clothing on Dermal Exposure to Phthalates: Observations and Insights from Sampling Both Skin and Clothing. Environ. Sci. Technol. 50, 4350–4357. https://doi.org/10.1021/acs.est.6b00113 Goodyer, C.G., Poon, S., Aleksa, K., Hou, L., Atehortua, V., Carnevale, A., Jednak, R., Emil, S., Bagli, D., Dave, S., Hales, B.F., Chevrier, J., 2017. A case-control study of maternal polybrominated diphenyl ether (PBDE) exposure and cryptorchidism in Canadian populations. Environ. Health Perspect. 125, 1–9. https://doi.org/10.1289/EHP522 Gouin, T., Harner, T., Blanchard, P., Mackay, D., 2005. Passive and Active Air Samplers as Complementary Methods for Investigating Persistent Organic Pollutants in the Great Lakes Basin. Environ. Sci. Technol. 39, 9115–9122. https://doi.org/10.1021/es051397f Goverment of Canada, 2017. Phthalates Regulations Règlement sur les phtalates 21–23. Government of Canada, 2019. Cosmetic Ingredient Hotlist [WWW Document]. URL https://www.canada.ca/en/health-canada/services/consumer-product- safety/cosmetics/cosmetic-ingredient-hotlist-prohibited-restricted- ingredients/hotlist.html#tbl1 (accessed 5.4.20). Government of Canada, 2016. Toxic substances list: PBDEs [WWW Document]. Government of Canada, 2012. Regulations Amending the Prohibition of Certain Toxic Substances Regulations, 2012 [WWW Document]. Canada Gaz. Part II. URL http://www.gazette.gc.ca/rp-pr/p2/2016/2016-10-05/pdf/g2-15020.pdf (accessed 2.18.21). Government of Ontario, 2018. Waste management [WWW Document]. URL https://www.ontario.ca/page/waste-management (accessed 12.9.18). Graham, P.R., 1973. Phthalate ester plasticizers—why and how they are used. Environ. Health Perspect. 3, 3–12. https://doi.org/10.1289/ehp.73033 Grant, K., Goldizen, F.C., Sly, P.D., Brune, M.-N., Neira, M., van den Berg, M., Norman, R.E., 2013. Health consequences of exposure to e-waste: a systematic review. Lancet Glob. Heal. 1, e350–e361. https://doi.org/10.1016/S2214-109X(13)70101-3 Gravel, S., Bakhiyi, B., Lavoué, J., Verner, M.-A., Zayed, J., Labreche, F., 2019a. Electronic waste recycling exposure and hormone levels in workers., in: 27th EPICOH International Symposium on Epidemiology in Occupational Health. Wellington, NewZealand. Gravel, S., Diamond, M.L., Jantunen, L.M., Verner, M.-A., Zayed, J., Labrèche, F., 2019b. Is airborne concentration of BDE209 associated with serum concentration in recycling workers?, in: 9th International Symposium on Flame Retardants BFR 2019. Montreal,

245

Canada. Gravel, S., Lavoué, J., Bakhiyi, B., Diamond, M.L., Jantunen, L.M., Lavoie, J., Roberge, B., Verner, M.-A., Zayed, J., Labrèche, F., 2019c. Halogenated flame retardants and organophosphate esters in the air of electronic waste recycling facilities: Evidence of high concentrations and multiple exposures. Environ. Int. 128, 244–253. https://doi.org/10.1016/j.envint.2019.04.027 Gravel, S., Lavoué, J., Bakhiyi, B., Lavoie, J., Roberge, B., Patry, L., Bouchard, M.F., Verner, M., Zayed, J., Labrèche, F., 2020. Multi-exposures to suspected endocrine disruptors in electronic waste recycling workers: Associations with thyroid and reproductive hormones. Int. J. Hyg. Environ. Health 225, 113445. https://doi.org/10.1016/j.ijheh.2019.113445 Guo, J., Lin, K., Deng, J., Fu, X., Xu, Z., 2015. Polybrominated diphenyl ethers in indoor air during waste TV recycling process. J. Hazard. Mater. 283, 439–446. https://doi.org/10.1016/j.jhazmat.2014.09.044 Guo, Y., Kannan, K., 2013. A survey of phthalates and parabens in personal care products from the United States and its implications for human exposure. Environ. Sci. Technol. 47, 14442–14449. https://doi.org/10.1021/es4042034 Guo, Y., Kannan, K., 2011. Comparative Assessment of Human Exposure to Phthalate Esters from House Dust in China and the United States. Environ. Sci. Technol. 45, 3788–3794. https://doi.org/10.1021/es2002106 Hammel, S., Hoffman, K., Webster, T.F., Anderson, K.A., Stapleton, H.M., 2016. Measuring Personal Exposure to Organophosphate Flame Retardants using Silicone Wristbands and Hand Wipes. Environ. Sci. Technol. acs.est.6b00030. https://doi.org/10.1021/acs.est.6b00030 Hammel, S.C., Phillips, A.L., Hoffman, K., Stapleton, H.M., 2018. Evaluating the Use of Silicone Wristbands To Measure Personal Exposure to Brominated Flame Retardants. Environ. Sci. Technol. 52, acs.est.8b03755. https://doi.org/10.1021/acs.est.8b03755 Harley, K.G., Marks, A.R., Chevrier, J., Bradman, A., Sjödin, A., Eskenazi, B., 2010. PBDE Concentrations in Women’s Serum and Fecundability. Environ. Health Perspect. 118, 699–704. https://doi.org/10.1289/ehp.0901450 Harner, T., Bartkow, M., Holoubek, I., Klanova, J., Wania, F., Gioia, R., Moeckel, C., Sweetman, A.J., Jones, K.C., 2006. Passive air sampling for persistent organic pollutants: Introductory remarks to the special issue. Environ. Pollut. 144, 361–364. https://doi.org/10.1016/j.envpol.2005.12.044 Hartmann, P.C., Burgi, D., Giger, W., 2004. Organophosphate flame retardants and plasticizers in indoor air. Chemosphere 57, 781–787. https://doi.org/10.1016/j.chemosphere.2004.08.051 Hays, S.M., Kirman, C.R., 2017. Risk assessment and Biomonitoring Equivalent for 2- ethylhexyl-2,3,4,5 tetrabromobenzoate (TBB) and tetrabromobenzoic acid (TBBA). Regul. Toxicol. Pharmacol. 89, 186–192. https://doi.org/10.1016/j.yrtph.2017.07.022 Hazrati, S., Harrad, S., 2006. Causes of Variability in Concentrations of Polychlorinated Biphenyls and Polybrominated Diphenyl Ethers in Indoor air. Environ. Sci. Technol. 40, 7584–7589. https://doi.org/10.1021/es0617082

246

Heacock, M., Kelly, C.B., Asante, K.A., Birnbaum, L.S., Bergman, Å.L., Bruné, M.-N., Buka, I., Carpenter, D.O., Chen, A., Huo, X., Kamel, M., Landrigan, P.J., Magalini, F., Diaz-Barriga, F., Neira, M., Omar, M., Pascale, A., Ruchirawat, M., Sly, L., Sly, P.D., Van den Berg, M., Suk, W.A., 2015. E-Waste and Harm to Vulnerable Populations: A Growing Global Problem. Environ. Health Perspect. 124, 550–555. https://doi.org/10.1289/ehp.1509699 Heudorf, U., Mersch-Sundermann, V., Angerer, J., 2007. Phthalates: Toxicology and exposure. Int. J. Hyg. Environ. Health 210, 623–634. https://doi.org/10.1016/j.ijheh.2007.07.011 Hill, K.L., Hamers, T., Kamstra, J.H., Willmore, W.G., Letcher, R.J., 2018. Organophosphate triesters and selected metabolites enhance binding of thyroxine to human transthyretin in vitro. Toxicol. Lett. 285, 87–93. https://doi.org/10.1016/j.toxlet.2017.12.030 Hites, R.A., 2004. Polybrominated Diphenyl Ethers in the Environment and in People: A Meta-Analysis of Concentrations. Environ. Sci. Technol. 38, 945–956. https://doi.org/10.1021/es035082g Hoffman, K., Butt, C.M., Webster, T.F., Preston, E. V., Hammel, S.C., Makey, C., Lorenzo, A.M., Cooper, E.M., Carignan, C., Meeker, J.D., Hauser, R., Soubry, A., Murphy, S.K., Price, T.M., Hoyo, C., Mendelsohn, E., Congleton, J., Daniels, J.L., Stapleton, H.M., 2017a. Temporal Trends in Exposure to Organophosphate Flame Retardants in the United States. Environ. Sci. Technol. Lett. 4, 112–118. https://doi.org/10.1021/acs.estlett.6b00475 Hoffman, K., Lorenzo, A., Butt, C.M., Hammel, S.C., Henderson, B.B., Roman, S.A., Scheri, R.P., Stapleton, H.M., Sosa, J.A., 2017b. Exposure to flame retardant chemicals and occurrence and severity of papillary thyroid cancer: A case-control study. Environ. Int. 107, 235–242. https://doi.org/10.1016/j.envint.2017.06.021 Holmes, A.K., Koller, K.R., Kieszak, S.M., Sjodin, A., Calafat, A.M., Sacco, F.D., Varner, D.W., Lanier, A.P., Rubin, C.H., 2014. Case–control study of breast cancer and exposure to synthetic environmental chemicals among Alaska Native women. Int. J. Circumpolar Health 73, 25760. https://doi.org/10.3402/ijch.v73.25760 Hou, R., Xu, Y., Wang, Z., 2016. Review of OPFRs in animals and humans: Absorption, bioaccumulation, metabolism, and internal exposure research. Chemosphere 153, 78– 90. https://doi.org/10.1016/j.chemosphere.2016.03.003 Hubinger, J.C., Havery, D.C., 2006. Analysis of consumer cosmetic products for phthalate esters. J. Cosmet. Sci. 57, 127–37. Hutter, H.-P., Haluza, D., Piegler, K., Hohenblum, P., Fröhlich, M., Scharf, S., Uhl, M., Damberger, B., Tappler, P., Kundi, M., Wallner, P., Moshammer, H., 2013. Semivolatile compounds in schools and their influence on cognitive performance of children. Int. J. Occup. Med. Environ. Health 26, 628–635. https://doi.org/10.2478/s13382-013-0125-z IARC Working Group on the Evaluation of Carcinogenic Risks to Humans, 2013. Some chemicals present in industrial and consumer products, food and drinking-water. IARC Monogr. Eval. Carcinog. Risks Hum. 101, 9–549. Igharo, O.G., Anetor, J.I., Osibanjo, O., Osadolor, H.B., Odazie, E.C., Uche, Z.C., 2018.

247

Endocrine disrupting metals lead to alteration in the gonadal hormone levels in Nigerian e-waste workers. Universa Med. 37, 65. https://doi.org/10.18051/UnivMed.2018.v37.65-74 Iqbal, M., Syed, J.H., Breivik, K., Chaudhry, M.J.I., Li, J., Zhang, G., Malik, R.N., 2017. E- Waste Driven Pollution in Pakistan: The First Evidence of Environmental and Human Exposure to Flame Retardants (FRs) in Karachi City. Environ. Sci. Technol. 51, 13895– 13905. https://doi.org/10.1021/acs.est.7b03159 Jacobson, M.H., Barr, D.B., Marcus, M., Muir, A.B., Lyles, R.H., Howards, P.P., Pardo, L., Darrow, L.A., 2016. Serum polybrominated diphenyl ether concentrations and thyroid function in young children. Environ. Res. 149, 222–230. https://doi.org/10.1016/j.envres.2016.05.022 Jarema, K.A., Hunter, D.L., Shaffer, R.M., Behl, M., Padilla, S., 2015. Acute and developmental behavioral effects of flame retardants and related chemicals in zebrafish. Neurotoxicol. Teratol. 52, 194–209. https://doi.org/10.1016/j.ntt.2015.08.010 Julander, A., Westberg, H., Engwall, M., van Bavel, B., 2005. Distribution of brominated flame retardants in different dust fractions in air from an electronics recycling facility. Sci. Total Environ. 350, 151–160. https://doi.org/10.1016/j.scitotenv.2005.01.015 Kahhat, R., Williams, E., 2012. Materials flow analysis of e-waste: Domestic flows and exports of used computers from the United States. Resour. Conserv. Recycl. 67, 67–74. https://doi.org/10.1016/j.resconrec.2012.07.008 Kammerer, F., 2017. Safe Drinking Water and Toxic Enforcement Act of 1986. Environ. Heal. 1–22. Kile, M.L., Scott, R.P., O’Connell, S.G., Lipscomb, S., MacDonald, M., McClelland, M., Anderson, K.A., Gibson, E.A., Stapleton, H.M., Calero, L., Holmes, D., Burke, K., Martinez, R., Cortes, B., Nematollahi, A., Evans, D., Anderson, K.A., Herbstman, J.B., Fisher, M., Arbuckle, T.E., MacPherson, S., Braun, J.M., Feeley, M., Gaudreau, É., Dixon, H.M., Scott, R.P., Holmes, D., Calero, L., Kincl, L.D., Waters, K.M., Camann, D.E., Calafat, A.M., Herbstman, J.B., Anderson, K.A., Bohlin, P., Jones, K.C., Levin, J.O., Lindahl, R., Strandberg, B., 2019. Using silicone wristbands to evaluate preschool children’s exposure to flame retardants. Chemosphere 219, 567–573. https://doi.org/10.1007/s00216-018-0992-z Kim, E.-H., Jeon, B.-H., Kim, J., Kim, Y.-M., Han, Y., Ahn, K., Cheong, H.-K., 2017. Exposure to phthalates and bisphenol A are associated with atopic dermatitis symptoms in children: a time-series analysis. Environ. Heal. 16, 24. https://doi.org/10.1186/s12940-017-0225-5 Kim, Y.H., Wyrzykowska-Ceradini, B., Touati, A., Krantz, Q.T., Dye, J.A., Linak, W.P., Gullett, B., Gilmour, M.I., 2015. Characterization of Size-Fractionated Airborne Particles Inside an Electronic Waste Recycling Facility and Acute Toxicity Testing in Mice. Environ. Sci. Technol. 49, 11543–11550. https://doi.org/10.1021/acs.est.5b03263 Koniecki, D., Wang, R., Moody, R.P., Zhu, J., 2011. Phthalates in cosmetic and personal care products: Concentrations and possible dermal exposure. Environ. Res. 111, 329– 336. https://doi.org/10.1016/j.envres.2011.01.013 Kuo, L., Cade, S.E., Cullinan, V., Schultz, I.R., 2019. Polybrominated diphenyl ethers (PBDEs) in plasma from E-waste recyclers, outdoor and indoor workers in the Puget

248

Sound, WA region. Chemosphere 219, 209–216. https://doi.org/10.1016/j.chemosphere.2018.12.006 Kuriyama, S.N., Talsness, C.E., Grote, K., Chahoud, I., 2005. Developmental exposure to low-dose PBDE-99: Effects on male fertility and neurobehavior in rat offspring. Environ. Health Perspect. 113, 149–154. https://doi.org/10.1289/ehp.7421 La Guardia, M.J., Hale, R.C., Harvey, E., 2006. Detailed Polybrominated Diphenyl Ether (PBDE) Congener Composition of the Widely Used Penta-, Octa-, and Deca-PBDE Technical Flame-retardant Mixtures. Environ. Sci. Technol. 40, 6247–6254. https://doi.org/10.1021/es060630m Labunska, I., Harrad, S., Wang, M., Santillo, D., Johnston, P., 2014. Human Dietary Exposure to PBDEs Around E-Waste Recycling Sites in Eastern China. Environ. Sci. Technol. 48, 5555–5564. https://doi.org/10.1021/es500241m Lam, J., Lanphear, B.P., Bellinger, D., Axelrad, D.A., McPartland, J., Sutton, P., Davidson, L., Daniels, N., Sen, S., Woodruff, T.J., 2017. Developmental PBDE Exposure and IQ/ADHD in Childhood: A Systematic Review and Meta-analysis. Environ. Health Perspect. 125. https://doi.org/10.1289/EHP1632 Lenters, V., Portengen, L., Rignell-Hydbom, A., Jönsson, B.A.G., Lindh, C.H., Piersma, A.H., Toft, G., Bonde, J.P., Heederik, D., Rylander, L., Vermeulen, R., 2016. Prenatal Phthalate, Perfluoroalkyl Acid, and Organochlorine Exposures and Term Birth Weight in Three Birth Cohorts: Multi-Pollutant Models Based on Elastic Net Regression. Environ. Health Perspect. 124, 365–372. https://doi.org/10.1289/ehp.1408933 Li, F., Xie, Q., Li, X., Li, N., Chi, P., Chen, J., Wang, Z., Hao, C., 2010. Hormone Activity of Hydroxylated Polybrominated Diphenyl Ethers on Human Thyroid Receptor-β: In Vitro and In Silico Investigations. Environ. Health Perspect. 118, 602–606. https://doi.org/10.1289/ehp.0901457 Lilienthal, H., Hack, A., Roth-Härer, A., Grande, S.W., Talsness, C.E., 2006. Effects of developmental exposure to 2,2′,4,4′, 5-pentabromodiphenyl ether (PBDE-99) on sex steroids, sexual development, and sexually dimorphic behavior in rats. Environ. Health Perspect. 114, 194–201. https://doi.org/10.1289/ehp.8391 Lippmann, M., 1998. The 1997 US EPA Standards for Particulate Matter and Ozone, in: Air Pollution and Health. pp. 75–100. https://doi.org/10.1039/9781847550095-00075 Little, J.C., Weschler, C.J., Nazaroff, W.W., Liu, Z., Cohen Hubal, E.A., 2012. Rapid Methods to Estimate Potential Exposure to Semivolatile Organic Compounds in the Indoor Environment. Environ. Sci. Technol. 46, 11171–11178. https://doi.org/10.1021/es301088a Liu, C., Zhang, Y., Weschler, C.J., 2017. Exposure to SVOCs from Inhaled Particles: Impact of Desorption. Environ. Sci. Technol. 51, 6220–6228. https://doi.org/10.1021/acs.est.6b05864 Lu, S.Y., Li, Y.X., Zhang, T., Cai, D., Ruan, J.J., Huang, M.Z., Wang, L., Zhang, J.Q., Qiu, R.L., 2017. Effect of E-waste Recycling on Urinary Metabolites of Organophosphate Flame Retardants and Plasticizers and Their Association with Oxidative Stress. Environ. Sci. Technol. 51, 2427–2437. https://doi.org/10.1021/acs.est.6b05462 Lucas, D., Petty, S.M., Keen, O., Luedeka, B., Schlummer, M., Weber, R., Barlaz, M.,

249

Yazdani, R., Riise, B., Rhodes, J., Nightingale, D., Diamond, M.L., Vijgen, J., Lindeman, A., Blum, A., Koshland, C.P., 2017. Methods of Responsibly Managing End-of-Life Foams and Plastics Containing Flame Retardants: Part I. Environ. Eng. Sci. https://doi.org/10.1089/ees.2017.0147 Ma, J., Addink, R., Yun, S., Cheng, J., Wang, W., Kannan, K., 2009. Polybrominated Dibenzo- p -dioxins/Dibenzofurans and Polybrominated Diphenyl Ethers in Soil, Vegetation, Workshop-Floor Dust, and Electronic Shredder Residue from an Electronic Waste Recycling Facility and in Soils from a Chemical Industrial Complex in Ea. Environ. Sci. Technol. 43, 7350–7356. https://doi.org/10.1021/es901713u MacIntosh, D.L., Minegishi, T., Fragala, M.A., Allen, J.G., Coghlan, K.M., Stewart, J.H., McCarthy, J.F., 2012. Mitigation of building-related polychlorinated biphenyls in indoor air of a school. Environ. Heal. A Glob. Access Sci. Source 11, 1–10. https://doi.org/10.1186/1476-069X-11-24 Mäkinen, M.S.E., Mäkinen, M.R.A., Koistinen, J.T.B., Pasanen, A.-L., Pasanen, P.O., Kalliokoski, P.J., Korpi, A.M., 2009. Respiratory and Dermal Exposure to Organophosphorus Flame Retardants and Tetrabromobisphenol A at Five Work Environments. Environ. Sci. Technol. 43, 941–947. https://doi.org/10.1021/es802593t Marek, R.F., Thorne, P.S., Herkert, N.J., Awad, A.M., Hornbuckle, K.C., 2017. Airborne PCBs and OH-PCBs Inside and Outside Urban and Rural U.S. Schools. Environ. Sci. Technol. 51, 7853–7860. https://doi.org/10.1021/acs.est.7b01910 Meeker, J.D., Cooper, E.M., Stapleton, H.M., Hauser, R., 2013. Exploratory analysis of urinary metabolites of phosphorus-containing flame retardants in relation to markers of male reproductive health. Endocr. Disruptors 1, e26306. https://doi.org/10.4161/endo.26306 Meeker, J.D., Stapleton, H.M., 2009. House Dust Concentrations of Organophosphate Flame Retardants in Relation to Hormone Levels and Semen Quality Parameters. Environ. Health Perspect. 118, 318–323. https://doi.org/10.1289/ehp.0901332 Meironyté, D., Norén, K., Bergman, Å., 1999. Analysis of polybrominated diphenyl ethers in swedish human milk. A time-related trend study, 1972–1997. J. Toxicol. Environ. Heal. - Part A 58, 329–341. https://doi.org/10.1080/009841099157197 Melymuk, L., Robson, M., Helm, P.A., Diamond, M.L., 2011. Evaluation of passive air sampler calibrations: Selection of sampling rates and implications for the measurement of persistent organic pollutants in air. Atmos. Environ. 45, 1867–1875. https://doi.org/10.1016/j.atmosenv.2011.01.011 Mendelsohn, E., Hagopian, A., Hoffman, K., Butt, C.M., Lorenzo, A., Congleton, J., Webster, T.F., Stapleton, H.M., 2016. Nail polish as a source of exposure to triphenyl phosphate. Environ. Int. 86, 45–51. https://doi.org/10.1016/j.envint.2015.10.005 Moeckel, C., Harner, T., Nizzetto, L., Strandberg, B., Lindroth, A., Jones, K.C., 2009. Use of depuration compounds in passive air samplers: Results from active sampling-supported field deployment, potential uses, and recommendations. Environ. Sci. Technol. 43, 3227–3232. https://doi.org/10.1021/es802897x Morrison, G.C., Weschler, C.J., Bekö, G., Koch, H.M., Salthammer, T., Schripp, T., Toftum, J., Clausen, G., 2016. Role of clothing in both accelerating and impeding dermal absorption of airborne SVOCs. J. Expo. Sci. Environ. Epidemiol. 26, 113–118.

250

https://doi.org/10.1038/jes.2015.42 Muenhor, D., Harrad, S., Ali, N., Covaci, A., 2010. Brominated flame retardants (BFRs) in air and dust from electronic waste storage facilities in Thailand. Environ. Int. 36, 690– 698. https://doi.org/10.1016/j.envint.2010.05.002 Nalli, S., Horn, O.J., Grochowalski, A.R., Cooper, D.G., Nicell, J.A., 2006. Origin of 2- ethylhexanol as a VOC. Environ. Pollut. 140, 181–185. https://doi.org/10.1016/j.envpol.2005.06.018 National Academies of Sciences Engineering and Medicine, 2017. Application of Systematic Review Methods in an Overall Strategy for Evaluating Low-Dose Toxicity from Endocrine Active Chemicals. The National Academies Press, Washington,DC. https://doi.org/10.17226/24758 Nguyen, L. V., Diamond, M.L., Venier, M., Stubbings, W.A., Romanak, K., Bajard, L., Melymuk, L., Jantunen, L.M., Arrandale, V.H., 2019. Exposure of Canadian electronic waste dismantlers to flame retardants. Environ. Int. 129, 95–104. https://doi.org/10.1016/j.envint.2019.04.056 Nguyen, L. V., Gravel, S., Labrèche, F., Bakhiyi, B., Verner, M.A., Zayed, J., Jantunen, L.M., Arrandale, V.H., Diamond, M.L., 2020. Can Silicone Passive Samplers be Used for Measuring Exposure of e-Waste Workers to Flame Retardants? Environ. Sci. Technol. 54, 15277–15286. https://doi.org/10.1021/acs.est.0c05240 North, M.L., Takaro, T.K., Diamond, M.L., Ellis, A.K., 2014. Effects of phthalates on the development and expression of allergic disease and asthma. Ann. Allergy, Asthma Immunol. 112, 496–502. https://doi.org/10.1016/j.anai.2014.03.013 NTP, 1991. Toxicology and Carcinogenesis Studies of TRIS(2- CHLOROETHYL)PHOSPHATE (CAS NO. 115-96-8) in F344 / N Rats. Natl. Toxicol. Program Tech. Rep. Ser. 409, 1–171. O’Connell, S.G., Kincl, L.D., Anderson, K.A., 2014. Silicone Wristbands as Personal Passive Samplers. Environ. Sci. Technol. 48, 3327–3335. https://doi.org/10.1021/es405022f Okeme, J.O., Nguyen, L. V., Lorenzo, M., Dhal, S., Pico, Y., Arrandale, V.H., Diamond, M.L., 2018a. Polydimethylsiloxane (silicone rubber) brooch as a personal passive air sampler for semi-volatile organic compounds. Chemosphere 208, 1002–1007. https://doi.org/10.1016/j.chemosphere.2018.05.196 Okeme, J.O., Nguyen, L. V., Lorenzo, M., Dhal, S., Pico, Y., Arrandale, V.H., Diamond, M.L., 2018b. Polydimethylsiloxane (silicone rubber) brooch as a personal passive air sampler for semi-volatile organic compounds. Chemosphere 208, 1002–1007. https://doi.org/10.1016/j.chemosphere.2018.05.196 Okeme, J.O., Parnis, J.M., Poole, J., Diamond, M.L., Jantunen, L.M., 2016a. Polydimethylsiloxane-air partition ratios for semi-volatile organic compounds by GC- based measurement and COSMO-RS estimation: Rapid measurements and accurate modelling. Chemosphere 156, 204–211. https://doi.org/10.1016/j.chemosphere.2016.04.094 Okeme, J.O., Rodgers, T.F.M., Jantunen, L.M., Diamond, M.L., 2018c. Examining the Gas- Particle Partitioning of Organophosphate Esters: How Reliable Are Air Measurements?

251

Environ. Sci. Technol. 52, 13834–13844. https://doi.org/10.1021/acs.est.8b04588 Okeme, J.O., Saini, A., Yang, C., Zhu, J., Smedes, F., Klánová, J., Diamond, M.L., 2016b. Calibration of polydimethylsiloxane and XAD-Pocket passive air samplers (PAS) for measuring gas- and particle-phase SVOCs. Atmos. Environ. 143, 202–208. https://doi.org/10.1016/j.atmosenv.2016.08.023 Okeme, J.O., Yang, C., Abdollahi, A., Dhal, S., Harris, S.A., Jantunen, L.M., Tsirlin, D., Diamond, M.L., 2018d. Passive air sampling of flame retardants and plasticizers in Canadian homes using PDMS, XAD-coated PDMS and PUF samplers. Environ. Pollut. 239, 109–117. https://doi.org/10.1016/j.envpol.2018.03.103 Okonski, K., Degrendele, C., Melymuk, L., Landlová, L., Kukučka, P., Vojta, Š., Kohoutek, J., Čupr, P., Klánová, J., 2014. Particle Size Distribution of Halogenated Flame Retardants and Implications for Atmospheric Deposition and Transport. Environ. Sci. Technol. 48, 14426–14434. https://doi.org/10.1021/es5044547 Ospina, M., Jayatilaka, N.K., Wong, L.-Y., Restrepo, P., Calafat, A.M., 2018. Exposure to organophosphate flame retardant chemicals in the U.S. general population: Data from the 2013–2014 National Health and Nutrition Examination Survey. Environ. Int. 110, 32–41. https://doi.org/10.1016/j.envint.2017.10.001 Park, S.A., Gwak, S., Choi, S., 2014. Assessment of occupational symptoms and chemical exposures for nail salon technicians in Daegu City, Korea. J. Prev. Med. Public Heal. 47, 169–176. https://doi.org/10.3961/jpmph.2014.47.3.169 Pawar, G., 2017. Exploring the utility of 3-D skin models to evaluate trans-dermal uptake of flame retardants from indoor dust and consumer product. University of Birmingham. Pelucchi, C., Negri, E., Gallus, S., Boffetta, P., Tramacere, I., La Vecchia, C., 2009. Long- term particulate matter exposure and mortality: a review of European epidemiological studies. BMC Public Health 9, 453. https://doi.org/10.1186/1471-2458-9-453 Percy, Z., Vuong, A.M., Ospina, M., Calafat, A.M., La Guardia, M.J., Xu, Y., Hale, R.C., Dietrich, K.N., Xie, C., Lanphear, B.P., Braun, J.M., Cecil, K.M., Yolton, K., Chen, A., 2020. Organophosphate esters in a cohort of pregnant women: Variability and predictors of exposure. Environ. Res. 184, 109255. https://doi.org/10.1016/j.envres.2020.109255 Pettersson-Julander, A., van Bavel, B., Engwall, M., Westberg, H., 2004. Personal air sampling and analysis of polybrominated diphenyl ethers and other bromine containing compounds at an electronic recycling facility in Sweden. J. Environ. Monit. 6, 874. https://doi.org/10.1039/b408381d Philippat, C., Bennett, D., Calafat, A.M., Picciotto, I.H., Xu, F., Giovanoulis, G., Van Waes, S., Padilla-Sanchez, J.A., Papadopoulou, E., Magnér, J., Haug, L.S., Neels, H., Covaci, A., 2016. Exposure to select phthalates and phenols through use of personal care products among Californian adults and their children. Environ. Res. 50, 7752–7760. https://doi.org/10.1021/acs.est.6b00246 Pinson, A., Bourguignon, J.P., Parent, A.S., 2016. Exposure to endocrine disrupting chemicals and neurodevelopmental alterations. Andrology 4, 706–722. https://doi.org/10.1111/andr.12211 Pope III, C.A., 2002. Lung Cancer, Cardiopulmonary Mortality, and Long-term Exposure to

252

Fine Particulate Air Pollution. JAMA 287, 1132. https://doi.org/10.1001/jama.287.9.1132 Quach, T., Gunier, R., Tran, A., Von Behren, J., Doan-Billings, P.-A., Nguyen, K.-D., Okahara, L., Lui, B.Y.-B., Nguyen, M., Huynh, J., Reynolds, P., 2011. Characterizing Workplace Exposures in Vietnamese Women Working in California Nail Salons. Am. J. Public Health 101, S271–S276. https://doi.org/10.2105/AJPH.2010.300099 Radke, E.G., Braun, J.M., Meeker, J.D., Cooper, G.S., Agency, U.S.E.P., States, U., 2018. Phthalate exposure and male reproductive outcomes : A systematic review of the human epidemiological evidence. Environ. Int. 121, 764–793. https://doi.org/10.1016/j.envint.2018.07.029 Rakkestad, K.E., Dye, C.J., Yttri, K.E., Holme, J.A., Hongslo, J.K., Schwarze, P.E., Becher, R., 2007. Phthalate levels in Norwegian indoor air related to particle size fraction. J. Environ. Monit. 9, 1419. https://doi.org/10.1039/b709947a Rengasamy, S., Eimer, B., Shaffer, R.E., 2010. Simple respiratory protection - Evaluation of the filtration performance of cloth masks and common fabric materials against 20-1000 nm size particles. Ann. Occup. Hyg. 54, 789–798. https://doi.org/10.1093/annhyg/meq044 Richman, K.E., Butt, C.M., Young, C.J., 2018. Size-resolved particle measurements of polybrominated diphenyl ethers indoors: Implications for sources and human exposure. Environ. Toxicol. Chem. 37, 481–490. https://doi.org/10.1002/etc.3981 Robinson, B.H., 2009. E-waste: An assessment of global production and environmental impacts. Sci. Total Environ. 408, 183–191. https://doi.org/10.1016/j.scitotenv.2009.09.044 Rodes, C.E., Kamens, R.M., Wiener, R.W., 1991. The Significance and Characteristics of the Personal Activity Cloud on Exposure Assessment Measurements for Indoor Contaminants. Indoor Air 1, 123–145. https://doi.org/10.1111/j.1600-0668.1991.03- 12.x Romanak, K.A., Wang, S., Stubbings, W.A., Hendryx, M., Venier, M., Salamova, A., 2019. Analysis of brominated and chlorinated flame retardants, organophosphate esters, and polycyclic aromatic hydrocarbons in silicone wristbands used as personal passive samplers. J. Chromatogr. A 1588, 41–47. https://doi.org/10.1016/j.chroma.2018.12.041 Romero-Franco, M., Hernández-Ramírez, R.U., Calafat, A.M., Cebrián, M.E., Needham, L.L., Teitelbaum, S., Wolff, M.S., López-Carrillo, L., 2011. Personal care product use and urinary levels of phthalate metabolites in Mexican women. Environ. Int. 37, 867– 871. https://doi.org/10.1016/j.envint.2011.02.014 Rosenberg, C., Hämeilä, M., Tornaeus, J., Säkkinen, K., Puttonen, K., Korpi, A., Kiilunen, M., Linnainmaa, M., Hesso, A., 2011. Exposure to Flame Retardants in Electronics Recycling Sites. Ann. Occup. Hyg. 55, 658–665. https://doi.org/10.1093/annhyg/mer033 Saini, A., Okeme, J.O., Goosey, E., Diamond, M.L., 2015. Calibration of two passive air samplers for monitoring phthalates and brominated flame-retardants in indoor air. Chemosphere 137, 166–173. https://doi.org/10.1016/j.chemosphere.2015.06.099 Saini, A., Okeme, J.O., Mark Parnis, J., McQueen, R.H., Diamond, M.L., 2016. From air to

253

clothing: characterizing the accumulation of semi-volatile organic compounds to fabrics in indoor environments. Indoor Air. https://doi.org/10.1111/ina.12328 SCHETTLER, T., 2006. Human exposure to phthalates via consumer products. Int. J. Androl. 29, 134–139. https://doi.org/10.1111/j.1365-2605.2005.00567.x Schreder, E.D., Uding, N., La Guardia, M.J., 2016. Inhalation a significant exposure route for chlorinated organophosphate flame retardants. Chemosphere 150, 499–504. https://doi.org/10.1016/j.chemosphere.2015.11.084 Schwartz, J., Neas, L.M., 2000. Fine particles are more strongly associated than coarse particleswithacute respiratoryhealtheffectsinschoolchildren. Epidemiology 11, 6–10. Shi, T., Chen, S.-J., Luo, X.-J., Zhang, X.-L., Tang, C.-M., Luo, Y., Ma, Y.-J., Wu, J.-P., Peng, X.-Z., Mai, B.-X., 2009. Occurrence of brominated flame retardants other than polybrominated diphenyl ethers in environmental and biota samples from southern China. Chemosphere 74, 910–916. https://doi.org/10.1016/j.chemosphere.2008.10.047 Shoeib, M., Harner, T., 2002. Characterization and Comparison of Three Passive Air Samplers for Persistent Organic Pollutants. Environ. Sci. Technol. 36, 4142–4151. https://doi.org/10.1021/es020635t Sindiku, O., Babayemi, J., Osibanjo, O., Schlummer, M., Schluep, M., Watson, A., Weber, R., 2015. Polybrominated diphenyl ethers listed as Stockholm Convention POPs, other brominated flame retardants and heavy metals in e-waste polymers in Nigeria. Environ. Sci. Pollut. Res. 22, 14489–14501. https://doi.org/10.1007/s11356-014-3266-0 Singh, M., Thind, P.S., John, S., 2018. Health risk assessment of the workers exposed to the heavy metals in e-waste recycling sites of Chandigarh and Ludhiana, Punjab, India. Chemosphere 203, 426–433. https://doi.org/10.1016/j.chemosphere.2018.03.138 Sjödin, A., Carlsson, H., Thuresson, K., Sjölin, S., Bergman, Å., Östman, C., 2001. Flame Retardants in Indoor Air at an Electronics Recycling Plant and at Other Work Environments. Environ. Sci. Technol. 35, 448–454. https://doi.org/10.1021/es000077n Slotkin, T.A., Skavicus, S., Stapleton, H.M., Seidler, F.J., 2017. Brominated and organophosphate flame retardants target different neurodevelopmental stages, characterized with embryonic neural stem cells and neuronotypic PC12 cells. Toxicology 390, 32–42. https://doi.org/10.1016/j.tox.2017.08.009 Smil, V., 2017. PLANET OF THE COWS. IEEE Spectr. 54, 24. Snedeker, S.M., 2014. Toxicants in Food Packaging and Household Plastics, Molecular and Integrative Toxicology. Springer London, London. https://doi.org/10.1007/978-1-4471- 6500-2 Staaf, T., Ostman, C., 2005. Organophosphate triesters in indoor environments. J. Environ. Monit. 7, 883–887. https://doi.org/10.1039/b506631j Stapleton, H.M., Allen, J.G., Kelly, S.M., Konstantinov, A., Klosterhaus, S., Watkins, D., McClean, M.D., Webster, T.F., 2008a. Alternate and New Brominated Flame Retardants Detected in U.S. House Dust. Environ. Sci. Technol. 42, 6910–6916. https://doi.org/10.1021/es801070p Stapleton, H.M., Kelly, S.M., Allen, J.G., McClean, M.D., Webster, T.F., Stapleton, M.H., Kelly, S.M., Allen, J.G., McClean, M.D., Webster, T.F., Stapleton, H.M., Kelly, S.M.,

254

Allen, J.G., McClean, M.D., Webster, T.F., 2008b. Measurement of Polybrominated Diphenyl Ethers on Hand Wipes: Estimating Exposure from Hand-to-Mouth Contact. Environ. Sci. Technol. 42, 3329–3334. https://doi.org/10.1021/es7029625 Statistics Canada, 2016. EnviroStats Trash talking: Dealing with Canadian household e- waste. [WWW Document]. URL http://www.statcan.gc.ca/pub/16-002- x/2016001/article/14570-eng.htm (accessed 7.15.18). Stubbings, W.A., Nguyen, L. V., Romanak, K., Jantunen, L., Melymuk, L., Arrandale, V., Diamond, M.L., Venier, M., 2019a. Flame retardants and plasticizers in a Canadian waste electrical and electronic equipment (WEEE) dismantling facility. Sci. Total Environ. 675, 594–603. https://doi.org/10.1016/j.scitotenv.2019.04.265 Stubbings, W.A., Nguyen, L. V., Romanak, K., Jantunen, L., Melymuk, L., Arrandale, V., Diamond, M.L., Venier, M., 2019b. Flame retardants and plasticizers in a Canadian waste electrical and electronic equipment (WEEE)dismantling facility. Sci. Total Environ. 675, 594–603. https://doi.org/10.1016/j.scitotenv.2019.04.265 Suzuki, G., Tue, N.M., Malarvannan, G., Sudaryanto, A., Takahashi, S., Tanabe, S., Sakai, S., Brouwer, A., Uramaru, N., Kitamura, S., Takigami, H., 2013. Similarities in the Endocrine-Disrupting Potencies of Indoor Dust and Flame Retardants by Using Human Osteosarcoma (U2OS) Cell-Based Reporter Gene Assays. Environ. Sci. Technol. 47, 2898–2908. https://doi.org/10.1021/es304691a Swedish Chemicals Inspectorate, 2003. Brominated flame retardants – Prospects of a national ban. KemI Report 4/03. Takigami, H., Suzuki, G., Hirai, Y., Sakai, S., 2008. Transfer of brominated flame retardants from components into dust inside television cabinets. Chemosphere 73, 161–169. https://doi.org/10.1016/j.chemosphere.2008.06.032 Tansel, B., 2017. From electronic consumer products to e-wastes: Global outlook, waste quantities, recycling challenges. Environ. Int. 98, 35–45. https://doi.org/10.1016/j.envint.2016.10.002 Thuresson, K., Höglund, P., Hagmar, L., Sjödin, A., Bergman, Å., Jakobsson, K., 2006. Apparent Half-Lives of Hepta- to Decabrominated Diphenyl Ethers in Human Serum as Determined in Occupationally Exposed Workers. Environ. Health Perspect. 114, 176– 181. https://doi.org/10.1289/ehp.8350 Tran, T.M., Kannan, K., 2015. Occurrence of Phthalate Diesters in Particulate and Vapor Phases in Indoor Air and Implications for Human Exposure in Albany, New York, USA. Arch. Environ. Contam. Toxicol. 68, 489–499. https://doi.org/10.1007/s00244- 015-0140-0 Tran, T.M., Le, H.T., Minh, T.B., Kannan, K., 2017. Occurrence of phthalate diesters in indoor air from several Northern cities in Vietnam, and its implication for human exposure. Sci. Total Environ. 601–602, 1695–1701. https://doi.org/10.1016/j.scitotenv.2017.06.016 Traore, I.T., Gravel, S., Diamond, M.L., Jantunen, L., Nguyen, L.V., Yang, C., Bernstein, S., Zayed, J., Labrèche, F., Verner, M.-A., 2018. Urinary Metabolites of Organophosphate Esters (OPEs) in Electronic Waste Recycling Workers from the Province of Quebec, Canada. ISEE Conf. Abstr. 2018, isesisee.2018.P01.3100. https://doi.org/10.1289/isesisee.2018.P01.3100

255

Tromp, P.C., Beeltje, H., Okeme, J.O., Vermeulen, R., Pronk, A., Diamond, M.L., 2019. Calibration of polydimethylsiloxane and polyurethane foam passive air samplers for measuring semi volatile organic compounds using a novel exposure chamber design. Chemosphere 227, 435–443. https://doi.org/10.1016/j.chemosphere.2019.04.043 Tue, N.M., Takahashi, S., Suzuki, G., Isobe, T., Viet, P.H., Kobara, Y., Seike, N., Zhang, G., Sudaryanto, A., Tanabe, S., 2013. Contamination of indoor dust and air by polychlorinated biphenyls and brominated flame retardants and relevance of non-dietary exposure in Vietnamese informal e-waste recycling sites. Environ. Int. 51, 160–167. https://doi.org/10.1016/j.envint.2012.11.006 U.S.Bureau of Labor, 2020. Occupational Outlook Handbook [WWW Document]. UCLA Labor Center, 2018. Nail Files: A study of nail salon workers and industry in United States. UNEP, 2019. A New Circular Vision for Electronics Time for a Global Reboot 24. UNEP, 2016. GEO-6 North America Regional Assessment [WWW Document]. URL http://wedocs.unep.org/bitstream/handle/20.500.11822/7611/GEO_North_America_201 611.pdf?sequence=1&isAllowed=y (accessed 6.27.18). UNEP, 2010. Technical review of the implications of recycling commercial pentabromodiphenyl ether and commercial octabromodi- phenyl ether. UNEP, 2008. Report of the Persistent Organic Pollutants Review Committee on the work of its fourth meeting. United States Department of Labor, 2017. Occupational Employment and Wages, May 2017 [WWW Document]. URL https://www.bls.gov/oes/current/oes395092.htm#st US EPA, 2018a. IRIS Assessments [WWW Document]. URL https://cfpub.epa.gov/ncea/iris2/atoz.cfm (accessed 6.27.18). US EPA, 2018b. Chemistry Dashboard [WWW Document]. URL https://comptox.epa.gov/dashboard (accessed 6.27.18). US EPA, 2018c. 2,2’,4,4’,5-Pentabromodiphenyl ether (BDE-99) [WWW Document]. URL https://cfpub.epa.gov/ncea/iris2/chemicalLanding.cfm?substance_nmbr=1008 (accessed 6.27.18). US EPA, 2011. September 2011 EXPOSURE FACTORS HANDBOOK : 2011 EDITION National Center for Environmental Assessment Office of Research and Development U . S . Environmental Protection Agency Washington , DC 20460 Exposure Factors Handbook. Exposure. USEPA, 2020. CHEMICALS KNOWN TO THE STATE TO CAUSE CANCER OR REPRODUCTIVE TOXICITY January 3, 2020. Veen, I. Van Der, Boer, J. De, 2012. Chemosphere Phosphorus flame retardants : Properties , production , environmental occurrence , toxicity and analysis. Chemosphere 88, 1119– 1153. https://doi.org/10.1016/j.chemosphere.2012.03.067 Venier, M., Ma, Y., Hites, R.A., 2012. Brominated flame retardants in the Great Lakes atmosphere. Environ. Sci. Technol. 46, 8653–8660. https://doi.org/dx.doi.org/10.1021/es3015919

256

Viberg, H., Fredriksson, A., Eriksson, P., 2004. Investigations of strain and/or gender differences in developmental neurotoxic effects of polybrominated diphenyl ethers in mice. Toxicol. Sci. 81, 344–353. https://doi.org/10.1093/toxsci/kfh215 Viberg, H., Fredriksson, A., Jakobsson, E., Orn, U., Erikson, P., 2003. Neurobehavioral derangements in adult mice receiving decabrominated diphenyl ether (PBDE 209) during a defined period of neonatal brain development. Toxicol. Sci. 76, 112–120. https://doi.org/10.1093/toxsci/kfg210 Vojta, Š., Bečanová, J., Melymuk, L., Komprdová, K., Kohoutek, J., Kukučka, P., Klánová, J., 2017. Screening for halogenated flame retardants in European consumer products, building materials and wastes. Chemosphere 168, 457–466. https://doi.org/10.1016/j.chemosphere.2016.11.032 Vuong, A.M., Braun, J.M., Webster, G.M., Thomas Zoeller, R., Hoofnagle, A.N., Sjödin, A., Yolton, K., Lanphear, B.P., Chen, A., 2018. Polybrominated diphenyl ether (PBDE) exposures and thyroid hormones in children at age 3 years. Environ. Int. 117, 339–347. https://doi.org/10.1016/j.envint.2018.05.019 Vuong, A.M., Yolton, K., Xie, C., Webster, G.M., Sjödin, A., Braun, J.M., Dietrich, K.N., Lanphear, B.P., Chen, A., 2017. Childhood polybrominated diphenyl ether (PBDE) exposure and neurobehavior in children at 8 years. Environ. Res. 158, 677–684. https://doi.org/10.1016/j.envres.2017.07.028 Vykoukalová, M., Venier, M., Vojta, Š., Melymuk, L., Bečanová, J., Romanak, K., Prokeš, R., Okeme, J.O., Saini, A., Diamond, M.L., Klánová, J., 2017. Organophosphate esters flame retardants in the indoor environment. Environ. Int. 106, 97–104. https://doi.org/10.1016/j.envint.2017.05.020 Wallace, L., 2000. Correlations of personal exposure to particles with outdoor air measurements: A review of recent studies. Aerosol Sci. Technol. 32, 15–25. https://doi.org/10.1080/027868200303894 Wallner, P., Kundi, M., Hohenblum, P., Scharf, S., Hutter, H., 2016. Phthalate Metabolites, Consumer Habits and Health Effects. Int. J. Environ. Res. Public Health 13, 717. https://doi.org/10.3390/ijerph13070717 Wan, Y., Diamond, M.L., Siegel, J.A., 2020. Elevated Concentrations of Semivolatile Organic Compounds in Social Housing Multiunit Residential Building Apartments. Environ. Sci. Technol. Lett. 7, 191–197. https://doi.org/10.1021/acs.estlett.0c00068 Wang, D.G., Alaee, M., Byer, J.D., Brimble, S., Pacepavicius, G., 2013. Human health risk assessment of occupational and residential exposures to dechlorane plus in the manufacturing facility area in China and comparison with e-waste recycling site. Sci. Total Environ. 445–446, 329–336. https://doi.org/10.1016/j.scitotenv.2012.12.059 Wang, S., Romanak, K.A., Stubbings, W.A., Arrandale, V.H., Hendryx, M., Diamond, M.L., Salamova, A., Venier, M., 2019. Silicone wristbands integrate dermal and inhalation exposures to semi-volatile organic compounds (SVOCs). Environ. Int. 132, 105104. https://doi.org/10.1016/j.envint.2019.105104 Wang, Y., Peris, A., Rifat, M.R., Ahmed, S.I., Aich, N., Nguyen, L. V., Urík, J., Eljarrat, E., Vrana, B., Jantunen, L.M., Diamond, M.L., 2020. Measuring exposure of e-waste dismantlers in Dhaka Bangladesh to organophosphate esters and halogenated flame retardants using silicone wristbands and T-shirts. Sci. Total Environ. 720, 137480.

257

https://doi.org/10.1016/j.scitotenv.2020.137480 Wei, G.-L., Li, D.-Q., Zhuo, M.-N., Liao, Y.-S., Xie, Z.-Y., Guo, T.-L., Li, J.-J., Zhang, S.- Y., Liang, Z.-Q., 2015. Organophosphorus flame retardants and plasticizers: Sources, occurrence, toxicity and human exposure. Environ. Pollut. 196, 29–46. https://doi.org/10.1016/j.envpol.2014.09.012 Wei, W., Bonvallot, N., Gustafsson, Å., Raffy, G., Glorennec, P., Krais, A., Ramalho, O., Le Bot, B., Mandin, C., 2018. Bioaccessibility and bioavailability of environmental semi- volatile organic compounds via inhalation: A review of methods and models. Environ. Int. 113, 202–213. https://doi.org/10.1016/j.envint.2018.01.024 Wei, W., Mandin, C., Ramalho, O., 2017. Reactivity of Semivolatile Organic Compounds with Hydroxyl Radicals, Nitrate Radicals, and Ozone in Indoor Air. Int. J. Chem. Kinet. 49, 506–521. https://doi.org/10.1002/kin.21093 Weschler, C.J., Nazaroff, W.W., 2014. Dermal Uptake of Organic Vapors Commonly Found in Indoor Air. Environ. Sci. Technol. 48, 1230–1237. https://doi.org/10.1021/es405490a Weschler, C.J., Nazaroff, W.W., 2012. SVOC exposure indoors: Fresh look at dermal pathways. Indoor Air. https://doi.org/10.1111/j.1600-0668.2012.00772.x Weschler, C.J., Nazaroff, W.W., 2010. SVOC partitioning between the gas phase and settled dust indoors. Atmos. Environ. 44, 3609–3620. https://doi.org/10.1016/j.atmosenv.2010.06.029 Weschler, C.J., Nazaroff, W.W., 2008. Semivolatile organic compounds in indoor environments. Atmos. Environ. 42, 9018–9040. https://doi.org/10.1016/j.atmosenv.2008.09.052 Whitman, W.G., 1962. The two film theory of gas absorption. Int. J. Heat Mass Transf. 5, 429–433. https://doi.org/10.1016/0017-9310(62)90032-7 Wielsøe, M., Kern, P., Bonefeld-Jørgensen, E.C., 2017. Serum levels of environmental pollutants is a risk factor for breast cancer in Inuit: a case control study. Environ. Heal. 16, 56. https://doi.org/10.1186/s12940-017-0269-6 Wong, C.S.C., Duzgoren-Aydin, N.S., Aydin, A., Wong, M.H., 2007. Evidence of excessive releases of metals from primitive e-waste processing in Guiyu, China. Environ. Pollut. 148, 62–72. https://doi.org/10.1016/j.envpol.2006.11.006 Wu, C.-C., Bao, L.-J., Tao, S., Zeng, E.Y., 2016. Dermal Uptake from Airborne Organics as an Important Route of Human Exposure to E-Waste Combustion Fumes. Environ. Sci. Technol. 50, 6599–6605. https://doi.org/10.1021/acs.est.5b05952 Xu, F., Zhang, G., Wang, J., Zhang, W., Liu, L., Lin, K., 2015. Polybrominated diphenyl ethers in air and fallouts from an e-waste polluted region in southeast China: insight into levels, compositional profiles, and seasonal variation. Environ. Sci. Pollut. Res. 22, 19676–19686. https://doi.org/10.1007/s11356-015-5168-1 Xu, Y., Cohen Hubal, E.A., Clausen, P.A., Little, J.C., 2009. Predicting Residential Exposure to Phthalate Plasticizer Emitted from Vinyl Flooring: A Mechanistic Analysis. Environ. Sci. Technol. 43, 2374–2380. https://doi.org/10.1021/es801354f Xu, Y., Cohen Hubal, E.A., Little, J.C., 2010. Predicting residential exposure to phthalate plasticizer emitted from vinyl flooring: Sensitivity, uncertainty, and implications for

258

biomonitoring. Environ. Health Perspect. 118, 253–258. https://doi.org/10.1289/ehp.0900559 Yang, C., Harris, S.A., Jantunen, L.M., Kvasnicka, J., Nguyen, L. V., Diamond, M.L., 2020a. Phthalates: Relationships between Air, Dust, Electronic Devices, and Hands with Implications for Exposure. Environ. Sci. Technol. 54, acs.est.0c00229. https://doi.org/10.1021/acs.est.0c00229 Yang, C., Harris, S.A., Jantunen, L.M., Siddique, S., Kubwabo, C., Tsirlin, D., Latifovic, L., Fraser, B., St-Jean, M., De La Campa, R., You, H., Kulka, R., Diamond, M.L., 2018. Are cell phones an indicator of personal exposure to organophosphate flame retardants and plasticizers? Environ. Int. in press, 1–13. https://doi.org/10.1016/j.envint.2018.10.021 Yang, C., Jílková, S.R., Melymuk, L., Harris, S.A., Jantunen, L.M., Pertili, J., Winn, L., Diamond, M.L., 2020b. Are We Exposed to Halogenated Flame Retardants from both Primary and Secondary Sources? Environ. Sci. Technol. Lett. 7, 585–593. https://doi.org/10.1021/acs.estlett.0c00268 Young, A.S., Allen, J.G., Kim, U.-J.J., Seller, S., Webster, T.F., Kannan, K., Ceballos, D.M., 2018. Phthalate and Organophosphate Plasticizers in Nail Polish: Evaluation of Labels and Ingredients. Environ. Sci. Technol. 52, acs.est.8b04495. https://doi.org/10.1021/acs.est.8b04495 Zabiegała, B., Zygmunt, B., Przyk, E., Namieśnik, J., 2000. Applicability of silicone membrane passive samplers for monitoring of indoor air quality. Anal. Lett. 33, 1361– 1372. https://doi.org/10.1080/00032710008543127 Zeng, X., Yang, C., Chiang, J.F., Li, J., 2017. Innovating e-waste management: From macroscopic to microscopic scales. Sci. Total Environ. 575, 1–5. https://doi.org/10.1016/j.scitotenv.2016.09.078 Zhang, H., Yolton, K., Webster, G.M., Sjödin, A., Calafat, A.M., Dietrich, K.N., Xu, Y., Xie, C., Braun, J.M., Lanphear, B.P., Chen, A., 2016. Prenatal PBDE and PCB Exposures and Reading, Cognition, and Externalizing Behavior in Children. Environ. Health Perspect. 125, 7–16. https://doi.org/10.1289/EHP478 Zhang, X., Diamond, M.L., Robson, M., Harrad, S., 2011. Sources, emissions, and fate of polybrominated diphenyl ethers and polychlorinated biphenyls indoors in Toronto, Canada. Environ. Sci. Technol. 45, 3268–3274. https://doi.org/10.1021/es102767g Zhang, Z., Sun, Z.-Z., Xiao, X., Zhou, S., Wang, X.X.-C., Gu, J., Qiu, L.-L., Zhang, X.-H., Xu, Q., Zhen, B., Wang, X.X.-C., Wang, S.-L., 2013a. Mechanism of BDE209-induced impaired glucose homeostasis based on gene microarray analysis of adult rat liver. Arch. Toxicol. 87, 1557–1567. https://doi.org/10.1007/s00204-013-1059-8 Zhang, Z., Zhang, X., Sun, Z., Dong, H., Qiu, L., Gu, J., Zhou, J., Wang, X., Wang, S.L., 2013b. Cytochrome P450 3A1 Mediates 2,2′,4,4′-Tetrabromodiphenyl Ether-Induced Reduction of Spermatogenesis in Adult Rats. PLoS One 8. https://doi.org/10.1371/journal.pone.0066301 Zheng, X., Xu, F., Chen, K., Zeng, Y., Luo, X., Chen, S., Mai, B., Covaci, A., 2015. Flame retardants and organochlorines in indoor dust from several e-waste recycling sites in South China: Composition variations and implications for human exposure. Environ. Int. 78, 1–7. https://doi.org/10.1016/j.envint.2015.02.006

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Zota, A.R., Rudel, R.A., Morello-Frosch, R.A., Brody, J.G., 2008. Elevated House Dust and Serum Concentrations of PBDEs in California: Unintended Consequences of Furniture Flammability Standards? Environ. Sci. Technol. 42, 8158–8164. https://doi.org/10.1021/es801792z

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Appendix 2: Supporting Information for Chapter 3

-1 Table A3.1. Full names, CAS numbers, molecular weights (g mol ) and log KOA values, calculated using EPISuite’s Koawinn module, of target compounds for analysis of silicone passive samplers in Chapter 3.

Acronym Full name CAS number Molecular Log Koa weight Novel halogenated flame retardants (NHFRs) ATE Tribromophenyl allyl ether 3278-89-5 371 8.6 PBBZ Pentabromobenzene 608-90-2 473 9.1 PBT Pentabromotoluene 87-83-2 487 9.6 PBEB Pentabromoetheyl benzene 85-22-3 501 10 HBB Hexabromobenzene 87-82-1 552 9.1 EHTBB Ethylhexyl-tetrabromobenzoate 183658-27-7 550 12.3 BEHTBP Bis(2-ethlyhexyl) tetrabromophthalate 26040-51-7 706 16.9 OBIND Octabromotrimethylphenyl indane 1084889-51-9 867 18.3 DBDPE Decabromodiphenylethane 84852-53-9 971 19.2 s-DP Dechlorane Plus (syn isomers) 13560-89-9 654 14.8 a-DP Dechlorane Plus (anti isomers) 13560-89-9 654 14.8 Polybrominated diphenyl ethers (PBDEs) BDE-47 2,2',4,4'-Tetrabromodiphenyl ether 5436-43-1 486 10.7 BDE-49 2,2',4,5'-Tetrabromodiphenyl ether 243982-82-3 486 10.7 BDE-66 2,3',4,4'-Tetrabromodiphenyl ether 189084-61-5 486 10.7 BDE-71 2,3',4',6-Tetrabromodiphenyl ether 189084-62-6 486 10.7 BDE-85 2,2',3,4,4'-Pentabromodiphenyl ether 182346-21-0 565 11.2 BDE-99 2,2',4,4',5-Pentabromodiphenyl ether 60348-60-6 565 11.2 BDE-138 2,2',3,4,4',5'-Hexabromodiphenyl ether 182677-30-1 644 13.3 BDE-154 2,2',4,4',5,6'-Hexabromodiphenyl ether 207122-15-4 644 13.3 BDE-183 2,2',3,4,4',5',6-Heptabromodiphenyl ether 207122-16-5 722 14.6 BDE-190 2,2',3',4,4',5',6-Heptabromodiphenyl ether 189084-68-2 722 14.6 BDE-209 Decabromodiphenyl ether 1163-19-5 959 18.4 Organophosphate esters (OPEs) TCEP Tris(2-chloroethyl) phosphate 115-96-8 286 5.3 TCIPP Tris(2-chloroisopropyl) phosphate 13674-84-5 328 8.2 TPhP Triphenyl phosphate 115-86-6 326 8.5 EHDPP 2-Ethylhexyl diphenyl phosphate 1241-94-7 362 8.4 ToCP Tri-o-cresyl phosphate 78-30-8 368 9.6 TmCP Tri-m-cresyl phosphate 563-04-2 368 8.8 TpCP Tri-p-cresyl phosphate 78-32-0 368 8.8 2IPPDPP 2-isopropylphenyl diphenyl phosphate 64532-94-1 368 11.7 4IPPDPP 4-isopropylphenyl diphenyl phosphate 55864-04-5 368 11.7 TBOEP Tris(2-butoxyethyl)phosphate 78-51-3 398 13.1 24DIPPDPP 2,4-diisopropylphenyl diphenyl phosphate 58570-87-9 410 12.8 B2IPPPP Bis(2-isopropylphenyl) phenyl phosphate 69500-29-4 410 12.8 TDClPP Tris(1,3-dichloro-2-propyl) phosphate 13674-87-8 431 10.6 TEHP Tris(2-ethylhexyl) phosphate 78-42-2 435 15.0 T2IPPP Tris(2-isopropyl phenyl) phosphate 26967-76-0 453 14.0

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A3.1 – Sample preparation

OSHA Versatile Sampler (OVS) tubes, which consist of a GFF and a PUF/XAD-2/PUF sandwich (Sigma Aldrich, Canada), were pre-cleaned with methanol followed by a mixture of

Acetone : Hexane : DCM, (1:1:1), and then dried under a flow of nitrogen. The tubes were wrapped in aluminium foil and kept in pre-cleaned amber glass vials (VWR International,

Canada) at 4 oC until use.

Silicone brooches, wristbands and armbands were pre-cleaned using a Soxhlet apparatus with ethyl acetate for 3 days. Then all silicone samplers were soak in methanol for at least 1 day to rinse off ethyl acetate before deployment. The aluminum housings, staples and wires were washed with soap, rinsed with deionized water, and then sonicated in methanol.

Brooches, armbands and wristbands were assembled and then stored in pre-cleaned 500mL and 250mL pre-cleaned amber jars (VWR International, Canada) at 4 oC until deployment.

A3.2 – Extraction methods

Extraction of active air and personal passive samplers

Prior to extraction, all samples and blanks were spiked with the surrogate standards to

13 13 assess extraction efficiencies. C6-PBBz and C6-HBB were used as surrogate standards for

NHFRs (AccuStandards Inc., USA), F-BDE-100, F-BDE-154, F-BDE-208 for PBDEs

13 (AccuStandard Inc., USA) and d12-TCEP, d15-TDCiPP, C18-TPhP for OPEs (Wellington

Laboratories, Canada).

The GFF and PUF/XAD-2/PUF sandwich in the OVS tubes were extracted together to give a bulk air concentration. Extraction was done using a Supelco vacuum chamber

(Bellefonte, PA, USA). After spiking surrogates standards, OVS tubes were extracted with 15 mL of Acetone : DCM : Hexane (1:1:1) mixture. The extracts were concentrated to 0.5 ml,

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transferred to gas chromatography vials, blown down to near dryness under a gentle stream of nitrogen, and reconstituted to approximately 0.5 mL in isooctane.

Silicone brooches, wristbands and armbands were extracted by shaking and soaking with 30 mL of acetonitrile using Wrist Action Shaker (Burrell Corporation, USA). The extracts were reduced to 0.5 mL by using a Turbovap (Biotage, USA). The particles from the extracts were filtered by using 17 mm Teflon syringe filters (Thermo Scientific, USA) with pore size of 0.2 µm. Extracts were then stored in gas chromatography vials and blown down to near dryness under a gentle stream of nitrogen and reconstituted to approximately 0.5 mL in isooctane.

Internal standards (Mirex for OPEs and BDE-118 for NFRs and PBDEs) were added to all extracts for volume correction and time reference before analysis.

Extraction of urinary and plasma samples

Details of extraction methods for PBDEs in blood plasma and OPE urinary metabolites were described in Gravel et al. (2020) The methods are briefly described below.

Full names of targeted urinary OPE metabolites and PBDEs in plasma are listed in

Table A3.4. For urinary analysis of OPE metabolites (except from DPhP and pOH-DPhP), a volume of 250 µL urine samples was spiked with labeled internal standards (BDCiPP-d12,

13 13 BDBrPrP-d10, BDCliPrP-d10, BmTyP-d14, DiBP-d14, DPhP- C2, 4-MLBF- C4, and 4- methylumbelliferone glucuronide). The extracts were then hydrolyzed with 250 µL of β- glucuronidase enzyme solution 1 % (from E.coli K12, Roche Diagnostics, Hoffmann-La

Roche Limited; Ontario, Canada) in acetate buffer 1 M for 90 minutes at 37°C and acidified with hydrochloric acid 10 %. Afterwards, samples were extracted with ethyl acetate (3 mL) using a liquid-liquid extraction. The extracts were evaporated completely and reconstituted in

100 µL of acetonitrile 40 % solution.

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DPhP and pOH-DPhP were analyzed separately from the other OPE metabolites.

13 Volumes of 250 µL of urine were spiked with labeled internal standards (DPhP- C2 and pOH-

DPhP-d5) and hydrolyzed with 250 µL of β-glucuronidase enzyme solution 1 % (from E.coli

K12, Roche Diagnostics, Hoffmann-La Roche Limited; Ontario, Canada) in an acetate buffer

1 M over 90 minutes at 37°C. The extracts were then acidified with formic acid 5 % before solid phase extraction (SPE) with SiliaPrepX WAX cartridges (3 mL, 100 mg; SiliCycle,

Quebec, Canada). The SPE cartridges were conditioned with NH4OH 0.5 %, followed by formic acid 1 %. The extracts were then washed with water and methanol, and elution of the analytes was done with 2 mL of NH4OH 0.5 % in methanol. The extracts were evaporated completely and reconstituted in 250 µL of acetonitrile 5 % solution.

The tubes for PBDE analysis were centrifuged within 4h of collection for isolation of the plasma. Plasma was then transferred into 2 mL silane pre-treated chromatography vials

(Supelco® Analytical, Pa, USA), then frozen at -20 °C until analysis.

A3.3 - Instrumental analysis

Extracts (except from urinary OPE metabolites) were analyzed on an Agilent

6890N/5973 or 5975 gas chromatograph/ inert mass selective detector (GC-MSD) system.

Electron capture negative ionization (ECNI) mode was used for NHFRs, PBDEs and TDCIPP whereas electron impact ionization (EI) mode was used for other OPEs. Ions monitored are listed in Table A3.3.

GC separation of the NHFRs, PBDEs and TDCIPP was achieved using a DB-5 MS column (Agilent Technologies, 15 m x 0.25 mm i.d. x 0.25 µm film thickness) with the following temperature program: initial at 100°C hold for 1.5 min, 12°C/min to 250°C, then

6°C/min to 290°C, hold for 3 min, and 60°C/min to 320°C, hold for 12 min. Post run at 310

°C for 2 mins.

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Separation of OPE compounds (except TDCIPP) was performed using a DB-5 MS column (Agilent Technologies, 30 m x 0.25 mm i.d. x 0.25 µm film thickness). The oven temperature program was: initial at 75°C hold for 3 min, 15°C/min to 195°C and hold for 5 min, 3°C/min to 255°C and hold for 1 min, 20°C/min to 315°C and hold for 10 min. Post run at 310 °C for 2 mins.

Details of instrument analysis for PBDEs in plasma and OPE urinary metabolites were described by Gravel et al. (2020).

A3.4 - Quality Assurance and Quality Control

Field blanks of silicone brooches (n = 4) and silicone wristbands/armbands (n = 4) were collected, one per sampling day. Additionally, one lab blank and one matrix spike were analyzed per batch of silicone brooches, wristbands/armband samples (in total five for each matrix). The masses of the target compounds in each sample were compared to the mean mass in the field blanks on a matrix specific basis. Blank levels were treated as follows, as described by Saini et al. (2015): no correction if the blank level was < 5% of the measured level; blank level was subtracted from the measured level if the blank level was 5 - 35 % of the measured level; the sample was discarded if the blank level was >35 % of the measured level. No blank correction was necessary in this study. Instrument detection limits (IDLs) were calculated by the ratio of signal to noise of 10:1 for the low concentrations of individual compounds in calibration standards (Table A3.3). Here, since all FR concentrations in field blanks were lower than limit of detection, method detection limits (MDLs) were calculated by normalizing IDLs by the average of sampling time and surface area of silicone samplers. Surrogate standard recoveries and matrix spike recoveries were considered satisfactory if they were between 50 –

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150 % and no recovery correction was applied. Surrogate recoveries were considered satisfactory when two out of three recoveries were within the range 50-150 %.

Details of QA/QC for PBDEs in plasma and OPE urinary metabolites were described by Gravel et al. (2020).

A3.5 – Theory of passive air sampling for silicone brooch

The theory of gas-phase uptake by a passive air sampler (PAS) has been described by

Shoeib and Harner (2002) and Bartkow et al. (2005) and is based on the two-film model of

Whitman (1962) with the assumption of a uniform distribution of chemical within the PAS.

Briefly, the accumulation of a gas-phase chemical from air in the PAS (e.g., silicone brooch) through molecular diffusion is equivalent to the rate of uptake minus the rate of loss of the

PAS for that chemical as described in the following equation:

푑푀푃퐴푆 퐶푃퐴푆 퐶푃퐴푆 = 푘퐴𝑖푟퐴푃퐴푆 (퐶퐴𝑖푟 − ) (퐶퐴𝑖푟 − ) 푑푡 퐾푃퐴푆−퐴𝑖푟 퐾푃퐴푆−퐴𝑖푟

where 푀푃퐴푆 (ng) is the mass of chemical collected by the PAS; t (s) is the PAS deployment

-3 time; 퐶푃퐴푆 and 퐶퐴𝑖푟 (ng m ) are the concentrations of a chemical in the PAS and air

-1 2 respectively; 푘퐴𝑖푟 (cm s ) is the air-side mass transfer coefficient; 퐴푃퐴푆 (cm ) is the exposed surface area of the PAS; and 퐾푃퐴푆−퐴𝑖푟 (dimensionless) is the PAS-air partition coefficient that can be determined from 퐾푂퐴 (Shoeib and Harner, 2002). For SVOCs which have a high 퐾푂퐴 (

7 >10 ) the term 퐶푃퐴푆/퐾푃퐴푆−퐴𝑖푟 is very small when the uptake of chemical in the PAS is in the linear uptake phase with low 퐶푃퐴푆. Thus, the accumulation of SVOCs in the linear uptake phase is independent of 퐾푂퐴 or log 퐾푂퐴.

According to Shoeib and Harner (2002) the uptake of a PAS continues through the linear and curvi-linear sampling phases until reaching the equilibrium partitioning phase

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between air and the PAS. The linear uptake phase is the ideal region where the loss rate of a compound from PAS is considered insignificant relative to the uptake rate, so that the uptake rate (or sampling rate) is constant over time. Moreover, the uptake of gas-phase compounds in the PAS is mainly driven by air-side mass transfer rate (i.e. 푘퐴𝑖푟) which is an inverse of resistance posed by the air-side boundary layer.

However, PAS can collect chemicals in both gas and particles phases (Melymuk et al.,

2011; Okeme et al., 2018a, 2016b). Thus, PAS sampling rates should be derived based on bulk

(gas + particle) air concentrations (Melymuk et al., 2011; Okeme et al., 2018a, 2016b). Hence, the sampling rate of the silicone brooch in this study was derived by using the time specific method (Bohlin et al., 2010b; Pernilla Bohlin et al., 2014) with the derived-concentrations in bulk air from time integrated active sampling and mass of compounds accumulated on the brooch.

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Figure A3.1: Worker wearing OSHA Versatile Sampler (OVS) sampler, silicone brooch and wristband.

Figure A3.2: Worker wearing OSHA Versatile Sampler (OVS) sampler, silicone brooch and armband. Note that this worker is wearing high cut-proof sleeves that prevented the use of a wristband

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Table A3.2. Median concentrations of selected FRs in active air samplers and wristbands from the 2nd and 3rd sampling facilities where workers worn wristbands directly on their wrists and on the top of the protective suit’s cuff, respectively. Difference in median concentrations were calculated by dividing the median concentrations from the 3rd facility by median concentrations from 2nd facility. Comparisons between air and wristbands concentrations from two facilities were completed by using Wilcoxon rank sum test. Numbers in bold are statistically significant with p-value < 0.05.

Active air samplers Wristbands Difference in Difference in Median p- Median p- median median concentrations value concentrations value concentrations concentrations 2nd 3rd 2nd 3rd facility facility facility facility (n=5) (n=23) (n=5) (n=23) ATE 0.2 0.4 2 0.07 0.1 0.1 1 0.81 PBBz 0.2 0.4 2 <0.01 0.1 0.1 2 0.04 PBT 0.1 0.3 4 <0.01 0.0 0.1 2 0.01 HBB 1.2 5.4 4 <0.01 0.4 2.5 6 0.02 BEHTBP 6.0 6.7 1 0.90 176 7.7 0 0.01 s-DP 2.7 8.4 3 <0.01 10 4.9 0 0.41 a-DP 2.7 15 5 <0.01 14 8.3 1 0.86 OBIND 11.8 49 4 <0.01 0.5 12 25 <0.01 BDE-47 0.8 1.9 3 <0.01 1.6 0.9 1 0.08 BDE-49 0.4 1.6 5 <0.01 0.3 0.5 2 0.01 BDE-66 0.2 0.4 2 <0.01 0.3 0.5 2 0.01 BDE-99 1.3 3.7 3 <0.01 2.2 1.5 1 0.09 BDE-154 0.4 1.1 3 <0.01 0.5 0.4 1 0.41 BDE-183 2.1 16 8 <0.01 5.7 5.2 1 1 BDE-209 13.6 4150 305 <0.01 41 3150 77 <0.01 TCEP 130 100 1 0.2 66 35 1 0.2 TCIPP 109 525 5 <0.01 71 62 1 0.77 TDCIPP 9.8 18 2 0.4 124 27 0.2 0.01 TPhP 20 203 10 <0.01 50 63 1 0.34 EHDPP 2.8 11 4 0.04 16 3.4 0.2 0.02 TBOEP 50 89 2 <0.01 264 211 1 0.21 TmCP 2.1 8.7 4 <0.01 4.7 2.4 1 0.02 T2IPPP 1.3 1.1 1 0.4 0.0 0.2 18 0.52 ∑23 FRs 368 5,220 847 3,600

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Table A3.3. Monitored quantifier and qualifier ions for target compounds for analysis of silicone passive samplers.

MDL for MDL for Acronym Target ion Qualifier ions brooch wristbands (ng dm-2 h-1) (ng dm-2 h-1) Novel halogenated flame retardants (NHFRs) ATE 79 81 290 0.02 0.02 PBBZ 472 470 394 0.003 0.003 PBT 79 81 486 0.02 0.02 PBEB 79 81 502 500 0.01 0.01 HBB 550 470 472 0.01 0.01 EHTBB 79 81 357 359 0.10 0.11 BEHTBP 79 515 1.11 1.15 OBIND 79 81 0.29 0.30 DBDPE 81 79 7.73 7.97 s-DP 652 654 656 0.01 0.01 a-DP 654 652 656 0.01 0.01 Polybrominated diphenyl ethers (PBDEs) BDE-47 79 81 0.09 0.10 BDE-49 79 81 0.07 0.08 BDE-66 81 79 0.03 0.03 BDE-71 79 81 0.02 0.02 BDE-85 79 81 0.11 0.11 BDE-99 79 81 0.03 0.03 BDE-138 81 79 0.07 0.08 BDE-154 79 81 484 564 0.02 0.02 BDE-183 81 79 484 562 0.07 0.07 BDE-190 79 81 0.07 0.07 BDE-209 489 81 79 0.18 0.19 Organophosphate esters (OPEs) TCEP 249 251 0.08 0.09 TCIPP 99 125 0.01 0.01 TPhP 326 325 0.003 0.003 EHDPP 251 250 0.01 0.01 ToCP 368 367 0.003 0.003 TmCP 368 367 0.003 0.003 TpCP 368 367 0.003 0.003 2IPPDPP 118 251 368 0.01 0.01 4IPPDPP 353 368 0.01 0.01 TBOEP 57 85 0.42 0.43 24DIPPDPP 145 160 410 0.01 0.01 B2IPPPP 118 510 251 0.01 0.01 TDClPP 317 319 0.01 0.01 TEHP 99 113 0.01 0.01 T2IPPP 118 452 0.01 0.01 Average sampling time = 8h; brooch surface area = 0.495 dm2; wristband surface area = 0.48 dm2

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Table A3.4. Acronyms, monitored target and qualifier ions for surrogate and internal standards for analysis of silicone passive samplers.

Compounds Full name Target Qualifier ions ion Surrogate standards 13C6-PBBZ Pentabromo[13C6]benzene 480 482 400 13 C6-HBB Hexabromo[13C6]benzene 562 529 482 F-BDE-100 3-Fluoro-2,2',4,4',6- 502 423 - pentabromodiphenyl ether F-BDE-154 3'-Fluoro-2,2',4,4',5,6'- 81 79 502 hexabromodiphenyl ether F-BDE-208 4'-Fluoro- 2,2',3,3',4,5,5',6,6'- 489 487 81 nonabromodiphenyl ether d12-TCEP Tris(2-chloroethyl) 261 251 205 phosphate-d12 d15-TDCIPP Tris(1,3-dichloro-2-propyl) 329 327 331 phosphate-d15 13 13 C18-TPhP C18-Triphenyl phosphate 343 344 342 Internal standards BDE-118 2,3’,4,4’,5- 81 79 - Pentabromodiphenyl ether Mirex 1,2,3,4,5,5,6,7,8,9,10,10- dodecachloropentacyclo[5.3 272 274 270 .0.02,6.03,9.04,8]decane

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Table A3.5. Full names and detection frequencies (DF as %) of PBDEs in plasma and OPE metabolites in urine samples collected from workers in three Québec e-waste facilities.

Biomarkers Acronym DF (%) PBDEs (Parent compound in serum) 2,4,4'-Tribromodiphenyl ether BDE-28 5 2,2',4,4'-Tetrabromodiphenyl ether BDE-47 44 2,2',4,4',5-Pentabromodiphenyl ether BDE-99 26 2,2',4,4',5,6'-Hexabromodiphenyl ether BDE-154 9 2,2',3,4,4',5',6-Heptabromodiphenyl ether BDE-183 40 2,2',3',4,4',5',6-Heptabromodiphenyl ether BDE-190 44 Decabromodiphenyl ether BDE-209 93 OPEs (Metabolites in urine) Acronym DF (%) Known OPE parent compounds

Bis (2-chloroethyl) carboxymethyl phosphate BCECMP 72 Tris(2-chloroethyl) phosphate (TCEP) Bis (2-chloroethyl) 2-hydroxyethyl phosphate BCEHEP 51 Tris(2-chloroethyl) phosphate (TCEP) Bis (2-chloroisopropyl) carboxyethyl phosphate BCiPCEP 86 Tris(1-chloro-2-propyl) phosphate (TCIPP) Bis (1-chloro-2-propyl) 1-hydroxy-2-propyl BCiPHiPP 100 Tris(1-chloro-2-propyl) phosphate (TCIPP) phosphate Bis (1,3-dichloropropyl) phosphate BDCiPP 74 Tris(1,3-dichloro-2-propyl) phosphate (TDCIPP) Diphenyl phosphate DPhP 95 Triphenyl phosphate (TPhP) 2-Tert-butylphenyl diphenyl phosphate (BPDP) Resorcinol bis(diphenyl phosphate) (PBDPP) Ethylhexyldiphenyl phosphate (EHDPP) Isopropyl triphenyl phosphate (iP-TPhP) Para-hydroxyphenyl phenyl phosphate pOH-DPhP 77 Triphenyl phosphate (TPhP) Bis (2-butoxyehyl) phosphate BBOEP 2 Tris(2-butoxyethyl)phosphate (TBOEP)

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Table A3.6. Detection frequencies (in %) of 37 target FRs in silicone brooches, wristbands and armbands. Brooches Wristbands Brooches Armbands paired with (n = 28) paired with (n = 9) wristbands armbands (n = 28) (n = 9) Halogenated flame retardants (HFRs) ATE 96 100 22 89 PBBZ 100 100 100 100 PBT 86 96 100 100 PBEB 89 86 100 100 HBB 96 100 100 100 EHTBB 100 96 100 100 BEHTBP 100 93 100 100 OBIND 86 93 100 100 DBDPE 82 82 100 100 s-DP 100 100 100 100 a-DP 100 100 100 100 Polybrominated diphenyl ethers (PBDEs) BDE-47 96 96 100 100 BDE-49 82 96 100 100 BDE-66 86 96 100 100 BDE-71 93 96 100 100 BDE-85 21 36 33 89 BDE-99 100 100 100 100 BDE-138 7 29 0 78 BDE-154 100 100 100 100 BDE-183 100 100 100 100 BDE-190 89 68 100 44 BDE-209 100 100 100 100 Organophosphate esters (OPEs) TCEP 96 96 100 78 TCIPP 100 93 100 67 TDCIPP 100 100 100 100 TPhP 100 96 100 78 EHDPP 100 96 100 78 TBOEP 100 96 100 78 TEHP 4 21 0 0 ToCP 0 7 0 0 TmCP 100 93 100 78 TpCP 43 75 59 67 T2IPPP 71 61 100 67 2IPPDPP 96 46 100 42 B2IPPPP 96 50 89 9 4IPPDPP 57 43 22 29 24DIPPDP 89 64 100 6

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Table A3.7. Correlations between concentrations (ng dm-2 h-1 for silicone brooches, wristbands and armbands) of FRs with detection frequencies >60% in paired sample matrices as indicated by Spearman’s correlation coefficients (rho). Numbers in bold indicate a statistically significant correlation with p-value < 0.05.

Brooches vs Brooches vs Acronym Wristbands Armbands Novel halogenated flame retardants (NHFRs) ATE 0.35 0.25 PBBZ 0.38 0.43 PBT 0.37 -0.2 HBB 0.47 -0.32 s-DP 0.64 0.75 a-DP 0.18 0.25 BEHTBP 0.64 0.63 OBIND 0.37 0.02 Polybrominated diphenyl ethers (PBDEs) BDE-47 0.26 0.02 BDE-49 0.48 0.07 BDE-66 0.37 0.15 BDE-99 0.22 -0.35 BDE-154 0.23 0.60 BDE-183 0.37 0.65 BDE-209 0.69 0.68 Organophosphate esters (OPES) TCEP 0.09 -0.55 TCIPP 0.12 0.15 TPhP 0.45 -0.37 EHDPP 0.17 0.47 TmCP 0.05 -0.57 TBOEP 0.31 0.43 TDClPP 0.21 0.02 T2IPPP 0.65 -0.03

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Figure A3.3. Log-transformed BDE-209 in serum and months worked in the e-waste recycling industry.

Spearman’s rho = -0.27 p-value > 0.05

Table A3.8. Spearman’s rank correlation coefficients (rho) and p-values (p) for levels of OPE urinary metabolites and numbers of months workers worked in the e-waste recycling industry.

Numbers of months worked in the e-waste recycling industry OPE urinary metabolites Spearman’s rho p-value BCECMP -0.35 0.02 BCiPCEP -0.14 0.36 BCiPHiPP 0.03 0.85 BDCiPP -0.11 0.46 DPhP -0.24 0.12 pOH-DPhP -0.23 0.14

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(a) (b)

Figure A3.4: Log-transformed OPE metabolites in urine versus (a) log-transformed OPE concentrations in brooches and (b) log-transformed BDE-209 in wristband.

3 Table A3.9. Average and standard deviation (SD) of sampling rates, 푅푠, of the brooch (m day-1 or m3 day-1 dm-2) for selected FRs. We propose the average values as the generic sampling rate for the brooch under conditions reported here. SD Average SD Average Compounds (m3 day-1) (m3 day-1 dm- (m3 day-1 dm- (m3 day-1) 2) 2) Novel halogenated flame retardants (HFRs) s-DP 9.1 5.4 18 11 a-DP 7.6 4.2 15 8.5 Polybrominated diphenyl ethers (PBDEs) BDE-99 5.5 4.8 11 10 BDE-209 11 11 23 23 Organophosphate esters (OPEs) TCIPP 2.8 7.2 5.7 14 TPhP 8.8 18 18 36 TDCIPP 20 15 40 30 Average (Generic sampling rate) 9.3 19 SD 5.4 11

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Table A3.10. Estimation of 푡25, the length (in day) of the linear uptake phase of silicone 3 brooch (t25) for individual compounds (see Equation 3). 푉푆𝑖푙𝑖푐표푛푒 퐵푟표표푐ℎ (m ) is the volume of ′ a silicone brooch; 퐾푆𝑖푙𝑖푐표푛푒 −퐴𝑖푟, 퐸푥푝 (dimensionless) is the silicone-to-air partition 3 -1 coefficient, and 푅푠 (m day ) is the sampling rate of the silicone brooch for an individual ′ compound. Values of 퐾푆𝑖푙𝑖푐표푛 퐵푟표표푐ℎ−퐴𝑖푟, 퐸푥푝 were taken from Okeme et al. (2016a).

′ ′ Compounds 푽푺풊풍풊풄풐풏풆 푩풓풐풐풄풉 풍풐품 푲푺풊풍풊풄풐풏 푩풓풐풐풄풉−푨풊풓, 푬풙풑 푲푺풊풍풊풄풐풏 푩풓풐풐풄풉−푨풊풓, 푬풙풑 푹풔 t25 (m3) (m3 day-1) (day) Novel halogenated flame retardants (HFRs) s-DP 49.5 x 10-6 8.56 108.56 9.1 2,740 a-DP 49.5 x 10-6 9.51 109.51 7.6 29,200 Polybrominated diphenyl ethers (PBDEs) BDE-99 49.5 x 10-6 8.77 108.77 5.5 7,350 BDE-209 49.5 x 10-6 NA NA 11 NA Organophosphate esters (OPEs) TCIPP 49.5 x 10-6 7.87 107.87 2.8 1,820 TPhP 49.5 x 10-6 8.45 108.45 8.8 2,200 TDCIPP 49.5 x 10-6 8.24 108.24 20 596 NA: Not available

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Canada. Gravel, S., Lavoué, J., Bakhiyi, B., Diamond, M.L., Jantunen, L.M., Lavoie, J., Roberge, B., Verner, M.-A., Zayed, J., Labrèche, F., 2019c. Halogenated flame retardants and organophosphate esters in the air of electronic waste recycling facilities: Evidence of high concentrations and multiple exposures. Environ. Int. 128, 244–253. https://doi.org/10.1016/j.envint.2019.04.027 Gravel, S., Lavoué, J., Bakhiyi, B., Lavoie, J., Roberge, B., Patry, L., Bouchard, M.F., Verner, M., Zayed, J., Labrèche, F., 2020. Multi-exposures to suspected endocrine disruptors in electronic waste recycling workers: Associations with thyroid and reproductive hormones. Int. J. Hyg. Environ. Health 225, 113445. https://doi.org/10.1016/j.ijheh.2019.113445 Guo, J., Lin, K., Deng, J., Fu, X., Xu, Z., 2015. Polybrominated diphenyl ethers in indoor air during waste TV recycling process. J. Hazard. Mater. 283, 439–446. https://doi.org/10.1016/j.jhazmat.2014.09.044 Guo, Y., Kannan, K., 2013. A survey of phthalates and parabens in personal care products from the United States and its implications for human exposure. Environ. Sci. Technol. 47, 14442–14449. https://doi.org/10.1021/es4042034 Guo, Y., Kannan, K., 2011. Comparative Assessment of Human Exposure to Phthalate Esters from House Dust in China and the United States. Environ. Sci. Technol. 45, 3788–3794. https://doi.org/10.1021/es2002106 Hammel, S., Hoffman, K., Webster, T.F., Anderson, K.A., Stapleton, H.M., 2016. Measuring Personal Exposure to Organophosphate Flame Retardants using Silicone Wristbands and Hand Wipes. Environ. Sci. Technol. acs.est.6b00030. https://doi.org/10.1021/acs.est.6b00030 Hammel, S.C., Phillips, A.L., Hoffman, K., Stapleton, H.M., 2018. Evaluating the Use of Silicone Wristbands To Measure Personal Exposure to Brominated Flame Retardants. Environ. Sci. Technol. 52, acs.est.8b03755. https://doi.org/10.1021/acs.est.8b03755 Harley, K.G., Marks, A.R., Chevrier, J., Bradman, A., Sjödin, A., Eskenazi, B., 2010. PBDE Concentrations in Women’s Serum and Fecundability. Environ. Health Perspect. 118, 699–704. https://doi.org/10.1289/ehp.0901450 Harner, T., Bartkow, M., Holoubek, I., Klanova, J., Wania, F., Gioia, R., Moeckel, C., Sweetman, A.J., Jones, K.C., 2006. Passive air sampling for persistent organic pollutants: Introductory remarks to the special issue. Environ. Pollut. 144, 361–364. https://doi.org/10.1016/j.envpol.2005.12.044 Hartmann, P.C., Burgi, D., Giger, W., 2004. Organophosphate flame retardants and plasticizers in indoor air. Chemosphere 57, 781–787. https://doi.org/10.1016/j.chemosphere.2004.08.051 Hays, S.M., Kirman, C.R., 2017. Risk assessment and Biomonitoring Equivalent for 2- ethylhexyl-2,3,4,5 tetrabromobenzoate (TBB) and tetrabromobenzoic acid (TBBA). Regul. Toxicol. Pharmacol. 89, 186–192. https://doi.org/10.1016/j.yrtph.2017.07.022 Hazrati, S., Harrad, S., 2006. Causes of Variability in Concentrations of Polychlorinated Biphenyls and Polybrominated Diphenyl Ethers in Indoor air. Environ. Sci. Technol. 40, 7584–7589. https://doi.org/10.1021/es0617082

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Appendix 3: Supporting Information for Chapter 4

A4.1 – Sample preparation

OSHA Versatile Sampler (OVS) tubes, which consist of a GFF and a PUF/XAD-2/PUF sandwich (Sigma Aldrich, Canada), were pre-cleaned with methanol followed by a mixture of

Acetone : Hexane : DCM, (1:1:1), and then dried under a flow of nitrogen. The tubes were wrapped in aluminium foil and kept in pre-cleaned amber glass vials (VWR International,

Canada) at 4 oC until use.

Silicone brooches and wristbands were pre-cleaned by using an Accelerated Solvent

Extractor (ASE) (Dionex ASE-350, Dionex Corporation, CA) with ethyl acetate following the method of Okeme et al. (2018). All silicone samplers were then soaked in methanol for at least

1 day to rinse off ethyl acetate before deployment. The aluminum housings and wires were washed with soap, rinsed with deionized water and then sonicated in methanol. Silicone brooches and wristbands were stored in pre-cleaned 500mL and 250mL pre-cleaned amber jars (VWR International, Canada) at 4 oC until deployment.

A4.2 – Extraction methods

Prior to extraction, all samples and blanks were spiked with the surrogate standards to assess extraction efficiencies. DEP-d4, DnBP-d4 and DEHP-d4 were used as surrogate standards for phthalates (AccuStandards Inc., USA) and TEP-d15, TPrP-d21, TBP-d27,

TDCIPP-d15, TCEP-d12 and MTPhP for OPEs (Wellington Laboratories, Canada).

Extraction of active air samplers (OVS)

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The GFF-OVS and a PUF/XAD-2/PUF sandwich in OVS tubes were extracted together to report he bulk air concentrations. Extraction was done using a Supelco vacuum chamber (Bellefonte, PA, USA). After spiking surrogates standards, OVS tubes were extracted with 15 mL of Acetone : DCM : Hexane (1:1:1) mixture. The extracts were concentrated to

0.5 mL, transferred to gas chromatography vials, blown down to near dryness under a gentle stream of Nitrogen, and reconstituted to approximately 0.5 mL in isooctane

Extraction of silicone passive samplers

Silicone brooches and wristbands were extracted by shaking and soaking with 30 mL of acetonitrile using Wrist Action Shaker (Burrell Corporation, USA). The extracts were reduced to 0.5 mL by using a Turbovap (Biotage, USA). The extracts were filtered by using

17 mm Teflon syringe filters (Thermo Scientific, USA) with pore size of 0.2 µm to remove particles from extracts and then stored in gas chromatography vials. Extracts were blown down to near dryness under a gentle stream of nitrogen and reconstituted to approximately 0.5 mL in isooctane.

Internal standards (Mirex for OPEs and Fluoranthene-d10 for phthalates) were added to all extracts for volume correction and time reference before analysis.

A4.3 - Instrumental analysis

Extracts were analyzed on an Agilent 6890N/5973 or 5975 gas chromatograph/ inert mass selective detector (GC-MSD) system. A negative chemical ionization (ENCI) source was used for TDCPP and an electron impact ionization (EI) source for phthalates and all other

OPEs measured here. All samples and blanks were analyzed for 11 phthalates and 19 OPEs which are listed in Table A4.1. Ions monitored are listed in Table A4.2.

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TDCIPP analysis was performed using a DB-5 MS column (Agilent Technologies, 15 m x 0.25 mm i.d. x 0.25 µm film thickness) with the following oven temperature program: initial at 100°C hold for 1.5 min, 12°C/min to 250°C, then 6°C/min to 290°C, hold for 3 min, and 60°C/min to 320°C, hold for 12 min. Post run at 310 °C for 2 mins.

Phthalates analysis was performed using 30 m DB-5 MS column (Agilent technologies,

0.25 mm i.d. and 0.25 µm film thickness) on EI source at following oven temperature program: initial at 750 C hold for 3 mins, 100 C min-1 to 3200 C and hold for 3 min.

A4.4 - Quality Assurance and Quality Control

Field blanks (n = 26 for OVS samplers, n = 29 for silicone brooches, n = 29 for silicone wristbands) were collected each day and analyzed along with laboratory blanks for all sample types. In addition, one laboratory blank and one matrix spike were analyzed per batch of each sample type (in total 10 for each matrix). The masses of the target compounds in each sample were compared to the mean mass in the field blanks on a matrix specific basis. Blank levels were treated according to the criteria described by Saini et al. (2015): no correction if the blank level was <5% of the measured level; blank level was subtracted from the measured level if the blank level was 5 - 35 % of the measured level; the sample was reported as “non-detect” if the blank level was >35 % of the measured level. No blank correction was necessary for

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most compounds in all matrices, except from DnOP and DEHtP in silicone brooches and wristbands.

Instrument detection limits (IDLs) were calculated as the standard deviation from 10 replicate injections of a low concentration calibration standard multiplied by three. Since most compounds from field blanks of all matrices (except from DnOP and DEHtP in silicone brooches and wristbands) were below IDLs, method of detection limits (MDLs) for active air samplers were calculated by normalizing IDLs by the average sampling rate of active air samplers and average of deployment time 8 hours (Table A4.6). Method of detection limits

(MDLs) for most compounds (except DnOP and DEHtP) silicone samplers were calculated by normalizing IDLs by the surface area of silicone samplers and average of deployment time 8 hours (Table A4.6). To obtain MDLs of DnOP and DEHtP, the sum of the average of field blanks and three times of field blanks’ standard deviations in silicone wristbands and brooches matrix were normalized by the surface area of silicone samplers and average of deployment time 8 hours. (Table A4.6)

Surrogate standard recoveries and matrix spike recoveries were considered satisfactory if they were between 50 – 150. Surrogate recoveries were considered satisfactory two thirds of recoveries were within the range 50-150 %. Since only five out of nine surrogates were within the range of 50-150%, results were recovery corrected for individual target compounds.

Figure A4.1: Nail technician wearing OVS sampler, silicone brooch and wristband.

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Table A4.1: Characteristics of 45 study participants from 18 salons in this study. Variables Number of Median Range workers Age 37a 21 – 58a Sex Female 42 Male 3 Years worked (years) In any salons 5a <1 – 30a In the sampling salon 2a <1 – 19a Hours worked (per week) In any salons 48b 8 – 83b In the sampling salon 48b 8 – 83b Workers’ participation Workers participated once 30 Workers participated for 2 times 14 Workers participated for 3 times 1 a: Years; b: Hours

Table A4.2: Types and numbers of services performed on sampling days.

Number of sampling days where Number of services performed Types of services service was performed, n (%) on sampling day, Median (IQR) Any services▲ 59 (98) 7 (5-8) Manicure 51 (85) 3 (2-4) Pedicure 50 (83) 2 (1-3) Artificial nails 17 (28) 1 (0-2) Other services* 26 (43) 1 (0-1) ▲Any services included one service among manicure, pedicure, artificial nail and other services. *Other services included eyebrows/eyelash service, waxing, facial service and massage. IQR: Interquartile range

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Table A4.3. Full names, CAS numbers, molecular weights (g mol-1) and log KOA values (calculated with EPISUITE Koawinn module) of target compounds.

Acronym Full name CAS Molecular Log KOA number weight Phthalate esters DMP Dimethyl phthalate 131-11-3 194 6.7 DEP Diethyl phthalate 84-66-2 222 7.0 DiBP Diisobutyl phthalate 84-69-5 278 8.4 DnBP Di-n-butyl phthalate 84-74-2 278 8.6 BzBP Benzylbutyl phthalate 85-68-7 312 9.0 DEHP Bis(2-ethylhexyl) phthalate 117-81-7 390 12.6 DEHtP Bis(2-ethylhexyl) tera phthalate 117-81-7 390 12.6 DnOP Di-n-octyl phthalate 117-84-0 391 12.1 DiNP Diisononyl phthalate 68515-48-0 418 12.6 DiDP Diidodecyl phthalate 26761-40-0 447 14.7 Organophosphate esters (OPEs) TEP Triethylphosphate 78-40-0 182 6.6 TiPP Tri-isopropyl phosphate 513-02-0 224 6.4 TPrP Tripropyl phosphate 513-08-6 224 6.4 TBP Tributyl phosphate 126-73-8 266 8.2 TBPO Tributylphosphine oxide 814-29-9 218 5.4 TCEP Tris(2-chloroethyl) phosphate 115-96-8 285 5.3 TCIPP Tris(2-chloroisopropyl) phosphate 13674-84-5 328 8.2 TPP Tripentyl phosphate 2528-38-3 308 8.8 TDCIPP Tris(1,3-dichloro-2-propyl) phosphate 13674-87-8 431 10.6 TPhP Triphenyl phosphate 115-86-6 326 8.5 EHDPP 2-Ethylhexyl diphenyl phosphate 1241-94-7 362 8.4 TBOEP Tris(2-butoxyethyl) phosphate 78-51-3 398 13.1 TEHP Tris(2-ethylhexyl) phosphate 78-42-2 435 15.0 TPPO Triphenylphosphine oxide 791-28-6 278 10.5 ToCP Tri-o-cresyl phosphate 78-30-8 368 9.6 DOPP Dioctyl phenylphosphonate 1754-47-8 383 11.7 TmCP Tri-m-cresyl phosphate 563-04-2 368 8.8 TpCP Tri-p-cresyl phosphate 78-32-0 368 12.0 T2IPPP Tris(2-isopropyl phenyl) phosphate 26967-76-0 453 14.0

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Table A4.4. Monitored quantifier and qualifier ions for target compounds.

Compounds Quantifier Qualifier Phthalate esters DMP 163 77 DEP 149 177, 150 DiBP 149 150, 57

DnBP 223 167, 205, 149 BzBP 206 91, 149 DEHP 279 167, 149 DEHtP 261 149, 279 DnOP 279 149, 167, 261 DiNP 293 149, 167 Organophosphate esters (OPEs) TEP 155 99, 127 TiPP 99 125 TPrP 99 141, 183 TBP 99 155, 211 TBPO 189 147 TCEP 261 263 TCIPP 99 125, 157 TPP 99 169 TDCIPP 319 317, 321 TPhP 326 325 EHDPP 251 250 TBOEP 57 85, 125 TEHP 99 113 TPPO 277 278 ToCP 368 165, 277 DOPP 159 271 TmCP 368 367 TpCP 368 367 T2IPPP 118 452, 251

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Table A4.5. Acronyms, monitored target and qualifier ions for surrogate and internal standards. Compounds Full name Targe Qualifier ions t ion Surrogate standards DEP-d4 Diethyl Phthalate-d4 153 DnBP-d4 Di-n-butyl phthalate-d4 153 DEHP-d4 Bis(2-ethylhexyl) phthalate-d4 153 TEP-d15 Tri-ethyl phosphate-d15 167 103 135 TPrP-d21 Tri-n-propyl phosphate-d21 103 151 131 TBP-d27 Tri-n-butyl phosphate-d27 103 TCEP-d12 Tris(2-chloroethyl) phosphate-d12 249 TDCIPP-d15 Tris(1,3-dichloro-2-propyl) phosphate-d15 329 13 MTPhP C18-Triphenyl phosphate 343 Internal standards Fluoranthene d-10 Fluoranthene d-10 212 Mirex 1,2,3,4,5,5,6,7,8,9,10,10- dodecachloropentacyclo[5.3.0.02,6.03,9.0 272 274 270 4,8]decane

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Table A4.6. Instrumental limit of detections (IDLs) and method limit of detection (MDL) of OVS samplers, silicone brooches and wristbands.

Acronym IDL (ng) MDL for OVS MDL for silicone MDL for silicone (ng m-3) brooches wristbands (ng dm-2 h-1) (ng dm-2 h-1) Phthalate esters DMP 0.1 0.0001 0.03 0.03 DEP 0.2 0.0002 0.05 0.1 DiBP 0.1 0.0001 0.03 0.03 DnBP 1.1 0.001 0.3 0.3 BzBP 0.6 0.001 0.2 0.2 DEHP 0.9 0.001 0.2 0.2 DEHtP 1.2 0.001 0.3 0.3 DnOP 50 0.05 12 13 DiNP 0.8 0.001 0.2 0.2 DiDP 25 0.03 6 6 Organophosphate esters (OPEs) TEP 140 0.14 33 35 TiPP 75 0.08 19 20 TPrP 3 0.003 0.8 0.8 TBP 0.8 0.001 0.2 0.2 TBPO 21 0.02 5 5 TCEP 1.4 0.001 0.4 0.4 TCIPP 9 0.01 2 2 TPP 1.3 0.001 0.3 0.3 TDCIPP 0.1 0.0001 0.03 0.03 TPhP 2.2 0.002 0.6 0.6 EHDPP 1.1 0.001 0.3 0.3 TBOEP 54 0.06 13 14 TEHP 1.7 0.002 0.4 0.4 TPPO 0.7 0.001 0.2 0.2 ToCP 2.9 0.003 0.7 0.8 DOPP 0.6 0.001 0.2 0.2 TmCP 1.6 0.002 0.4 0.4 TpCP 1.2 0.001 0.3 0.3 T2IPPP 3.6 0.004 0.9 0.9 Average sampling time = 8h; average sampling rate for active air samplers = 2 L min-1; brooch surface area = 0.5 dm2; wristband surface area = 0.48 dm2

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Table A4.7. Detection frequencies (%) of 10 phthalates and 19 OPEs in active air samplers, silicone brooches and wristbands worn by nail salon workers. Active air samplers Silicone brooches Silicone wristbands Compounds (n = 60) (n = 58) (n = 60) Phthalate esters DMP 100 100 97 DEP 100 100 100 DiBP 100 100 100 DnBP 100 97 98 BzBP 18 59 98 DEHP 87 98 100 DEHtP 83 0 100 DnOP 0 98 98 DiNP 0 97 100 DiDP 0 90 100 Organophosphate esters (OPEs) TEP 5 14 13 TiPP 0 0 0 TPrP 0 0 0 TBP 0 0 0 TBPO 0 0 0 TCEP 98 93 98 TCIPP 98 98 97 TPP 0 0 0 TDCIPP 77 100 100 TPhP 95 98 100 EHDPP 0 0 0 TBOEP 0 36 95 TEHP 0 0 30 TPPO 0 10 27 ToCP 0 0 0 DOPP 0 0 0 TmCP 0 0 10 TpCP 0 0 0 T2IPPP 0 0 0

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Table A4.8. Spearman’s rank correlation coefficients between selected phthalates and OPEs that have at least 70% detection in active air samplers. Numbers in bold are statistically significant with p-value < 0.05.

DMP DMP DEP 0.50 DEP DiBP 0.54 0.63 DiBP Phthalates DnBP 0.54 0.64 0.99 DnBP DEHP -0.22 0.11 -0.05 -0.01 DEHP DEHtP -0.19 0.2 0.18 0.19 0.50 DEHtP TCEP 0.26 0.57 0.28 0.3 0.03 0.05 TCEP Organophosphorus esters TCIPP 0.001 0.2 0.11 0.1 -0.11 0.02 0.21 TCIPP (OPEs) TDCIPP -0.32 -0.22 -0.18 -0.16 0.45 0.26 -0.05 -0.18 TDCIPP TPhP -0.15 0.06 -0.001 0.03 0.31 0.23 -0.05 -0.09 -0.09

Strength of the correlation 0.00 - 0.19: very weak 0.20 - 0.39: weak 0.40 - 0.59: moderate 0.60 - 0.79: strong 0.80 - 1.00: very strong

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Table A4.9. Comparison of median concentrations of phthalates and OPEs (in ng dm-2 h-1 and ng g-1 h-1) in silicone wristbands from nail salon workers in this study and other occupational and non-occupational studies.

Exposed population, type of DMP DEP DiBP DnBP DEHP DiNP DEHtP TCEP TCIPP TDCIPP TPhP wristband, numbers of samples (reference) Median concentrations in wristbands in ng dm-2 h-1 Nail salon workers in this study, 16 156 292 453 8,770 3,230 5,800 37 225 212 244 customized wristbands, n = 60 E-waste workers in Canada, ------43 63 38 61 customized wristbands, n = 45 (Nguyen et al., 2020)(Nguyen et al., 2020) E-waste workers in Bangladesh, ------57 15 74 29 customized wristbands, n = 9 (Wang et al., 2020)(Wang et al., 2020)

Median concentrations in wristbands in ng g-1 h-1 Nail salon workers in this study, 1.4 14 26 40 780 287 515 3.3 20 19 22 customized wristbands, n = 60 Nail salon workers in US, commercial- <0.2 <3.5 <2 <124 4.7 5.6 2.3 <3.4 4.4 1.7 15 available, n = 9 (Craig et al., 2019)(Craig et al., 2019)

Non-occupational participants at US ------0.2 0.6 1.5 1.2 homes, commercial-available wristbands, n = 10 (Wang et al., 2019)(Wang et al., 2019) “-“: No information; nd: non-detects

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Table A4.10. Median air concentrations (ng m-3) of selected phthalates and OPEs in active air samplers worn by workers performing different numbers of services (including any services, manicure, pedicure, artificial nails and others) per shift. Comparisons between air concentrations and numbers of services performed in each category were completed using Kruskal-Wallis test and Mann-Whitney U test. Numbers in bold are statistically significant with p-value < 0.05.

Number of Median Phthalate Concentration Median OPE Concentration workers (ng m-3) (ng m-3) Numbers of services performed per performed shift services DMP DEP DiBP DnBP DEHP DEHtP TCEP TCIPP TDCIPP TPhP Any services▲ 0 – 5 22 51 460 358 355 37 14 88 307 0.8 11 6 – 10 29 37 449 327 317 39 15 169 369 1.1 12 >10 9 48 471 506 493 36 26 158 252 1.6 12 Kruskal-Wallis test, p-value 0.48 0.48 0.48 0.48 0.48 0.48 0.48 0.48 0.48 0.48 Manicure services 0 services 9 65 553 598 573 43 24 166 521 1.0 11 1 – 3 31 36 399 331 322 41 19 144 300 1.1 10 >3 20 44 422 262 252 30 10 121 310 1.2 13 Kruskal-Wallis test, p-value 0.48 0.48 0.48 0.48 0.48 0.48 0.48 0.48 0.48 0.48 Pedicure services 0 10 56 713 566 550 54 38 169 424 1.5 14 1 – 3 36 41 399 277 266 36 14 90 294 1.0 10 >3 14 46 493 352 345 38 9 167 503 0.9 12 Kruskal-Wallis test, p-value 0.48 0.48 0.48 0.48 0.48 0.48 0.48 0.48 0.48 0.48 Artificial nail services 0 43 46 470 335 325 33 14 127 348 0.9 11 ≥ 1 17 45 471 338 328 50 26 154 204 1.2 12 Mann-Whitney U test, p-value 0.67 0.82 0.67 0.72 0.08 0.05 0.88 0.1 0.07 0.68 Other services* 0 34 34 365 259 251 38 15 108 327 1.1 11 ≥ 1 26 60 538 463 452 36 15 161 293 1.1 12 Mann-Whitney U test, p-value 0.002 0.03 0.01 0.01 0.77 0.52 0.58 0.67 0.96 0.96

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Table A4.11. Comparison of selected phthalates and OPEs levels in air (ng m-3) collected by personal active air samplers in this study and those collected by personal and stationary active air samplers from indoor environments in literature.

Study location, types of samples, number of samples Statistical (reference) parameters DEP DiBP DnBP DEHP TCEP TCIPP TDCIPP TPhP This study, personal samples, n = 60 Geometric mean 550 337 331 21 100 235 0.7 13 Median 471 337 331 36 129 303 1.1 11 Minimum 66 67 67 0.09 0.9 6.0 0.05 1.0 Maximum 13,700 1,033 1,015 125 590 1,130 9.3 870 Hair salons in Vietnam, stationary samples, n = 13 Median 488 666 162 257 - - - - (Tran et al., 2017) Minimum 62 29 2.6 38 - - - - Maximum 12,400 2,580 1,360 598 - - - - Nail and hair salons in US, stationary samples, n = 6 Median 1,680 305 373 78 - - - - (Tran and Kannan, 2015) Minimum 1,270 123 122 34 - - - - Maximum 2,250 1,380 1,170 706 - - - - Offices in Canada, stationary samples, n = 22 Average 60 nd 85 46 - - - - (Saini et al., 2015) Minimum 49 nd 64 32 - - - - Maximum 70 nd 101 58 - - - -

An office in Canada, personal samples, n = 5 Median 272 208 119 2,010 - - - - (Okeme et al., 2018a) Minimum 194 153 69 1,820 - - - - Maximum 281 323 140 2,230 - - - - Nail salons in US, personal samples, n =11 Median ------7.2 (Estill et al., 2020) E-waste recycling facilities, personal samples, n = 30 Geometric mean - - - - 130 - 25 100 (Gravel et al., 2019c)

Commercial recycling facilities, personal samples, n = 15 Geometric mean - - - - 2.4 - 3.6 25 (Gravel et al., 2019c)

Home in US, personal samples, n = 10 Median - - - - 4.6 11 1.9 1.4 (Wang et al., 2019) Minimum - - - - 1.4 3.4 1.0 1.0 Maximum - - - - 17 51 4.7 1.9 “-: No information; nd: non detects

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Figure A4.2: Scatter plots for median concentrations of active air samplers, brooches and wristbands versus Log Koa of selected compounds.

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References Abbasi, G., Buser, A.M., Soehl, A., Murray, M.W., Diamond, M.L., 2015. Stocks and flows of PBDEs in products from use to waste in the U.S. and canada from 1970 to 2020. Environ. Sci. Technol. 49, 1521–1528. https://doi.org/10.1021/es504007v Abbasi, G., Saini, A., Goosey, E., Diamond, M.L., 2016. Product screening for sources of halogenated flame retardants in Canadian house and office dust. Sci. Total Environ. 545– 546, 299–307. https://doi.org/10.1016/j.scitotenv.2015.12.028 Abdallah, M.A.-E., Pawar, G., Harrad, S., 2015a. Evaluation of 3D-human skin equivalents for assessment of human dermal absorption of some brominated flame retardants. Environ. Int. 84, 64–70. https://doi.org/10.1016/j.envint.2015.07.015 Abdallah, M.A.-E., Pawar, G., Harrad, S., 2015b. Effect of Bromine Substitution on Human Dermal Absorption of Polybrominated Diphenyl Ethers. Environ. Sci. Technol. 49, 10976– 10983. https://doi.org/10.1021/acs.est.5b03904 Abou-Elwafa Abdallah, M., Pawar, G., Harrad, S., 2016. Human dermal absorption of chlorinated organophosphate flame retardants; implications for human exposure. Toxicol. Appl. Pharmacol. 291, 28–37. https://doi.org/10.1016/j.taap.2015.12.004 ACGIH, 2018. TLVs ® and BEIs ® : Threshold limit values for chemical substances and physical agents biological exposure indices. American Conference of Governmental Industrial Hygienists, Cincinnati, OH, OH. ACGIH, 2001. Documentation of threshold limit values for substances in work environment. American Conference of Governmental Industrial Hygienists, Cincinnati, OH, OH. Ait, Y., Araki, A., Kawai, T., Tsuboi, T., Saito, I., Yoshioka, E., Kanazawa, A., 2014. Science of the Total Environment Associations of phthalate concentrations in fl oor dust and multi- surface dust with the interior materials in Japanese dwellings. Sci. Total Environ. 468–469, 147–157. https://doi.org/10.1016/j.scitotenv.2013.07.107 Akormedi, M., Asampong, E., Fobil, J.N., 2013. Working conditions and environmental exposures among electronic waste workers in Ghana. Int. J. Occup. Environ. Health 19, 278–286. https://doi.org/10.1179/2049396713Y.0000000034 Allen, J.G., McClean, M.D., Stapleton, H.M., Nelson, J.W., Webster, T.F., 2007. Personal Exposure to Polybrominated Diphenyl Ethers (PBDEs) in Residential Indoor Air. Environ. Sci. Technol. 41, 4574–4579. https://doi.org/10.1021/es0703170 Allen, J.O., Dookeran, N.M., Smith, K.A., Sarofim, A.F., Taghizadeh, K., Lafleur, A.L., 1996. Measurement of polycyclic aromatic hydrocarbons associated with size-segregated atmospheric aerosols in Massachusetts. Environ. Sci. Technol. 30, 1023–1031. https://doi.org/10.1021/es950517o Andersen, C., Krais, A.M., Eriksson, A.C., Jakobsson, J., Löndahl, J., Nielsen, J., Lindh, C.H., Pagels, J., Gudmundsson, A., Wierzbicka, A., 2018. Inhalation and Dermal Uptake of Particle and Gas-Phase Phthalates—A Human Exposure Study. Environ. Sci. Technol. 52, 12792–12800. https://doi.org/10.1021/acs.est.8b03761

315

Asante, K.A., Agusa, T., Biney, C.A., Agyekum, W.A., Bello, M., Otsuka, M., Itai, T., Takahashi, S., Tanabe, S., 2012. Multi-trace element levels and arsenic speciation in urine of e-waste recycling workers from Agbogbloshie, Accra in Ghana. Sci. Total Environ. 424, 63–73. https://doi.org/10.1016/j.scitotenv.2012.02.072 ATSDR, 2012. Toxicological Profile for Phosphate Ester Flame Retardants. ATSDR, 2005. Public Health Assessment Guidance Manual (2005 Update). Atlanta, Georgia. ATSDR, 2004. Toxicological profile for polybrominated biphenyl and polybrominated diphenyl ethers 1–599. Awasthi, A.K., Wang, M., Wang, Z., Awasthi, M.K., Li, J., 2018. E-waste management in India: A mini-review. Waste Manag. Res. 36, 408–414. https://doi.org/10.1177/0734242X18767038 Bakhiyi, B., Gravel, S., Ceballos, D., Flynn, M.A., Zayed, J., 2018. Has the question of e-waste opened a Pandora’s box? An overview of unpredictable issues and challenges. Environ. Int. 110, 173–192. https://doi.org/https://doi.org/10.1016/j.envint.2017.10.021 Balde, C.P., Forti, V., Gray, V., Kuehr, R., Stegmann, P., 2017. The global e-waste monitor 2017, United Nations University. https://doi.org/10.1016/j.proci.2014.05.148 Baldé, C.P., Wang, F., Kuehr, R., Huisman, J., 2015. The Global E-waste Monitor 2014: Quantitites, flows and resources. Bonn, Germany. https://doi.org/ISBN 978-92-808-4556-3 Bartkow, M.E., Booij, K., Kennedy, K.E., Müller, J.F., Hawker, D.W., 2005. Passive air sampling theory for semivolatile organic compounds. Chemosphere 60, 170–176. https://doi.org/10.1016/j.chemosphere.2004.12.033 Basel Convention, 2011. Electrical and electronic equipment when becoming waste (e-waste) such as personal computers, printers, televisions, mobile phones, refrigerators and air- conditioning units is one of the fastest growing waste streams in the world today. [WWW Document]. URL http://www.basel.int/Implementation/Ewaste/Overview/tabid/4063/Default.aspx (accessed 3.8.20). Beaucham, C.C., Ceballos, D., Page, E.H., Mueller, C., Calafat, A.M., Sjodin, A., Ospina, M., Guardia, M. La, Glassford, E., 2018. Evaluation of Exposure to Metals , Flame Retardants , and Nanomaterials at an Electronics Recycling Company 1–80. Behl, M., Hsieh, J.H., Shafer, T.J., Mundy, W.R., Rice, J.R., Boyd, W.A., Freedman, J.H., Hunter, E.S., Jarema, K.A., Padilla, S., Tice, R.R., 2015. Use of alternative assays to identify and prioritize organophosphorus flame retardants for potential developmental and neurotoxicity. Neurotoxicol. Teratol. 52, 181–193. https://doi.org/10.1016/j.ntt.2015.09.003 Behl, M., Rice, J.R., Smith, M. V., Co, C.A., Bridge, M.F., Hsieh, J.-H., Freedman, J.H., Boyd, W.A., 2016. Editor’s Highlight: Comparative Toxicity of Organophosphate Flame Retardants and Polybrominated Diphenyl Ethers to Caenorhabditis elegans. Toxicol. Sci. 154, 241–252. https://doi.org/10.1093/toxsci/kfw162 Bergh, C., Torgrip, R., Emenius, G., Östman, C., 2011. Organophosphate and phthalate esters in

316

air and settled dust - a multi-location indoor study. Indoor Air 21, 67–76. https://doi.org/10.1111/j.1600-0668.2010.00684.x Betts, K.S., 2002. Rapidly rising PBDE levels in North America. Environ. Sci. Technol. 36, 50A-52A. https://doi.org/10.1021/es022197w Bi, C., Liang, Y., Xu, Y., 2015. Fate and Transport of Phthalates in Indoor Environments and the Influence of Temperature: A Case Study in a Test House. Environ. Sci. Technol. 49, 9674–9681. https://doi.org/10.1021/acs.est.5b02787 Bidleman, T.F., 1988. Atmospheric processes. Environ. Sci. Technol. 22, 361–367. https://doi.org/10.1021/es00169a002 Blum, A., Behl, M., Birnbaum, L.S., Diamond, M.L., Phillips, A., Singla, V., Sipes, N.S., Stapleton, H.M., Venier, M., 2019. Organophosphate Ester Flame Retardants: Are They a Regrettable Substitution for Polybrominated Diphenyl Ethers? Environ. Sci. Technol. Lett. 6, 638–649. https://doi.org/10.1021/acs.estlett.9b00582 Bohlin, P., Audy, O., Škrdlíková, L., Kukučka, P., Přibylová, P., Prokeš, R., Vojta, Š., Klánová, J., 2014. Outdoor passive air monitoring of semi volatile organic compounds (SVOCs): a critical evaluation of performance and limitations of polyurethane foam (PUF) disks. Environ. Sci. Process. Impacts 16, 433–444. https://doi.org/10.1039/C3EM00644A Bohlin, Pernilla, Audy, O., Škrdlíková, L., Kukučka, P., Vojta, Š., Přibylová, P., Prokeš, R., Čupr, P., Klánová, J., 2014. Evaluation and guidelines for using polyurethane foam (PUF) passive air samplers in double-dome chambers to assess semi-volatile organic compounds (SVOCs) in non-industrial indoor environments. Environ. Sci. Process. Impacts 16, 2617– 2626. https://doi.org/10.1039/C4EM00305E Bohlin, P., Jones, K.C., Levin, J.-O., Lindahl, R., Strandberg, B., 2010a. Field evaluation of a passive personal air sampler for screening of PAH exposure in workplaces. J. Environ. Monit. 12, 1437. https://doi.org/10.1039/c0em00018c Bohlin, P., Jones, K.C., Strandberg, B., 2010b. Field evaluation of polyurethane foam passive air samplers to assess airborne PAHs in occupational environments. Environ. Sci. Technol. 44, 749–754. https://doi.org/10.1021/es902318g Bohlin, P., Jones, K.C., Strandberg, B., 2007. Occupational and indoor air exposure to persistent organic pollutants: A review of passive sampling techniques and needs. J. Environ. Monit. 9, 501. https://doi.org/10.1039/b700627f Bornehag, C.G., Nanberg, E., 2010. Phthalate exposure and asthma in children 33, 333–345. https://doi.org/10.1111/j.1365-2605.2009.01023.x Braun, J.M., Kalkbrenner, A.E., Just, A.C., Yolton, K., Calafat, A.M., Sjödin, A., Hauser, R., Webster, G.M., Chen, A., Lanphear, B.P., 2014. Gestational Exposure to Endocrine- Disrupting Chemicals and Reciprocal Social, Repetitive, and Stereotypic Behaviors in 4- and 5-Year-Old Children: The HOME Study. Environ. Health Perspect. 122, 513–520. https://doi.org/10.1289/ehp.1307261 Breul, S., Van Landuyt, K.L., Reichl, F.X., Högg, C., Hoet, P., Godderis, L., Van Meerbeek, B., Cokic, S.M., 2020. Filtration efficiency of surgical and FFP3 masks against composite dust. 317

Eur. J. Oral Sci. 128, 233–240. https://doi.org/10.1111/eos.12697 Brown, J., Gordon, T., Price, O., Asgharian, B., 2013. Thoracic and respirable particle deinitions for human health risk assessment. Part. Fibre Toxicol. 10, 1–12. Cahill, T.M., Groskova, D., Charles, M.J., Sanborn, J.R., Denison, M.S., Baker, L., 2007. Atmospheric concentrations of polybrominated diphenyl ethers at near-source sites. Environ. Sci. Technol. 41, 6370–6377. https://doi.org/10.1021/es070844j Callesen, M., Bekö, G., Weschler, C.J., Langer, S., Brive, L., Clausen, G., Toftum, J., Sigsgaard, T., Høst, A., Kold, T., 2014. International Journal of Hygiene and Phthalate metabolites in urine and asthma , allergic rhinoconjunctivitis and atopic dermatitis in preschool children. Int. J. Hyg. Environ. Health 217, 645–652. https://doi.org/10.1016/j.ijheh.2013.12.001 Cao, Z., Xu, F., Covaci, A., Wu, M., Wang, H., Yu, G., Wang, B., Deng, S., Huang, J., Wang, X., 2014. Distribution patterns of brominated, chlorinated, and phosphorus flame retardants with particle size in indoor and outdoor dust and implications for human exposure. Environ. Sci. Technol. 48, 8839–8846. https://doi.org/10.1021/es501224b Carignan, C.C., Mínguez-Alarcón, L., Butt, C.M., Williams, P.L., Meeker, J.D., Stapleton, H.M., Toth, T.L., Ford, J.B., Hauser, R., 2017. Urinary Concentrations of Organophosphate Flame Retardant Metabolites and Pregnancy Outcomes among Women Undergoing in Vitro Fertilization. Environ. Health Perspect. 125, 087018. https://doi.org/10.1289/EHP1021 Carignan, C.C., Mínguez-Alarcón, L., Williams, P.L., Meeker, J.D., Stapleton, H.M., Butt, C.M., Toth, T.L., Ford, J.B., Hauser, R., 2018. Paternal urinary concentrations of organophosphate flame retardant metabolites, fertility measures, and pregnancy outcomes among couples undergoing in vitro fertilization. Environ. Int. 111, 232–238. https://doi.org/10.1016/j.envint.2017.12.005 Castorina, R., Bradman, A., Stapleton, H.M., Butt, C., Avery, D., Harley, K.G., Gunier, R.B., Holland, N., Eskenazi, B., 2017. Current-use flame retardants: Maternal exposure and neurodevelopment in children of the CHAMACOS cohort. Chemosphere 189, 574–580. https://doi.org/10.1016/j.chemosphere.2017.09.037 Ceballos, D.M., Côté, D., Bakhiyi, B., Flynn, M.A., Zayed, J., Gravel, S., Herrick, R.F., Labrèche, F., 2020. Overlapping vulnerabilities in workers of the electronics recycling industry formal sector: A commentary. Am. J. Ind. Med. 63, 955–962. https://doi.org/10.1002/ajim.23173 Ceballos, D.M., Dong, Z., 2016. The formal electronic recycling industry: Challenges and opportunities in occupational and environmental health research. Environ. Int. 95, 157–166. https://doi.org/10.1016/j.envint.2016.07.010 CEPA, 1999. Canadian Environmental Protection Act. Cequier, E., Sakhi, A.K., Marcé, R.M., Becher, G., Thomsen, C., 2015. Human exposure pathways to organophosphate triesters — A biomonitoring study of mother–child pairs. Environ. Int. 75, 159–165. https://doi.org/10.1016/j.envint.2014.11.009 Chan, J.K.Y., Wong, M.H., 2013. A review of environmental fate, body burdens, and human 318

health risk assessment of PCDD/Fs at two typical electronic waste recycling sites in China. Sci. Total Environ. 463–464, 1111–1123. https://doi.org/10.1016/j.scitotenv.2012.07.098 Cherrie, J.W., 2003. CommentaryThe Beginning of the Science Underpinning Occupational Hygiene. Ann. Occup. Hyg. 47, 179–185. https://doi.org/10.1093/annhyg/meg030 City of Toronto, 2019. Search for an Establishment Monitored by BodySafe [WWW Document]. URL https://www.toronto.ca/community-people/health-wellness-care/health- programs-advice/bodysafe/search-for-an-establishment-space-holder-for-map/ (accessed 7.18.19). Consumer Product Safety Commission, 2008. Consumer Product Safety Improvement Act of 2008. Craig, J.A., Ceballos, D.M., Fruh, V., Petropoulos, Z.E., Allen, J.G., Calafat, A.M., Ospina, M., Stapleton, H.M., Hammel, S., Gray, R., Webster, T.F., 2019. Exposure of Nail Salon Workers to Phthalates, Di(2-ethylhexyl) Terephthalate, and Organophosphate Esters: A Pilot Study. Environ. Sci. Technol. 53, 14630–14637. https://doi.org/10.1021/acs.est.9b02474 de Winter-Sorkina, R., Bakker, M.., Wolterink, G., Zielmaker, M.J., 2006. Brominated flame retardants: occurrence, dietary intake and risk assessment [WWW Document]. URL https://www.rivm.nl/bibliotheek/rapporten/320100002.pdf (accessed 6.7.18). Delgado-Saborit, J.M., Stark, C., Harrison, R.M., 2014. Use of a versatile high efficiency multiparallel denuder for the sampling of PAHs in ambient air: Gas and particle phase concentrations, particle size distribution and artifact formation. Environ. Sci. Technol. 48, 499–507. https://doi.org/10.1021/es402937d Dixon, H.M., Scott, R.P., Holmes, D., Calero, L., Kincl, L.D., Waters, K.M., Camann, D.E., Calafat, A.M., Herbstman, J.B., Anderson, K.A., 2018. Silicone wristbands compared with traditional polycyclic aromatic hydrocarbon exposure assessment methods. Anal. Bioanal. Chem. 410, 3059–3071. https://doi.org/10.1007/s00216-018-0992-z Eakin, J.M., Champoux, D., MacEachen, E., 2017. Health and safety in small workplaces: refocusing upstream. Can. J. Public Health 101 Suppl, S29-33. EC, 2018. Waste Electrical & Electronic Equipment (WEEE) [WWW Document]. Eur. Comm. https://doi.org/10.1016/j.geb.2005.03.002 Ekelund, M., Azhdar, B., Gedde, U.W., 2010. Evaporative loss kinetics of di(2- ethylhexyl)phthalate (DEHP) from pristine DEHP and plasticized PVC. Polym. Degrad. Stab. 95, 1789–1793. https://doi.org/10.1016/j.polymdegradstab.2010.05.007 Eriksson, P., Jakobsson, E., Fredriksson, A., 2001. Brominated flame retardants: a novel class of developmental toxicants in our environment? Environ. Health Perspect. 109, 903–908. https://doi.org/10.1289/ehp.01109903 Estill, C.F., Slone, J., Mayer, A., Chen, I.-C., La Guardia, M.J., 2020. Worker exposure to flame retardants in manufacturing, construction and service industries. Environ. Int. 135, 105349. https://doi.org/10.1016/j.envint.2019.105349 319

European Commission, 2014. COMMUNICATION FROM THE COMMISSION on the finalisation of the restriction process on the four phthalates (DEHP, DBP, BBP and DIBP) under Regulation (EC) No 1907/2006 of the European Parliament and of the Council concerning Registration, Evaluation, Authori. Off. J. Eur. Union 73, 1–4. ExpoStats, 2015. NDExpo – Treatment of non-detects in industrial hygiene samples [WWW Document]. URL http://www.expostats.ca/site/app-local/NDExpo/ (accessed 2.20.20). Factor-Litvak, P., Insel, B., Calafat, A.M., Liu, X., Perera, F., Rauh, V.A., Whyatt, R.M., 2014. Persistent Associations between Maternal Prenatal Exposure to Phthalates on Child IQ at Age 7 Years. PLoS One 9, e114003. https://doi.org/10.1371/journal.pone.0114003 Federman, M.N., Harrington, D.E., Krynski, K.J., 2006. Vietnamese Manicurists: Are Immigrants Displacing Natives or Finding New Nails to Polish? ILR Rev. 59, 302–318. https://doi.org/10.1177/001979390605900207 Fisher, M., Arbuckle, T.E., MacPherson, S., Braun, J.M., Feeley, M., Gaudreau, É., 2019. Phthalate and BPA Exposure in Women and Newborns through Personal Care Product Use and Food Packaging. Environ. Sci. Technol. 53, 10813–10826. https://doi.org/10.1021/acs.est.9b02372 Flanagan, M.E., Seixas, N., Majar, M., Camp, J., Morgan, M., 2003. Silica Dust Exposures During Selected Construction Activities. AIHA J. 64, 319–328. https://doi.org/10.1080/15428110308984823 Fortia, V., Balde, C.P., Kuehr, R., Bel, G., 2020. The Global E-waste Monitor 2020: Quantitites, flows and circular economy potential [WWW Document]. URL https://collections.unu.edu/view/UNU:7737 (accessed 10.13.20). Fraser, A.J., Webster, T.F., McClean, M.D., 2009. Diet Contributes Significantly to the Body Burden of PBDEs in the General U.S. Population. Environ. Health Perspect. 117, 1520– 1525. https://doi.org/10.1289/ehp.0900817 Frazzoli, C., Orisakwe, O.E., Dragone, R., Mantovani, A., 2010. Diagnostic health risk assessment of electronic waste on the general population in developing countries’ scenarios. Environ. Impact Assess. Rev. 30, 388–399. https://doi.org/10.1016/j.eiar.2009.12.004 Frederiksen, M., Stapleton, H.M., Vorkamp, K., Webster, T.F., Jensen, N.M., Sørensen, J.A., Nielsen, F., Knudsen, L.E., Sørensen, L.S., Clausen, P.A., Nielsen, J.B., 2018. Dermal uptake and percutaneous penetration of organophosphate esters in a human skin ex vivo model. Chemosphere 197, 185–192. https://doi.org/10.1016/j.chemosphere.2018.01.032 Fromme, H., Becher, G., Hilger, B., Völkel, W., 2016. Brominated flame retardants - Exposure and risk assessment for the general population. Int. J. Hyg. Environ. Health 219, 1–23. https://doi.org/10.1016/j.ijheh.2015.08.004 Gaspar, F.W., Castorina, R., Maddalena, R.L., Nishioka, M.G., McKone, T.E., Bradman, A., 2014. Phthalate exposure and risk assessment in California child care facilities. Environ. Sci. Technol. 48, 7593–7601. https://doi.org/10.1021/es501189t Gevao, B., Al-Bahloul, M., Al-Ghadban, A.N., Ali, L., Al-Omair, A., Helaleh, M., Al-Matrouk, 320

K., Zafar, J., 2006. Polybrominated diphenyl ethers in indoor air in Kuwait: Implications for human exposure. Atmos. Environ. 40, 1419–1426. https://doi.org/10.1016/j.atmosenv.2005.10.053 Gioia, R., Steinnes, E., Thomas, G.O., Mejier, S.N., Jones, K.C., 2006. Persistent organic pollutants in European background air: derivation of temporal and latitudinal trends. J. Environ. Monit. 8, 700. https://doi.org/10.1039/b604821h Giovanoulis, G., Bui, T., Xu, F., Papadopoulou, E., Padilla-Sanchez, J.A., Covaci, A., Haug, L.S., Cousins, A.P., Magnér, J., Cousins, I.T., de Wit, C.A., 2018. Multi-pathway human exposure assessment of phthalate esters and DINCH. Environ. Int. 112, 115–126. https://doi.org/10.1016/j.envint.2017.12.016 Glazer, L., Hawkey, A.B., Wells, C.N., Drastal, M., Odamah, K.-A., Behl, M., Levin, E.D., 2018. Developmental Exposure to Low Concentrations of Organophosphate Flame Retardants Causes Life-Long Behavioral Alterations in Zebrafish. Toxicol. Sci. 165, 487– 498. https://doi.org/10.1093/toxsci/kfy173 Godwin, A.D., 2017. Plasticizers, in: Applied Plastics Engineering Handbook. Elsevier, pp. 533–553. Godwin, A.D., 2010. Uses of Phthalates and Other Plasticizers [WWW Document]. URL https://www.cpsc.gov/s3fs-public/godwin.pdf (accessed 10.21.20). Gong, M., Weschler, C.J., Zhang, Y., 2016. Impact of Clothing on Dermal Exposure to Phthalates: Observations and Insights from Sampling Both Skin and Clothing. Environ. Sci. Technol. 50, 4350–4357. https://doi.org/10.1021/acs.est.6b00113 Goodyer, C.G., Poon, S., Aleksa, K., Hou, L., Atehortua, V., Carnevale, A., Jednak, R., Emil, S., Bagli, D., Dave, S., Hales, B.F., Chevrier, J., 2017. A case-control study of maternal polybrominated diphenyl ether (PBDE) exposure and cryptorchidism in Canadian populations. Environ. Health Perspect. 125, 1–9. https://doi.org/10.1289/EHP522 Gouin, T., Harner, T., Blanchard, P., Mackay, D., 2005. Passive and Active Air Samplers as Complementary Methods for Investigating Persistent Organic Pollutants in the Great Lakes Basin. Environ. Sci. Technol. 39, 9115–9122. https://doi.org/10.1021/es051397f Goverment of Canada, 2017. Phthalates Regulations Règlement sur les phtalates 21–23. Government of Canada, 2019. Cosmetic Ingredient Hotlist [WWW Document]. URL https://www.canada.ca/en/health-canada/services/consumer-product- safety/cosmetics/cosmetic-ingredient-hotlist-prohibited-restricted- ingredients/hotlist.html#tbl1 (accessed 5.4.20). Government of Canada, 2016. Toxic substances list: PBDEs [WWW Document]. Government of Canada, 2012. Regulations Amending the Prohibition of Certain Toxic Substances Regulations, 2012 [WWW Document]. Canada Gaz. Part II. URL http://www.gazette.gc.ca/rp-pr/p2/2016/2016-10-05/pdf/g2-15020.pdf (accessed 2.18.21). Government of Ontario, 2018. Waste management [WWW Document]. URL https://www.ontario.ca/page/waste-management (accessed 12.9.18).

321

Graham, P.R., 1973. Phthalate ester plasticizers—why and how they are used. Environ. Health Perspect. 3, 3–12. https://doi.org/10.1289/ehp.73033 Grant, K., Goldizen, F.C., Sly, P.D., Brune, M.-N., Neira, M., van den Berg, M., Norman, R.E., 2013. Health consequences of exposure to e-waste: a systematic review. Lancet Glob. Heal. 1, e350–e361. https://doi.org/10.1016/S2214-109X(13)70101-3 Gravel, S., Bakhiyi, B., Lavoué, J., Verner, M.-A., Zayed, J., Labreche, F., 2019a. Electronic waste recycling exposure and hormone levels in workers., in: 27th EPICOH International Symposium on Epidemiology in Occupational Health. Wellington, NewZealand. Gravel, S., Diamond, M.L., Jantunen, L.M., Verner, M.-A., Zayed, J., Labrèche, F., 2019b. Is airborne concentration of BDE209 associated with serum concentration in recycling workers?, in: 9th International Symposium on Flame Retardants BFR 2019. Montreal, Canada. Gravel, S., Lavoué, J., Bakhiyi, B., Diamond, M.L., Jantunen, L.M., Lavoie, J., Roberge, B., Verner, M.-A., Zayed, J., Labrèche, F., 2019c. Halogenated flame retardants and organophosphate esters in the air of electronic waste recycling facilities: Evidence of high concentrations and multiple exposures. Environ. Int. 128, 244–253. https://doi.org/10.1016/j.envint.2019.04.027 Gravel, S., Lavoué, J., Bakhiyi, B., Lavoie, J., Roberge, B., Patry, L., Bouchard, M.F., Verner, M., Zayed, J., Labrèche, F., 2020. Multi-exposures to suspected endocrine disruptors in electronic waste recycling workers: Associations with thyroid and reproductive hormones. Int. J. Hyg. Environ. Health 225, 113445. https://doi.org/10.1016/j.ijheh.2019.113445 Guo, J., Lin, K., Deng, J., Fu, X., Xu, Z., 2015. Polybrominated diphenyl ethers in indoor air during waste TV recycling process. J. Hazard. Mater. 283, 439–446. https://doi.org/10.1016/j.jhazmat.2014.09.044 Guo, Y., Kannan, K., 2013. A survey of phthalates and parabens in personal care products from the United States and its implications for human exposure. Environ. Sci. Technol. 47, 14442–14449. https://doi.org/10.1021/es4042034 Guo, Y., Kannan, K., 2011. Comparative Assessment of Human Exposure to Phthalate Esters from House Dust in China and the United States. Environ. Sci. Technol. 45, 3788–3794. https://doi.org/10.1021/es2002106 Hammel, S., Hoffman, K., Webster, T.F., Anderson, K.A., Stapleton, H.M., 2016. Measuring Personal Exposure to Organophosphate Flame Retardants using Silicone Wristbands and Hand Wipes. Environ. Sci. Technol. acs.est.6b00030. https://doi.org/10.1021/acs.est.6b00030 Hammel, S.C., Phillips, A.L., Hoffman, K., Stapleton, H.M., 2018. Evaluating the Use of Silicone Wristbands To Measure Personal Exposure to Brominated Flame Retardants. Environ. Sci. Technol. 52, acs.est.8b03755. https://doi.org/10.1021/acs.est.8b03755 Harley, K.G., Marks, A.R., Chevrier, J., Bradman, A., Sjödin, A., Eskenazi, B., 2010. PBDE Concentrations in Women’s Serum and Fecundability. Environ. Health Perspect. 118, 699– 704. https://doi.org/10.1289/ehp.0901450

322

Harner, T., Bartkow, M., Holoubek, I., Klanova, J., Wania, F., Gioia, R., Moeckel, C., Sweetman, A.J., Jones, K.C., 2006. Passive air sampling for persistent organic pollutants: Introductory remarks to the special issue. Environ. Pollut. 144, 361–364. https://doi.org/10.1016/j.envpol.2005.12.044 Hartmann, P.C., Burgi, D., Giger, W., 2004. Organophosphate flame retardants and plasticizers in indoor air. Chemosphere 57, 781–787. https://doi.org/10.1016/j.chemosphere.2004.08.051 Hays, S.M., Kirman, C.R., 2017. Risk assessment and Biomonitoring Equivalent for 2- ethylhexyl-2,3,4,5 tetrabromobenzoate (TBB) and tetrabromobenzoic acid (TBBA). Regul. Toxicol. Pharmacol. 89, 186–192. https://doi.org/10.1016/j.yrtph.2017.07.022 Hazrati, S., Harrad, S., 2006. Causes of Variability in Concentrations of Polychlorinated Biphenyls and Polybrominated Diphenyl Ethers in Indoor air. Environ. Sci. Technol. 40, 7584–7589. https://doi.org/10.1021/es0617082 Heacock, M., Kelly, C.B., Asante, K.A., Birnbaum, L.S., Bergman, Å.L., Bruné, M.-N., Buka, I., Carpenter, D.O., Chen, A., Huo, X., Kamel, M., Landrigan, P.J., Magalini, F., Diaz- Barriga, F., Neira, M., Omar, M., Pascale, A., Ruchirawat, M., Sly, L., Sly, P.D., Van den Berg, M., Suk, W.A., 2015. E-Waste and Harm to Vulnerable Populations: A Growing Global Problem. Environ. Health Perspect. 124, 550–555. https://doi.org/10.1289/ehp.1509699 Heudorf, U., Mersch-Sundermann, V., Angerer, J., 2007. Phthalates: Toxicology and exposure. Int. J. Hyg. Environ. Health 210, 623–634. https://doi.org/10.1016/j.ijheh.2007.07.011 Hill, K.L., Hamers, T., Kamstra, J.H., Willmore, W.G., Letcher, R.J., 2018. Organophosphate triesters and selected metabolites enhance binding of thyroxine to human transthyretin in vitro. Toxicol. Lett. 285, 87–93. https://doi.org/10.1016/j.toxlet.2017.12.030 Hites, R.A., 2004. Polybrominated Diphenyl Ethers in the Environment and in People: A Meta- Analysis of Concentrations. Environ. Sci. Technol. 38, 945–956. https://doi.org/10.1021/es035082g Hoffman, K., Butt, C.M., Webster, T.F., Preston, E. V., Hammel, S.C., Makey, C., Lorenzo, A.M., Cooper, E.M., Carignan, C., Meeker, J.D., Hauser, R., Soubry, A., Murphy, S.K., Price, T.M., Hoyo, C., Mendelsohn, E., Congleton, J., Daniels, J.L., Stapleton, H.M., 2017a. Temporal Trends in Exposure to Organophosphate Flame Retardants in the United States. Environ. Sci. Technol. Lett. 4, 112–118. https://doi.org/10.1021/acs.estlett.6b00475 Hoffman, K., Lorenzo, A., Butt, C.M., Hammel, S.C., Henderson, B.B., Roman, S.A., Scheri, R.P., Stapleton, H.M., Sosa, J.A., 2017b. Exposure to flame retardant chemicals and occurrence and severity of papillary thyroid cancer: A case-control study. Environ. Int. 107, 235–242. https://doi.org/10.1016/j.envint.2017.06.021 Holmes, A.K., Koller, K.R., Kieszak, S.M., Sjodin, A., Calafat, A.M., Sacco, F.D., Varner, D.W., Lanier, A.P., Rubin, C.H., 2014. Case–control study of breast cancer and exposure to synthetic environmental chemicals among Alaska Native women. Int. J. Circumpolar Health 73, 25760. https://doi.org/10.3402/ijch.v73.25760

323

Hou, R., Xu, Y., Wang, Z., 2016. Review of OPFRs in animals and humans: Absorption, bioaccumulation, metabolism, and internal exposure research. Chemosphere 153, 78–90. https://doi.org/10.1016/j.chemosphere.2016.03.003 Hubinger, J.C., Havery, D.C., 2006. Analysis of consumer cosmetic products for phthalate esters. J. Cosmet. Sci. 57, 127–37. Hutter, H.-P., Haluza, D., Piegler, K., Hohenblum, P., Fröhlich, M., Scharf, S., Uhl, M., Damberger, B., Tappler, P., Kundi, M., Wallner, P., Moshammer, H., 2013. Semivolatile compounds in schools and their influence on cognitive performance of children. Int. J. Occup. Med. Environ. Health 26, 628–635. https://doi.org/10.2478/s13382-013-0125-z IARC Working Group on the Evaluation of Carcinogenic Risks to Humans, 2013. Some chemicals present in industrial and consumer products, food and drinking-water. IARC Monogr. Eval. Carcinog. Risks Hum. 101, 9–549. Igharo, O.G., Anetor, J.I., Osibanjo, O., Osadolor, H.B., Odazie, E.C., Uche, Z.C., 2018. Endocrine disrupting metals lead to alteration in the gonadal hormone levels in Nigerian e- waste workers. Universa Med. 37, 65. https://doi.org/10.18051/UnivMed.2018.v37.65-74 Iqbal, M., Syed, J.H., Breivik, K., Chaudhry, M.J.I., Li, J., Zhang, G., Malik, R.N., 2017. E- Waste Driven Pollution in Pakistan: The First Evidence of Environmental and Human Exposure to Flame Retardants (FRs) in Karachi City. Environ. Sci. Technol. 51, 13895– 13905. https://doi.org/10.1021/acs.est.7b03159 Jacobson, M.H., Barr, D.B., Marcus, M., Muir, A.B., Lyles, R.H., Howards, P.P., Pardo, L., Darrow, L.A., 2016. Serum polybrominated diphenyl ether concentrations and thyroid function in young children. Environ. Res. 149, 222–230. https://doi.org/10.1016/j.envres.2016.05.022 Jarema, K.A., Hunter, D.L., Shaffer, R.M., Behl, M., Padilla, S., 2015. Acute and developmental behavioral effects of flame retardants and related chemicals in zebrafish. Neurotoxicol. Teratol. 52, 194–209. https://doi.org/10.1016/j.ntt.2015.08.010 Julander, A., Westberg, H., Engwall, M., van Bavel, B., 2005. Distribution of brominated flame retardants in different dust fractions in air from an electronics recycling facility. Sci. Total Environ. 350, 151–160. https://doi.org/10.1016/j.scitotenv.2005.01.015 Kahhat, R., Williams, E., 2012. Materials flow analysis of e-waste: Domestic flows and exports of used computers from the United States. Resour. Conserv. Recycl. 67, 67–74. https://doi.org/10.1016/j.resconrec.2012.07.008 Kammerer, F., 2017. Safe Drinking Water and Toxic Enforcement Act of 1986. Environ. Heal. 1–22. Kile, M.L., Scott, R.P., O’Connell, S.G., Lipscomb, S., MacDonald, M., McClelland, M., Anderson, K.A., Gibson, E.A., Stapleton, H.M., Calero, L., Holmes, D., Burke, K., Martinez, R., Cortes, B., Nematollahi, A., Evans, D., Anderson, K.A., Herbstman, J.B., Fisher, M., Arbuckle, T.E., MacPherson, S., Braun, J.M., Feeley, M., Gaudreau, É., Dixon, H.M., Scott, R.P., Holmes, D., Calero, L., Kincl, L.D., Waters, K.M., Camann, D.E., Calafat, A.M., Herbstman, J.B., Anderson, K.A., Bohlin, P., Jones, K.C., Levin, J.O.,

324

Lindahl, R., Strandberg, B., 2019. Using silicone wristbands to evaluate preschool children’s exposure to flame retardants. Chemosphere 219, 567–573. https://doi.org/10.1007/s00216-018-0992-z Kim, E.-H., Jeon, B.-H., Kim, J., Kim, Y.-M., Han, Y., Ahn, K., Cheong, H.-K., 2017. Exposure to phthalates and bisphenol A are associated with atopic dermatitis symptoms in children: a time-series analysis. Environ. Heal. 16, 24. https://doi.org/10.1186/s12940-017-0225-5 Kim, Y.H., Wyrzykowska-Ceradini, B., Touati, A., Krantz, Q.T., Dye, J.A., Linak, W.P., Gullett, B., Gilmour, M.I., 2015. Characterization of Size-Fractionated Airborne Particles Inside an Electronic Waste Recycling Facility and Acute Toxicity Testing in Mice. Environ. Sci. Technol. 49, 11543–11550. https://doi.org/10.1021/acs.est.5b03263 Koniecki, D., Wang, R., Moody, R.P., Zhu, J., 2011. Phthalates in cosmetic and personal care products: Concentrations and possible dermal exposure. Environ. Res. 111, 329–336. https://doi.org/10.1016/j.envres.2011.01.013 Kuo, L., Cade, S.E., Cullinan, V., Schultz, I.R., 2019. Polybrominated diphenyl ethers (PBDEs) in plasma from E-waste recyclers, outdoor and indoor workers in the Puget Sound, WA region. Chemosphere 219, 209–216. https://doi.org/10.1016/j.chemosphere.2018.12.006 Kuriyama, S.N., Talsness, C.E., Grote, K., Chahoud, I., 2005. Developmental exposure to low- dose PBDE-99: Effects on male fertility and neurobehavior in rat offspring. Environ. Health Perspect. 113, 149–154. https://doi.org/10.1289/ehp.7421 La Guardia, M.J., Hale, R.C., Harvey, E., 2006. Detailed Polybrominated Diphenyl Ether (PBDE) Congener Composition of the Widely Used Penta-, Octa-, and Deca-PBDE Technical Flame-retardant Mixtures. Environ. Sci. Technol. 40, 6247–6254. https://doi.org/10.1021/es060630m Labunska, I., Harrad, S., Wang, M., Santillo, D., Johnston, P., 2014. Human Dietary Exposure to PBDEs Around E-Waste Recycling Sites in Eastern China. Environ. Sci. Technol. 48, 5555–5564. https://doi.org/10.1021/es500241m Lam, J., Lanphear, B.P., Bellinger, D., Axelrad, D.A., McPartland, J., Sutton, P., Davidson, L., Daniels, N., Sen, S., Woodruff, T.J., 2017. Developmental PBDE Exposure and IQ/ADHD in Childhood: A Systematic Review and Meta-analysis. Environ. Health Perspect. 125. https://doi.org/10.1289/EHP1632 Lenters, V., Portengen, L., Rignell-Hydbom, A., Jönsson, B.A.G., Lindh, C.H., Piersma, A.H., Toft, G., Bonde, J.P., Heederik, D., Rylander, L., Vermeulen, R., 2016. Prenatal Phthalate, Perfluoroalkyl Acid, and Organochlorine Exposures and Term Birth Weight in Three Birth Cohorts: Multi-Pollutant Models Based on Elastic Net Regression. Environ. Health Perspect. 124, 365–372. https://doi.org/10.1289/ehp.1408933 Li, F., Xie, Q., Li, X., Li, N., Chi, P., Chen, J., Wang, Z., Hao, C., 2010. Hormone Activity of Hydroxylated Polybrominated Diphenyl Ethers on Human Thyroid Receptor-β: In Vitro and In Silico Investigations. Environ. Health Perspect. 118, 602–606. https://doi.org/10.1289/ehp.0901457 Lilienthal, H., Hack, A., Roth-Härer, A., Grande, S.W., Talsness, C.E., 2006. Effects of

325

developmental exposure to 2,2′,4,4′, 5-pentabromodiphenyl ether (PBDE-99) on sex steroids, sexual development, and sexually dimorphic behavior in rats. Environ. Health Perspect. 114, 194–201. https://doi.org/10.1289/ehp.8391 Lippmann, M., 1998. The 1997 US EPA Standards for Particulate Matter and Ozone, in: Air Pollution and Health. pp. 75–100. https://doi.org/10.1039/9781847550095-00075 Little, J.C., Weschler, C.J., Nazaroff, W.W., Liu, Z., Cohen Hubal, E.A., 2012. Rapid Methods to Estimate Potential Exposure to Semivolatile Organic Compounds in the Indoor Environment. Environ. Sci. Technol. 46, 11171–11178. https://doi.org/10.1021/es301088a Liu, C., Zhang, Y., Weschler, C.J., 2017. Exposure to SVOCs from Inhaled Particles: Impact of Desorption. Environ. Sci. Technol. 51, 6220–6228. https://doi.org/10.1021/acs.est.6b05864 Lu, S.Y., Li, Y.X., Zhang, T., Cai, D., Ruan, J.J., Huang, M.Z., Wang, L., Zhang, J.Q., Qiu, R.L., 2017. Effect of E-waste Recycling on Urinary Metabolites of Organophosphate Flame Retardants and Plasticizers and Their Association with Oxidative Stress. Environ. Sci. Technol. 51, 2427–2437. https://doi.org/10.1021/acs.est.6b05462 Lucas, D., Petty, S.M., Keen, O., Luedeka, B., Schlummer, M., Weber, R., Barlaz, M., Yazdani, R., Riise, B., Rhodes, J., Nightingale, D., Diamond, M.L., Vijgen, J., Lindeman, A., Blum, A., Koshland, C.P., 2017. Methods of Responsibly Managing End-of-Life Foams and Plastics Containing Flame Retardants: Part I. Environ. Eng. Sci. https://doi.org/10.1089/ees.2017.0147 Ma, J., Addink, R., Yun, S., Cheng, J., Wang, W., Kannan, K., 2009. Polybrominated Dibenzo- p -dioxins/Dibenzofurans and Polybrominated Diphenyl Ethers in Soil, Vegetation, Workshop-Floor Dust, and Electronic Shredder Residue from an Electronic Waste Recycling Facility and in Soils from a Chemical Industrial Complex in Ea. Environ. Sci. Technol. 43, 7350–7356. https://doi.org/10.1021/es901713u MacIntosh, D.L., Minegishi, T., Fragala, M.A., Allen, J.G., Coghlan, K.M., Stewart, J.H., McCarthy, J.F., 2012. Mitigation of building-related polychlorinated biphenyls in indoor air of a school. Environ. Heal. A Glob. Access Sci. Source 11, 1–10. https://doi.org/10.1186/1476-069X-11-24 Mäkinen, M.S.E., Mäkinen, M.R.A., Koistinen, J.T.B., Pasanen, A.-L., Pasanen, P.O., Kalliokoski, P.J., Korpi, A.M., 2009. Respiratory and Dermal Exposure to Organophosphorus Flame Retardants and Tetrabromobisphenol A at Five Work Environments. Environ. Sci. Technol. 43, 941–947. https://doi.org/10.1021/es802593t Marek, R.F., Thorne, P.S., Herkert, N.J., Awad, A.M., Hornbuckle, K.C., 2017. Airborne PCBs and OH-PCBs Inside and Outside Urban and Rural U.S. Schools. Environ. Sci. Technol. 51, 7853–7860. https://doi.org/10.1021/acs.est.7b01910 Meeker, J.D., Cooper, E.M., Stapleton, H.M., Hauser, R., 2013. Exploratory analysis of urinary metabolites of phosphorus-containing flame retardants in relation to markers of male reproductive health. Endocr. Disruptors 1, e26306. https://doi.org/10.4161/endo.26306 Meeker, J.D., Stapleton, H.M., 2009. House Dust Concentrations of Organophosphate Flame Retardants in Relation to Hormone Levels and Semen Quality Parameters. Environ. Health

326

Perspect. 118, 318–323. https://doi.org/10.1289/ehp.0901332 Meironyté, D., Norén, K., Bergman, Å., 1999. Analysis of polybrominated diphenyl ethers in swedish human milk. A time-related trend study, 1972–1997. J. Toxicol. Environ. Heal. - Part A 58, 329–341. https://doi.org/10.1080/009841099157197 Melymuk, L., Robson, M., Helm, P.A., Diamond, M.L., 2011. Evaluation of passive air sampler calibrations: Selection of sampling rates and implications for the measurement of persistent organic pollutants in air. Atmos. Environ. 45, 1867–1875. https://doi.org/10.1016/j.atmosenv.2011.01.011 Mendelsohn, E., Hagopian, A., Hoffman, K., Butt, C.M., Lorenzo, A., Congleton, J., Webster, T.F., Stapleton, H.M., 2016. Nail polish as a source of exposure to triphenyl phosphate. Environ. Int. 86, 45–51. https://doi.org/10.1016/j.envint.2015.10.005 Moeckel, C., Harner, T., Nizzetto, L., Strandberg, B., Lindroth, A., Jones, K.C., 2009. Use of depuration compounds in passive air samplers: Results from active sampling-supported field deployment, potential uses, and recommendations. Environ. Sci. Technol. 43, 3227– 3232. https://doi.org/10.1021/es802897x Morrison, G.C., Weschler, C.J., Bekö, G., Koch, H.M., Salthammer, T., Schripp, T., Toftum, J., Clausen, G., 2016. Role of clothing in both accelerating and impeding dermal absorption of airborne SVOCs. J. Expo. Sci. Environ. Epidemiol. 26, 113–118. https://doi.org/10.1038/jes.2015.42 Muenhor, D., Harrad, S., Ali, N., Covaci, A., 2010. Brominated flame retardants (BFRs) in air and dust from electronic waste storage facilities in Thailand. Environ. Int. 36, 690–698. https://doi.org/10.1016/j.envint.2010.05.002 Nalli, S., Horn, O.J., Grochowalski, A.R., Cooper, D.G., Nicell, J.A., 2006. Origin of 2- ethylhexanol as a VOC. Environ. Pollut. 140, 181–185. https://doi.org/10.1016/j.envpol.2005.06.018 National Academies of Sciences Engineering and Medicine, 2017. Application of Systematic Review Methods in an Overall Strategy for Evaluating Low-Dose Toxicity from Endocrine Active Chemicals. The National Academies Press, Washington,DC. https://doi.org/10.17226/24758 Nguyen, L. V., Diamond, M.L., Venier, M., Stubbings, W.A., Romanak, K., Bajard, L., Melymuk, L., Jantunen, L.M., Arrandale, V.H., 2019. Exposure of Canadian electronic waste dismantlers to flame retardants. Environ. Int. 129, 95–104. https://doi.org/10.1016/j.envint.2019.04.056 Nguyen, L. V., Gravel, S., Labrèche, F., Bakhiyi, B., Verner, M.A., Zayed, J., Jantunen, L.M., Arrandale, V.H., Diamond, M.L., 2020. Can Silicone Passive Samplers be Used for Measuring Exposure of e-Waste Workers to Flame Retardants? Environ. Sci. Technol. 54, 15277–15286. https://doi.org/10.1021/acs.est.0c05240 North, M.L., Takaro, T.K., Diamond, M.L., Ellis, A.K., 2014. Effects of phthalates on the development and expression of allergic disease and asthma. Ann. Allergy, Asthma Immunol. 112, 496–502. https://doi.org/10.1016/j.anai.2014.03.013

327

NTP, 1991. Toxicology and Carcinogenesis Studies of TRIS(2- CHLOROETHYL)PHOSPHATE (CAS NO. 115-96-8) in F344 / N Rats. Natl. Toxicol. Program Tech. Rep. Ser. 409, 1–171. O’Connell, S.G., Kincl, L.D., Anderson, K.A., 2014. Silicone Wristbands as Personal Passive Samplers. Environ. Sci. Technol. 48, 3327–3335. https://doi.org/10.1021/es405022f Okeme, J.O., Nguyen, L. V., Lorenzo, M., Dhal, S., Pico, Y., Arrandale, V.H., Diamond, M.L., 2018a. Polydimethylsiloxane (silicone rubber) brooch as a personal passive air sampler for semi-volatile organic compounds. Chemosphere 208, 1002–1007. https://doi.org/10.1016/j.chemosphere.2018.05.196 Okeme, J.O., Nguyen, L. V., Lorenzo, M., Dhal, S., Pico, Y., Arrandale, V.H., Diamond, M.L., 2018b. Polydimethylsiloxane (silicone rubber) brooch as a personal passive air sampler for semi-volatile organic compounds. Chemosphere 208, 1002–1007. https://doi.org/10.1016/j.chemosphere.2018.05.196 Okeme, J.O., Parnis, J.M., Poole, J., Diamond, M.L., Jantunen, L.M., 2016a. Polydimethylsiloxane-air partition ratios for semi-volatile organic compounds by GC-based measurement and COSMO-RS estimation: Rapid measurements and accurate modelling. Chemosphere 156, 204–211. https://doi.org/10.1016/j.chemosphere.2016.04.094 Okeme, J.O., Rodgers, T.F.M., Jantunen, L.M., Diamond, M.L., 2018c. Examining the Gas- Particle Partitioning of Organophosphate Esters: How Reliable Are Air Measurements? Environ. Sci. Technol. 52, 13834–13844. https://doi.org/10.1021/acs.est.8b04588 Okeme, J.O., Saini, A., Yang, C., Zhu, J., Smedes, F., Klánová, J., Diamond, M.L., 2016b. Calibration of polydimethylsiloxane and XAD-Pocket passive air samplers (PAS) for measuring gas- and particle-phase SVOCs. Atmos. Environ. 143, 202–208. https://doi.org/10.1016/j.atmosenv.2016.08.023 Okeme, J.O., Yang, C., Abdollahi, A., Dhal, S., Harris, S.A., Jantunen, L.M., Tsirlin, D., Diamond, M.L., 2018d. Passive air sampling of flame retardants and plasticizers in Canadian homes using PDMS, XAD-coated PDMS and PUF samplers. Environ. Pollut. 239, 109–117. https://doi.org/10.1016/j.envpol.2018.03.103 Okonski, K., Degrendele, C., Melymuk, L., Landlová, L., Kukučka, P., Vojta, Š., Kohoutek, J., Čupr, P., Klánová, J., 2014. Particle Size Distribution of Halogenated Flame Retardants and Implications for Atmospheric Deposition and Transport. Environ. Sci. Technol. 48, 14426–14434. https://doi.org/10.1021/es5044547 Ospina, M., Jayatilaka, N.K., Wong, L.-Y., Restrepo, P., Calafat, A.M., 2018. Exposure to organophosphate flame retardant chemicals in the U.S. general population: Data from the 2013–2014 National Health and Nutrition Examination Survey. Environ. Int. 110, 32–41. https://doi.org/10.1016/j.envint.2017.10.001 Park, S.A., Gwak, S., Choi, S., 2014. Assessment of occupational symptoms and chemical exposures for nail salon technicians in Daegu City, Korea. J. Prev. Med. Public Heal. 47, 169–176. https://doi.org/10.3961/jpmph.2014.47.3.169 Pawar, G., 2017. Exploring the utility of 3-D skin models to evaluate trans-dermal uptake of

328

flame retardants from indoor dust and consumer product. University of Birmingham. Pelucchi, C., Negri, E., Gallus, S., Boffetta, P., Tramacere, I., La Vecchia, C., 2009. Long-term particulate matter exposure and mortality: a review of European epidemiological studies. BMC Public Health 9, 453. https://doi.org/10.1186/1471-2458-9-453 Percy, Z., Vuong, A.M., Ospina, M., Calafat, A.M., La Guardia, M.J., Xu, Y., Hale, R.C., Dietrich, K.N., Xie, C., Lanphear, B.P., Braun, J.M., Cecil, K.M., Yolton, K., Chen, A., 2020. Organophosphate esters in a cohort of pregnant women: Variability and predictors of exposure. Environ. Res. 184, 109255. https://doi.org/10.1016/j.envres.2020.109255 Pettersson-Julander, A., van Bavel, B., Engwall, M., Westberg, H., 2004. Personal air sampling and analysis of polybrominated diphenyl ethers and other bromine containing compounds at an electronic recycling facility in Sweden. J. Environ. Monit. 6, 874. https://doi.org/10.1039/b408381d Philippat, C., Bennett, D., Calafat, A.M., Picciotto, I.H., Xu, F., Giovanoulis, G., Van Waes, S., Padilla-Sanchez, J.A., Papadopoulou, E., Magnér, J., Haug, L.S., Neels, H., Covaci, A., 2016. Exposure to select phthalates and phenols through use of personal care products among Californian adults and their children. Environ. Res. 50, 7752–7760. https://doi.org/10.1021/acs.est.6b00246 Pinson, A., Bourguignon, J.P., Parent, A.S., 2016. Exposure to endocrine disrupting chemicals and neurodevelopmental alterations. Andrology 4, 706–722. https://doi.org/10.1111/andr.12211 Pope III, C.A., 2002. Lung Cancer, Cardiopulmonary Mortality, and Long-term Exposure to Fine Particulate Air Pollution. JAMA 287, 1132. https://doi.org/10.1001/jama.287.9.1132 Quach, T., Gunier, R., Tran, A., Von Behren, J., Doan-Billings, P.-A., Nguyen, K.-D., Okahara, L., Lui, B.Y.-B., Nguyen, M., Huynh, J., Reynolds, P., 2011. Characterizing Workplace Exposures in Vietnamese Women Working in California Nail Salons. Am. J. Public Health 101, S271–S276. https://doi.org/10.2105/AJPH.2010.300099 Radke, E.G., Braun, J.M., Meeker, J.D., Cooper, G.S., Agency, U.S.E.P., States, U., 2018. Phthalate exposure and male reproductive outcomes : A systematic review of the human epidemiological evidence. Environ. Int. 121, 764–793. https://doi.org/10.1016/j.envint.2018.07.029 Rakkestad, K.E., Dye, C.J., Yttri, K.E., Holme, J.A., Hongslo, J.K., Schwarze, P.E., Becher, R., 2007. Phthalate levels in Norwegian indoor air related to particle size fraction. J. Environ. Monit. 9, 1419. https://doi.org/10.1039/b709947a Rengasamy, S., Eimer, B., Shaffer, R.E., 2010. Simple respiratory protection - Evaluation of the filtration performance of cloth masks and common fabric materials against 20-1000 nm size particles. Ann. Occup. Hyg. 54, 789–798. https://doi.org/10.1093/annhyg/meq044 Richman, K.E., Butt, C.M., Young, C.J., 2018. Size-resolved particle measurements of polybrominated diphenyl ethers indoors: Implications for sources and human exposure. Environ. Toxicol. Chem. 37, 481–490. https://doi.org/10.1002/etc.3981 Robinson, B.H., 2009. E-waste: An assessment of global production and environmental impacts. 329

Sci. Total Environ. 408, 183–191. https://doi.org/10.1016/j.scitotenv.2009.09.044 Rodes, C.E., Kamens, R.M., Wiener, R.W., 1991. The Significance and Characteristics of the Personal Activity Cloud on Exposure Assessment Measurements for Indoor Contaminants. Indoor Air 1, 123–145. https://doi.org/10.1111/j.1600-0668.1991.03-12.x Romanak, K.A., Wang, S., Stubbings, W.A., Hendryx, M., Venier, M., Salamova, A., 2019. Analysis of brominated and chlorinated flame retardants, organophosphate esters, and polycyclic aromatic hydrocarbons in silicone wristbands used as personal passive samplers. J. Chromatogr. A 1588, 41–47. https://doi.org/10.1016/j.chroma.2018.12.041 Romero-Franco, M., Hernández-Ramírez, R.U., Calafat, A.M., Cebrián, M.E., Needham, L.L., Teitelbaum, S., Wolff, M.S., López-Carrillo, L., 2011. Personal care product use and urinary levels of phthalate metabolites in Mexican women. Environ. Int. 37, 867–871. https://doi.org/10.1016/j.envint.2011.02.014 Rosenberg, C., Hämeilä, M., Tornaeus, J., Säkkinen, K., Puttonen, K., Korpi, A., Kiilunen, M., Linnainmaa, M., Hesso, A., 2011. Exposure to Flame Retardants in Electronics Recycling Sites. Ann. Occup. Hyg. 55, 658–665. https://doi.org/10.1093/annhyg/mer033 Saini, A., Okeme, J.O., Goosey, E., Diamond, M.L., 2015. Calibration of two passive air samplers for monitoring phthalates and brominated flame-retardants in indoor air. Chemosphere 137, 166–173. https://doi.org/10.1016/j.chemosphere.2015.06.099 Saini, A., Okeme, J.O., Mark Parnis, J., McQueen, R.H., Diamond, M.L., 2016. From air to clothing: characterizing the accumulation of semi-volatile organic compounds to fabrics in indoor environments. Indoor Air. https://doi.org/10.1111/ina.12328 SCHETTLER, T., 2006. Human exposure to phthalates via consumer products. Int. J. Androl. 29, 134–139. https://doi.org/10.1111/j.1365-2605.2005.00567.x Schreder, E.D., Uding, N., La Guardia, M.J., 2016. Inhalation a significant exposure route for chlorinated organophosphate flame retardants. Chemosphere 150, 499–504. https://doi.org/10.1016/j.chemosphere.2015.11.084 Schwartz, J., Neas, L.M., 2000. Fine particles are more strongly associated than coarse particleswithacute respiratoryhealtheffectsinschoolchildren. Epidemiology 11, 6–10. Shi, T., Chen, S.-J., Luo, X.-J., Zhang, X.-L., Tang, C.-M., Luo, Y., Ma, Y.-J., Wu, J.-P., Peng, X.-Z., Mai, B.-X., 2009. Occurrence of brominated flame retardants other than polybrominated diphenyl ethers in environmental and biota samples from southern China. Chemosphere 74, 910–916. https://doi.org/10.1016/j.chemosphere.2008.10.047 Shoeib, M., Harner, T., 2002. Characterization and Comparison of Three Passive Air Samplers for Persistent Organic Pollutants. Environ. Sci. Technol. 36, 4142–4151. https://doi.org/10.1021/es020635t Sindiku, O., Babayemi, J., Osibanjo, O., Schlummer, M., Schluep, M., Watson, A., Weber, R., 2015. Polybrominated diphenyl ethers listed as Stockholm Convention POPs, other brominated flame retardants and heavy metals in e-waste polymers in Nigeria. Environ. Sci. Pollut. Res. 22, 14489–14501. https://doi.org/10.1007/s11356-014-3266-0

330

Singh, M., Thind, P.S., John, S., 2018. Health risk assessment of the workers exposed to the heavy metals in e-waste recycling sites of Chandigarh and Ludhiana, Punjab, India. Chemosphere 203, 426–433. https://doi.org/10.1016/j.chemosphere.2018.03.138 Sjödin, A., Carlsson, H., Thuresson, K., Sjölin, S., Bergman, Å., Östman, C., 2001. Flame Retardants in Indoor Air at an Electronics Recycling Plant and at Other Work Environments. Environ. Sci. Technol. 35, 448–454. https://doi.org/10.1021/es000077n Slotkin, T.A., Skavicus, S., Stapleton, H.M., Seidler, F.J., 2017. Brominated and organophosphate flame retardants target different neurodevelopmental stages, characterized with embryonic neural stem cells and neuronotypic PC12 cells. Toxicology 390, 32–42. https://doi.org/10.1016/j.tox.2017.08.009 Smil, V., 2017. PLANET OF THE COWS. IEEE Spectr. 54, 24. Snedeker, S.M., 2014. Toxicants in Food Packaging and Household Plastics, Molecular and Integrative Toxicology. Springer London, London. https://doi.org/10.1007/978-1-4471- 6500-2 Staaf, T., Ostman, C., 2005. Organophosphate triesters in indoor environments. J. Environ. Monit. 7, 883–887. https://doi.org/10.1039/b506631j Stapleton, H.M., Allen, J.G., Kelly, S.M., Konstantinov, A., Klosterhaus, S., Watkins, D., McClean, M.D., Webster, T.F., 2008a. Alternate and New Brominated Flame Retardants Detected in U.S. House Dust. Environ. Sci. Technol. 42, 6910–6916. https://doi.org/10.1021/es801070p Stapleton, H.M., Kelly, S.M., Allen, J.G., McClean, M.D., Webster, T.F., Stapleton, M.H., Kelly, S.M., Allen, J.G., McClean, M.D., Webster, T.F., Stapleton, H.M., Kelly, S.M., Allen, J.G., McClean, M.D., Webster, T.F., 2008b. Measurement of Polybrominated Diphenyl Ethers on Hand Wipes: Estimating Exposure from Hand-to-Mouth Contact. Environ. Sci. Technol. 42, 3329–3334. https://doi.org/10.1021/es7029625 Statistics Canada, 2016. EnviroStats Trash talking: Dealing with Canadian household e-waste. [WWW Document]. URL http://www.statcan.gc.ca/pub/16-002-x/2016001/article/14570- eng.htm (accessed 7.15.18). Stubbings, W.A., Nguyen, L. V., Romanak, K., Jantunen, L., Melymuk, L., Arrandale, V., Diamond, M.L., Venier, M., 2019a. Flame retardants and plasticizers in a Canadian waste electrical and electronic equipment (WEEE) dismantling facility. Sci. Total Environ. 675, 594–603. https://doi.org/10.1016/j.scitotenv.2019.04.265 Stubbings, W.A., Nguyen, L. V., Romanak, K., Jantunen, L., Melymuk, L., Arrandale, V., Diamond, M.L., Venier, M., 2019b. Flame retardants and plasticizers in a Canadian waste electrical and electronic equipment (WEEE)dismantling facility. Sci. Total Environ. 675, 594–603. https://doi.org/10.1016/j.scitotenv.2019.04.265 Suzuki, G., Tue, N.M., Malarvannan, G., Sudaryanto, A., Takahashi, S., Tanabe, S., Sakai, S., Brouwer, A., Uramaru, N., Kitamura, S., Takigami, H., 2013. Similarities in the Endocrine- Disrupting Potencies of Indoor Dust and Flame Retardants by Using Human Osteosarcoma (U2OS) Cell-Based Reporter Gene Assays. Environ. Sci. Technol. 47, 2898–2908.

331

https://doi.org/10.1021/es304691a Swedish Chemicals Inspectorate, 2003. Brominated flame retardants – Prospects of a national ban. KemI Report 4/03. Takigami, H., Suzuki, G., Hirai, Y., Sakai, S., 2008. Transfer of brominated flame retardants from components into dust inside television cabinets. Chemosphere 73, 161–169. https://doi.org/10.1016/j.chemosphere.2008.06.032 Tansel, B., 2017. From electronic consumer products to e-wastes: Global outlook, waste quantities, recycling challenges. Environ. Int. 98, 35–45. https://doi.org/10.1016/j.envint.2016.10.002 Thuresson, K., Höglund, P., Hagmar, L., Sjödin, A., Bergman, Å., Jakobsson, K., 2006. Apparent Half-Lives of Hepta- to Decabrominated Diphenyl Ethers in Human Serum as Determined in Occupationally Exposed Workers. Environ. Health Perspect. 114, 176–181. https://doi.org/10.1289/ehp.8350 Tran, T.M., Kannan, K., 2015. Occurrence of Phthalate Diesters in Particulate and Vapor Phases in Indoor Air and Implications for Human Exposure in Albany, New York, USA. Arch. Environ. Contam. Toxicol. 68, 489–499. https://doi.org/10.1007/s00244-015-0140-0 Tran, T.M., Le, H.T., Minh, T.B., Kannan, K., 2017. Occurrence of phthalate diesters in indoor air from several Northern cities in Vietnam, and its implication for human exposure. Sci. Total Environ. 601–602, 1695–1701. https://doi.org/10.1016/j.scitotenv.2017.06.016 Traore, I.T., Gravel, S., Diamond, M.L., Jantunen, L., Nguyen, L.V., Yang, C., Bernstein, S., Zayed, J., Labrèche, F., Verner, M.-A., 2018. Urinary Metabolites of Organophosphate Esters (OPEs) in Electronic Waste Recycling Workers from the Province of Quebec, Canada. ISEE Conf. Abstr. 2018, isesisee.2018.P01.3100. https://doi.org/10.1289/isesisee.2018.P01.3100 Tromp, P.C., Beeltje, H., Okeme, J.O., Vermeulen, R., Pronk, A., Diamond, M.L., 2019. Calibration of polydimethylsiloxane and polyurethane foam passive air samplers for measuring semi volatile organic compounds using a novel exposure chamber design. Chemosphere 227, 435–443. https://doi.org/10.1016/j.chemosphere.2019.04.043 Tue, N.M., Takahashi, S., Suzuki, G., Isobe, T., Viet, P.H., Kobara, Y., Seike, N., Zhang, G., Sudaryanto, A., Tanabe, S., 2013. Contamination of indoor dust and air by polychlorinated biphenyls and brominated flame retardants and relevance of non-dietary exposure in Vietnamese informal e-waste recycling sites. Environ. Int. 51, 160–167. https://doi.org/10.1016/j.envint.2012.11.006 U.S.Bureau of Labor, 2020. Occupational Outlook Handbook [WWW Document]. UCLA Labor Center, 2018. Nail Files: A study of nail salon workers and industry in United States. UNEP, 2019. A New Circular Vision for Electronics Time for a Global Reboot 24. UNEP, 2016. GEO-6 North America Regional Assessment [WWW Document]. URL http://wedocs.unep.org/bitstream/handle/20.500.11822/7611/GEO_North_America_201611

332

.pdf?sequence=1&isAllowed=y (accessed 6.27.18). UNEP, 2010. Technical review of the implications of recycling commercial pentabromodiphenyl ether and commercial octabromodi- phenyl ether. UNEP, 2008. Report of the Persistent Organic Pollutants Review Committee on the work of its fourth meeting. United States Department of Labor, 2017. Occupational Employment and Wages, May 2017 [WWW Document]. URL https://www.bls.gov/oes/current/oes395092.htm#st US EPA, 2018a. IRIS Assessments [WWW Document]. URL https://cfpub.epa.gov/ncea/iris2/atoz.cfm (accessed 6.27.18). US EPA, 2018b. Chemistry Dashboard [WWW Document]. URL https://comptox.epa.gov/dashboard (accessed 6.27.18). US EPA, 2018c. 2,2’,4,4’,5-Pentabromodiphenyl ether (BDE-99) [WWW Document]. URL https://cfpub.epa.gov/ncea/iris2/chemicalLanding.cfm?substance_nmbr=1008 (accessed 6.27.18). US EPA, 2011. September 2011 EXPOSURE FACTORS HANDBOOK : 2011 EDITION National Center for Environmental Assessment Office of Research and Development U . S . Environmental Protection Agency Washington , DC 20460 Exposure Factors Handbook. Exposure. USEPA, 2020. CHEMICALS KNOWN TO THE STATE TO CAUSE CANCER OR REPRODUCTIVE TOXICITY January 3, 2020. Veen, I. Van Der, Boer, J. De, 2012. Chemosphere Phosphorus flame retardants : Properties , production , environmental occurrence , toxicity and analysis. Chemosphere 88, 1119– 1153. https://doi.org/10.1016/j.chemosphere.2012.03.067 Venier, M., Ma, Y., Hites, R.A., 2012. Brominated flame retardants in the Great Lakes atmosphere. Environ. Sci. Technol. 46, 8653–8660. https://doi.org/dx.doi.org/10.1021/es3015919 Viberg, H., Fredriksson, A., Eriksson, P., 2004. Investigations of strain and/or gender differences in developmental neurotoxic effects of polybrominated diphenyl ethers in mice. Toxicol. Sci. 81, 344–353. https://doi.org/10.1093/toxsci/kfh215 Viberg, H., Fredriksson, A., Jakobsson, E., Orn, U., Erikson, P., 2003. Neurobehavioral derangements in adult mice receiving decabrominated diphenyl ether (PBDE 209) during a defined period of neonatal brain development. Toxicol. Sci. 76, 112–120. https://doi.org/10.1093/toxsci/kfg210 Vojta, Š., Bečanová, J., Melymuk, L., Komprdová, K., Kohoutek, J., Kukučka, P., Klánová, J., 2017. Screening for halogenated flame retardants in European consumer products, building materials and wastes. Chemosphere 168, 457–466. https://doi.org/10.1016/j.chemosphere.2016.11.032 Vuong, A.M., Braun, J.M., Webster, G.M., Thomas Zoeller, R., Hoofnagle, A.N., Sjödin, A.,

333

Yolton, K., Lanphear, B.P., Chen, A., 2018. Polybrominated diphenyl ether (PBDE) exposures and thyroid hormones in children at age 3 years. Environ. Int. 117, 339–347. https://doi.org/10.1016/j.envint.2018.05.019 Vuong, A.M., Yolton, K., Xie, C., Webster, G.M., Sjödin, A., Braun, J.M., Dietrich, K.N., Lanphear, B.P., Chen, A., 2017. Childhood polybrominated diphenyl ether (PBDE) exposure and neurobehavior in children at 8 years. Environ. Res. 158, 677–684. https://doi.org/10.1016/j.envres.2017.07.028 Vykoukalová, M., Venier, M., Vojta, Š., Melymuk, L., Bečanová, J., Romanak, K., Prokeš, R., Okeme, J.O., Saini, A., Diamond, M.L., Klánová, J., 2017. Organophosphate esters flame retardants in the indoor environment. Environ. Int. 106, 97–104. https://doi.org/10.1016/j.envint.2017.05.020 Wallace, L., 2000. Correlations of personal exposure to particles with outdoor air measurements: A review of recent studies. Aerosol Sci. Technol. 32, 15–25. https://doi.org/10.1080/027868200303894 Wallner, P., Kundi, M., Hohenblum, P., Scharf, S., Hutter, H., 2016. Phthalate Metabolites, Consumer Habits and Health Effects. Int. J. Environ. Res. Public Health 13, 717. https://doi.org/10.3390/ijerph13070717 Wan, Y., Diamond, M.L., Siegel, J.A., 2020. Elevated Concentrations of Semivolatile Organic Compounds in Social Housing Multiunit Residential Building Apartments. Environ. Sci. Technol. Lett. 7, 191–197. https://doi.org/10.1021/acs.estlett.0c00068 Wang, D.G., Alaee, M., Byer, J.D., Brimble, S., Pacepavicius, G., 2013. Human health risk assessment of occupational and residential exposures to dechlorane plus in the manufacturing facility area in China and comparison with e-waste recycling site. Sci. Total Environ. 445–446, 329–336. https://doi.org/10.1016/j.scitotenv.2012.12.059 Wang, S., Romanak, K.A., Stubbings, W.A., Arrandale, V.H., Hendryx, M., Diamond, M.L., Salamova, A., Venier, M., 2019. Silicone wristbands integrate dermal and inhalation exposures to semi-volatile organic compounds (SVOCs). Environ. Int. 132, 105104. https://doi.org/10.1016/j.envint.2019.105104 Wang, Y., Peris, A., Rifat, M.R., Ahmed, S.I., Aich, N., Nguyen, L. V., Urík, J., Eljarrat, E., Vrana, B., Jantunen, L.M., Diamond, M.L., 2020. Measuring exposure of e-waste dismantlers in Dhaka Bangladesh to organophosphate esters and halogenated flame retardants using silicone wristbands and T-shirts. Sci. Total Environ. 720, 137480. https://doi.org/10.1016/j.scitotenv.2020.137480 Wei, G.-L., Li, D.-Q., Zhuo, M.-N., Liao, Y.-S., Xie, Z.-Y., Guo, T.-L., Li, J.-J., Zhang, S.-Y., Liang, Z.-Q., 2015. Organophosphorus flame retardants and plasticizers: Sources, occurrence, toxicity and human exposure. Environ. Pollut. 196, 29–46. https://doi.org/10.1016/j.envpol.2014.09.012 Wei, W., Bonvallot, N., Gustafsson, Å., Raffy, G., Glorennec, P., Krais, A., Ramalho, O., Le Bot, B., Mandin, C., 2018. Bioaccessibility and bioavailability of environmental semi- volatile organic compounds via inhalation: A review of methods and models. Environ. Int. 113, 202–213. https://doi.org/10.1016/j.envint.2018.01.024

334

Wei, W., Mandin, C., Ramalho, O., 2017. Reactivity of Semivolatile Organic Compounds with Hydroxyl Radicals, Nitrate Radicals, and Ozone in Indoor Air. Int. J. Chem. Kinet. 49, 506–521. https://doi.org/10.1002/kin.21093 Weschler, C.J., Nazaroff, W.W., 2014. Dermal Uptake of Organic Vapors Commonly Found in Indoor Air. Environ. Sci. Technol. 48, 1230–1237. https://doi.org/10.1021/es405490a Weschler, C.J., Nazaroff, W.W., 2012. SVOC exposure indoors: Fresh look at dermal pathways. Indoor Air. https://doi.org/10.1111/j.1600-0668.2012.00772.x Weschler, C.J., Nazaroff, W.W., 2010. SVOC partitioning between the gas phase and settled dust indoors. Atmos. Environ. 44, 3609–3620. https://doi.org/10.1016/j.atmosenv.2010.06.029 Weschler, C.J., Nazaroff, W.W., 2008. Semivolatile organic compounds in indoor environments. Atmos. Environ. 42, 9018–9040. https://doi.org/10.1016/j.atmosenv.2008.09.052 Whitman, W.G., 1962. The two film theory of gas absorption. Int. J. Heat Mass Transf. 5, 429– 433. https://doi.org/10.1016/0017-9310(62)90032-7 Wielsøe, M., Kern, P., Bonefeld-Jørgensen, E.C., 2017. Serum levels of environmental pollutants is a risk factor for breast cancer in Inuit: a case control study. Environ. Heal. 16, 56. https://doi.org/10.1186/s12940-017-0269-6 Wong, C.S.C., Duzgoren-Aydin, N.S., Aydin, A., Wong, M.H., 2007. Evidence of excessive releases of metals from primitive e-waste processing in Guiyu, China. Environ. Pollut. 148, 62–72. https://doi.org/10.1016/j.envpol.2006.11.006 Wu, C.-C., Bao, L.-J., Tao, S., Zeng, E.Y., 2016. Dermal Uptake from Airborne Organics as an Important Route of Human Exposure to E-Waste Combustion Fumes. Environ. Sci. Technol. 50, 6599–6605. https://doi.org/10.1021/acs.est.5b05952 Xu, F., Zhang, G., Wang, J., Zhang, W., Liu, L., Lin, K., 2015. Polybrominated diphenyl ethers in air and fallouts from an e-waste polluted region in southeast China: insight into levels, compositional profiles, and seasonal variation. Environ. Sci. Pollut. Res. 22, 19676–19686. https://doi.org/10.1007/s11356-015-5168-1 Xu, Y., Cohen Hubal, E.A., Clausen, P.A., Little, J.C., 2009. Predicting Residential Exposure to Phthalate Plasticizer Emitted from Vinyl Flooring: A Mechanistic Analysis. Environ. Sci. Technol. 43, 2374–2380. https://doi.org/10.1021/es801354f Xu, Y., Cohen Hubal, E.A., Little, J.C., 2010. Predicting residential exposure to phthalate plasticizer emitted from vinyl flooring: Sensitivity, uncertainty, and implications for biomonitoring. Environ. Health Perspect. 118, 253–258. https://doi.org/10.1289/ehp.0900559 Yang, C., Harris, S.A., Jantunen, L.M., Kvasnicka, J., Nguyen, L. V., Diamond, M.L., 2020a. Phthalates: Relationships between Air, Dust, Electronic Devices, and Hands with Implications for Exposure. Environ. Sci. Technol. 54, acs.est.0c00229. https://doi.org/10.1021/acs.est.0c00229 Yang, C., Harris, S.A., Jantunen, L.M., Siddique, S., Kubwabo, C., Tsirlin, D., Latifovic, L.,

335

Fraser, B., St-Jean, M., De La Campa, R., You, H., Kulka, R., Diamond, M.L., 2018. Are cell phones an indicator of personal exposure to organophosphate flame retardants and plasticizers? Environ. Int. in press, 1–13. https://doi.org/10.1016/j.envint.2018.10.021 Yang, C., Jílková, S.R., Melymuk, L., Harris, S.A., Jantunen, L.M., Pertili, J., Winn, L., Diamond, M.L., 2020b. Are We Exposed to Halogenated Flame Retardants from both Primary and Secondary Sources? Environ. Sci. Technol. Lett. 7, 585–593. https://doi.org/10.1021/acs.estlett.0c00268 Young, A.S., Allen, J.G., Kim, U.-J.J., Seller, S., Webster, T.F., Kannan, K., Ceballos, D.M., 2018. Phthalate and Organophosphate Plasticizers in Nail Polish: Evaluation of Labels and Ingredients. Environ. Sci. Technol. 52, acs.est.8b04495. https://doi.org/10.1021/acs.est.8b04495 Zabiegała, B., Zygmunt, B., Przyk, E., Namieśnik, J., 2000. Applicability of silicone membrane passive samplers for monitoring of indoor air quality. Anal. Lett. 33, 1361–1372. https://doi.org/10.1080/00032710008543127 Zeng, X., Yang, C., Chiang, J.F., Li, J., 2017. Innovating e-waste management: From macroscopic to microscopic scales. Sci. Total Environ. 575, 1–5. https://doi.org/10.1016/j.scitotenv.2016.09.078 Zhang, H., Yolton, K., Webster, G.M., Sjödin, A., Calafat, A.M., Dietrich, K.N., Xu, Y., Xie, C., Braun, J.M., Lanphear, B.P., Chen, A., 2016. Prenatal PBDE and PCB Exposures and Reading, Cognition, and Externalizing Behavior in Children. Environ. Health Perspect. 125, 7–16. https://doi.org/10.1289/EHP478 Zhang, X., Diamond, M.L., Robson, M., Harrad, S., 2011. Sources, emissions, and fate of polybrominated diphenyl ethers and polychlorinated biphenyls indoors in Toronto, Canada. Environ. Sci. Technol. 45, 3268–3274. https://doi.org/10.1021/es102767g Zhang, Z., Sun, Z.-Z., Xiao, X., Zhou, S., Wang, X.X.-C., Gu, J., Qiu, L.-L., Zhang, X.-H., Xu, Q., Zhen, B., Wang, X.X.-C., Wang, S.-L., 2013a. Mechanism of BDE209-induced impaired glucose homeostasis based on gene microarray analysis of adult rat liver. Arch. Toxicol. 87, 1557–1567. https://doi.org/10.1007/s00204-013-1059-8 Zhang, Z., Zhang, X., Sun, Z., Dong, H., Qiu, L., Gu, J., Zhou, J., Wang, X., Wang, S.L., 2013b. Cytochrome P450 3A1 Mediates 2,2′,4,4′-Tetrabromodiphenyl Ether-Induced Reduction of Spermatogenesis in Adult Rats. PLoS One 8. https://doi.org/10.1371/journal.pone.0066301 Zheng, X., Xu, F., Chen, K., Zeng, Y., Luo, X., Chen, S., Mai, B., Covaci, A., 2015. Flame retardants and organochlorines in indoor dust from several e-waste recycling sites in South China: Composition variations and implications for human exposure. Environ. Int. 78, 1–7. https://doi.org/10.1016/j.envint.2015.02.006 Zota, A.R., Rudel, R.A., Morello-Frosch, R.A., Brody, J.G., 2008. Elevated House Dust and Serum Concentrations of PBDEs in California: Unintended Consequences of Furniture Flammability Standards? Environ. Sci. Technol. 42, 8158–8164. https://doi.org/10.1021/es801792z

336