s REPORT

M-1906 | 2020

Migration of chemical additives from products A literature review

COLOPHON

Executive institution

Norwegian Environment Agency

Project manager for the contractor Contact person in the Norwegian Environment Agency

Heidi Morka Marianne van der Hagen

M-no Year Pages Contract number

1906 2020 18 [Contract number]

Publisher The project is funded by

Norwegian Environment Agency Norwegian Environment Agency

Author(s)

Clare Andvik

Title – Norwegian and English

Migrasjon av tilsetningsstoffer fra plastprodukter: En vitenskapelig gjennomgang av litteratur Migration of chemical additives from plastic products: A literature review

Summary – sammendrag

Plastic polymers are often incorporated with various “additives”, which have the potential to migrate from plastic products and cause harm to both humans and the environment. This literature review gives an overview of the migration of chemical additives from plastic products used in building/construction materials, electronics, and furnishings/upholstery. Our scope was products used in the home, to reflect the possible exposure to consumers within the product lifetime. We found that within building/construction materials, the release of from plastic flooring is commonly measured, with DEHP having the highest migration rate and migration rates increasing with temperature. Within electronics, brominated flame retardants are often measured, but it is challenging to compare studies when differing measurement units are utilised. TCPP was commonly measured as emitted from furnishings/upholstery. These results will be used to commission an experiment to measure the release of chemical additives from plastic, with the aim of regulating chemical additives with high migration rates under REACH/CLP.

4 emneord 4 subject words

Tilsetningsstoffer; plast; migrasjon; utslipp Chemical additives; plastic; migration; release

Front page photo

Kjersti Moxness/Miljødirektoratet

Abbreviations

BBP butyl benzyl BDP bisphenolA-bis-biphenylphosphate BDE209 decabromodiphenyl ether BfR German Federal Institute for Risk Assessment (BfR) CLP Regulation (EC) No 1272/2008 on Classification, Labelling and Packaging of substances and mixtures DBP DEHA di(2-ethylhexyl) DEHP di-2-ethylhexyl phthalate DINCH diisononyl cyclohexane-1,2- dicarboxylate DINP diisononyl phthalate DnBP di-n-butyl phthalate ECHA European Chemicals Agency EE products Electric and electronic products EHDPP 2-Ethylhexyl diphenyl phosphate HBCD hexabromocyclododecane OECD Organisation for Economic Cooperation and Development OPE ester PLASI Plastic additives initiative PVC flooring Poly flooring REACH Regulation (EC) No 1907/2006 concerning Registration, Evaluation, Authorisation and Restriction of Chemicals RDP resorcinol-bis-biphenylphosphate SVOC Semi-volatile organic compounds

TBEB/TBOEP tris(2-butoxyethyl)phosphate TBP tributylphosphate TCEP tri(2- chloroethyl) phosphate TCIPP tris(chloropropyl)phosphate TCP tricrecylphosphate ΣTCPPs Sum of tris (2-chloro-isopropyl)phosphate isomers TDCIPP tris(1,3-dichloroisopropyl) phosphate TNBP tri-n-butyl phosphate

TPP/TPhP triphenylphosphate TVOCs Total volatile organic compounds

Migration of chemical additives from plastic products | M-1906

Content

1. Introduction ...... 1 1.1 Chemical additives in plastic ...... 1 1.2 Plastic additives initiative: PLASI ...... 1 1.3 Norwegian project ...... 2 2. Methods ...... 3 3. Results and discussion ...... 4 3.1 Building/construction materials ...... 4 3.2 Electronics ...... 7 3.3 Furnishings and upholstery ...... 11 4. Conclusion ...... 13 4.1 Knowledge gaps ...... 13 4.2 The next steps ...... 14 5. References ...... 15

Migration of chemical additives from plastic products | M-1906

1. Introduction

1.1 Chemical additives in plastic

Plastic polymers are widely used worldwide, including in consumer products, synthetic fibres, foams, coatings, adhesives and sealants, all of which have numerous applications (Hahladakis et al., 2018). The basic plastic polymer is often incorporated with various “additives”, which are chemical compounds added to improve the performance, functionality, appearance and/or aging quality of the polymer. Examples include flame retardants to reduce flammability, plasticisers to improve flexibility, stretchability and durability as well as antioxidants to delay the overall oxidative degradation of plastic if/when exposed to UV light (Hahladakis et al., 2018).

Many of these chemical additives have the potential to migrate from plastic products into the air, water and soil, and can cause harm to both humans and the environment. For example, cocktails of plastic-derived chemical additives have been shown to cause harm in zebra fish (Boyle et al., 2020), aquatic organisms (Capolupo et al., 2019), flame retardants from ingested plastic products can leach in avian digestive fluids (Guo et al., 2019), and many of the chemicals are harmful to humans (Lucattini et al., 2018). Identifying the magnitude and type of such emissions is a complex task, because it depends on many factors. In general, the fate of the polymer product, any substances released, any degradation process products and their persistence and bioaccumulation potential will affect the exposure to humans and the environment, both in the short and in the long term (Hahladakis et al., 2018). As such, migration of plastic additives has been a topic for many organisations such as United Nations Environment Programme (UNEP, 2019), the European Chemicals Agency (ECHA, PLASI project) and most recently a report on toxic additives in plastic and the circular economy coordinated by the Barcelona-based Regional Activity Centre for Sustainable Consumption and Production (SCP/RAC) in collaboration with the International Pollutants Elimination Network (IPEN) (SCP/RAP, 2020). The European Commission furthermore have a European Strategy for in a Circular Economy which includes controlling the release and exposure to humans and the environment of toxic chemical additives.

1.2 Plastic additives initiative: PLASI

In late 2016, the European Chemicals Agency (ECHA), along with 21 industry sector organisations, launched the plastic additives initiative (PLASI): a joint project to characterise the uses of plastic additives and the extent to which the additives may be released from plastic products. One of the objectives of the project was to help authorities (de)prioritise certain substances (ECHA, 2019, 2020). According to ECHA, plastic additives can be roughly divided into four groups: 1) functional additives (e.g. stabilisers, flame retardants and plasticisers), 2) colourants, 3) fillers and 4) reinforcements. The PLASI initiative addressed two of the four groups, functional additives and colourants (pigments), i.e. plastic additives with the following functions: Antioxidants, antistatics, flame retardants, nucleating agents,

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Migration of chemical additives from plastic products | M-1906 plasticisers, pigments, heat stabilisers, UV stabilisers, other stabilisers, and additives with other functions. The two-year project yielded a list of 418 substances that were confirmed by industry or registrants to be used as plastic additives in the EU. This is less than the ~10000 substances found to be associated with possible uses in plastics identified by ETH Zurich (Wiesinger et al., 2020). However, the ECHA plastic additives database includes only those chemicals registered with tonnages more than 100 tonnes per year under REACH. The substances in ECHA's list was identified as present in plastic based on non-confidential data and confirmed by the industry. The substance list furthermore does not include other additive types such as fillers, blowing agents or lubricants, monomers, polymers or transformation and degradation products. In addition to these 418 substances, additional possible plastic additives were identified which are also used in excess of 100 tonnes per year, but for which the status concerning their use as plastic additives is uncertain and that were identified (partly) on non- public data. Nearly 60% of the 418 identified substances are not under regulatory scrutiny under REACH or CLP so far (ECHA, 2019, 2020).

The PLASI project developed a method to compare the relative release potential of the various substances, i.e. the relationship between the additives in their ability to be released (migrate) from the plastic. This was determined by the physiochemical properties of the additives, i.e. chemical structure, molecular weight, and chemical-physical properties for neutral organic substances based on the OECD QSAR Toolbox, or chemical-physical properties for inorganic substances or salts based on data available via public dossiers published on ECHA’s dissemination website. Two indicator values for the relative release potential were developed, one corresponding to dermal exposure (also covering oral and water) and one corresponding to inhalation. Drivers for subsequent environmental exposure were not considered (e.g. mass-flow to product types and biodegradation). The method also did not compare exposure (per route) and risks, and nor was tested against measured data sets (ECHA, 2019, 2020). In ECHA (2019) the release indicators are explained in the following way: “The release indicators quantify the potential of the additive to be released from a particular polymer matrix compared to other additives in the same or different polymer matrix. The higher the figure, the higher the relative potential for release. For example, a substance with a release indicator value of -2 has a 10-fold release potential compared to a substance with an indicator value of -3.” The ranking methods have been applied to 155 organic plastic additives. The additive lists with assigned release indicators are not publicly available but are available to Member state competent authorities and to industry project partners. The release potential of plastic additives may be dependent on the type of plastic or product they are used in, but as this was not addressed in the PLASI report it is not considered further in this study.

1.3 Norwegian project

The Norwegian Environment Agency took an initiative to follow up on the results from the PLASI project, and this report is the first activity in a Norwegian project (provided funding is available for additional activities). The first phase of the project is a literature review to gather relevant measured datasets on the migration of chemical additives from plastic products (current report). In the following phases, we will consider commissioning real-life measurements of the migration of certain chemical additives from specific products. The final

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Migration of chemical additives from plastic products | M-1906 aim is to see if there are substances that should undergo regulatory scrutiny under REACH and CLP.

The scope of the project is chemical additives released from plastics used in building/construction materials, electric and electronic products (EE products) and furnishing/upholstery (e.g. plastic resin ) in the home. This thus represents sources of exposure in the indoor environment and reflects the use by consumers within the product lifetime (i.e. not during waste, landfill or recycling activities). Food contact materials and toys were excluded from this study due to large amounts of existing data available in these areas, for example from the German Federal Institute for Risk Assessment (BfR) who in 2012 published data on the release of phthalates in food packing and children’s toys (Umwelt & Gesundheit, 2012). Flame retardants are of particular interest to the Norwegian Environment Agency, who has already proposed such substances to regulatory action under REACH and CLP. We excluded flame-retardant treated textiles from the search as distinctions are often not drawn between plastic and natural fibre textiles. Our focus was plastic products used within the home, and thus we did not consider migration from plastic water pipes or leaching from roofs. Whilst we did not exclude oral/dermal exposure from the search, the types of products we were interested in testing meant inhalation would be the most dominating source of exposure, and thus migration to air was most likely to be measured.

2. Methods

A systematic review was conducted of all peer reviewed literature cited in the database Web of Science, which is one of the world’s largest publisher-independent global citation databases (Clarivate, 2020). The following search strings were utilised, based on topic:

“plastic additives” OR plasti* AND “chemical additives” OR “hazardous substances” AND plasti* AND migrat* OR leach* OR releas*

This resulted in 182 papers. After filtering for papers published in English between the years 2000 and 2020, 166 papers were then manually investigated for relevance and 19 added to the inventory.

The complementing document to the Organisation for Economic Cooperation and Development (OECD) emission scenario document on plastic additives, 2019 provided additional literature sources (OECD, 2019). A manual review of the reference list from key papers provided additional papers. Finally, we received suggestions and tips from members of the reference group for additional papers not captured in the original search. This yielded an additional 13 papers, and a final reference list of 32 papers.

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3. Results and discussion

We found that a large variation of units and methods were utilised in different studies to measure the release of chemical additives from plastic products. This made comparisons challenging, and is the reason for the wide range of units and/or test mechanisms in the following tables.

3.1 Building/construction materials

The scope of our project was emission of chemical additives from plastic products within the home, and thus our results from building/construction materials were focused on emissions from vinyl, poly vinyl chloride (PVC) and linoleum flooring (Table 1). Possible exposure from emissions are inhalation, and thus in all studies the emission rates were measured to air. Test chambers are commonly used to measure emissions, with defined temperature, humidity and air flow to allow reproducibility of experiments. Tenax TA tubes have also been utilised to estimate emissions from flooring to air.

Emission rates of plasticisers was the most commonly measured group of chemical additives. The phthalate DEHP has been measured the most frequently, and been used as a basis for estimating emission rates in other models (e.g. Delmaar, 2010; Liang et al., 2015). DEHP was found to have a faster release rate, likely due to its small molecule size and higher volatility in comparison to other phthalates such as DINP (Holmgren et al., 2012). In one study the Specific Area emission Rate (SER) was 3-fold lower for DINP compared to DEHP, and the SER of DINCH was 2-fold lower than DEHP (Holmgren et al., 2012, see table 1).

Total and semi-volatile organic compounds (TVOCs and SVOCs) from flooring were measured by the VTT technical research centre of Finland (Järnström et al., 2009). In all flooring types, the emission rates of TVOCs were higher than SVOCs. The SVOCs measured were difficult to identify from the mass spectra because of low concentration levels. Aliphatic hydrocarbons were however abundant. The VOCs identified were typical for the building products in question, i.e. aldehydes, glycols and glycolethers were the main compounds identified. No phthalates were detected from the air samples from any of the flooring types in this Finnish study, however, 218 µg of a phthalate compound was detected from the solvent used to rinse the walls of the chamber that was used to measure the PVC sample (Järnström et al., 2009).

Table 1.

Emission rates, emission factors or emission coefficients found in literature for building/construction materials Chemical Material Material Emission rate/ Unit Notes Reference name from to factor/coefficient DEHP Vinyl Air 1.6 x 10-4 – 5.4 x 10-4 μg/(m2s) Emission rate (Benning et flooring per surface al., 2013) area of flooring DEHP PVC Air 0.2-0.4 μg/(m2s) Controlled (Clausen et flooring chamber al., 2004) (CLIMPAQ)

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DEHP Vinyl Air 0.22±0.09 μg/(m2h) Specific area (Holmgren flooring emission rate et al., 2012) DINP Vinyl Air 0.073 ± 0.03 μg/(m2h) Specific area (Holmgren flooring emission rate et al., 2012) DINCH Vinyl Air 0.12 ± 0.05 μg/(m2h) Specific area (Holmgren flooring emission rate et al., 2012) DINP PVC floor Chamber 9.05 x 10-4 hmb(ms-1) (Cousins et walls al., 2014) DEHP Vinyl Air 0.8-0.9 μg/(m3days) Steady state (Xu et al., flooring after 20 days 2012)

DEHP PVC Air 10-10 m2/s Diffusion (Delmaar, flooring coefficient to 2010) air. TVOCs PVC Air- 2312 (23°C) μg/(m2h) Specific (Järnström flooring Tenax TA 9602 (40°C, after 60 emission rate. et al., tubes min) 2009) Main SVOCs PVC 2 (23°C) compounds flooring 5 (40°C, after 60 identified at min) 23°C: Ethanol,2- butoxy-, phenol, etha- nol, 2-(2- ethoxyethoxy)-, 2- pyrrolidone, 1-methyl-, ethanol, 2-(2- butoxyethanol)- , ethanol, phenoxy-, decanal

Main compounds identified at 40°C: Ethanol, 2-butoxy-, phenol, ethanol, 2-(2- ethoxyethoxy)-, 2-pyrrolidone, 1-methyl-, ethanol, 2-(2- butoxyethanol)- , ethanol, phenoxy-, decanal TVOCs Linoleum 572 (23°C) Main flooring 697 (40°C, after 60 compounds min) identified at 23°C: SVOCs Linoleum 7 (23°C) pentanal, flooring 48 (40°C, after 60 hexanal, min) nonanal, oc- tanal, acetic acid, hexanoic acid

Main compounds identified at 40°C: hexanal,

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nonanal, octanal, hexanoic acid, C16 => aliphatic hydrocarbons TVOCs Non-PVC 130 (23°C) Main plastic 303 (40°C, after 60 compounds flooring min) identified at 23°C and 40°C SVOCs Non-PVC 4 (23°C) : plastic 48 (40°C, after 60 aliphatic flooring min) hydrocarbons

In addition to the measured results in Table 1, other studies have looked at emissions from building/construction materials to estimate exposure. Based on the measured emission rate in Xu et al. (2012), it was estimated that the total emission of DEHP from vinyl flooring over 5 years would equate to just 0.001% of the total mass of DEHP in the product. The authors qualify this statement by stressing that the emission rate measured in the chambers might be different to that in real indoor environments. Despite small relative amounts emitted, it was estimated that the yearly emissions of DEHP from vinyl floors in Sweden was 210 kg in 2012 (Holmgren et al., 2012). This was higher than that estimated in other plasticisers (DINP: 40 kg per year and DINCH: 3.6 kg per year), but levels are likely to change in the coming years as many manufacturers substitute DINP with DINCH.

Dust has also been found to increase the emission rate in some circumstances. In one study, the dust layer was found to increase the emission rate of DEHP from flooring by increasing the external concentration gradient above the surface of the PVC. Dust was found to have sorbed about four times as much DEHP over a 68-day period as emitted in the gas- phase experiments (Clausen et al., 2004).

Emissions of chemical additives from flooring increase with increasing temperature (Liang and Xu, 2014; Järnström, Vares and Airaksinen, 2009). The emissions of the plasticisers DEHP, DINP, BBP, iso-DEHP, DnBP, DINCH and DEHA from vinyl flooring were measured in the air at four different temperatures: 25°C 36°C 45°C and 55°C (Liang and Xu, 2014). The emission rate was not calculated for each chemical additive, but rather the amount at which there was a steady state. Emissions increased significantly with increasing temperature, and it was estimated that a 10 degree increase in temperature in residential homes equates to an elevation of the gas-phase concentration of phthalates 10-fold. Similarly, the emission rate of TVOCs and SVOCs from flooring increased markedly when the temperature increased to 40°C (Järnström et al., 2009). The authors note that in real life, such temperatures can easily be reached on surfaces with direct sunlight during the summer, or in cases when floor heating is used.

Brominated flame retardants were measured but not found to be released from PVC and non- PVC flooring in Finland (Järnström et al., 2009). We could not find emission rates of these compounds from any other studies, although a study of 50 households in the Netherlands found that carpeted houses had significantly lower levels of flame retardants than homes with smooth floors such as laminate (Sugeng et al. 2018).

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3.2 Electronics

The main type of chemical additive used in electronics is flame retardants, and several studies have measured emission rates from electronic devices (Table 2). Kemmlein et al. (2003) found BDP to have the highest emission rate of several flame retardants tested from personal computers (44 ng h-1 unit-1). “Lower” BDEs (tri-, tetra-, penta- and hexa- BDEs) had higher emission rates from printed circuit boards than from TV set housings, whilst “higher” BDEs (hepta-, octa-, nona- and deca-) were only detected in TV set housings and not printed circuit boards (Kemmlein et al., 2003). Rauert et al. (2014) found TPHP to have the highest emission rate from computer monitors, and TDCIPP the lowest. Saito et al., (2007) found that TPHP was predominantly detected in computer monitors and TCEP in TV sets, with these having the highest median levels in each product respectively. Among the polybrominated compounds, only BDE- 47 was detected from a few old TV sets manufactured before 1995.

The phthalate DBP was also found in idle/operating notebook computers, with an estimated emission rate of 110-650 ng h-1 unit-1 (Hoshino, 2003). In general, emission rates increased with older devices and warmer temperatures, but comparisons between studies was challenging due to different units of emission and methods of calculation (e.g. to air vs. to chamber walls vs. to extraction disks). We found just one study estimating emission to artificial saliva: BDE-209 from TV casing (Ionas et al., 2016).

Table 2.

Emission rates, emission factors or emission coefficients found in literature for electronics Chemical Material from Material to Emission rate/ Unit Notes Reference name factor/coefficie nt RDP Personal Air 2 ng h-1 Unit: Desktop PCs (Kemmlein computers unit-1 in operation et al., 2003) BDP Personal 44 computers TCPP Personal 24 computers TPP Personal 25 computers DBP Personal Air 110-650 Unit: Notebook (Hoshino, computers computer 2003) idle/operating TriBDE TV set Air + n.d. ng Area specific (Kemmlein (BDE17) housing chamber m-2 h-1 emission rate at et al., walls 23°C. Production 2003) date <1979 Printed 0.6 ng h-1 Unit: printed circuit board unit-1 circuit board. Unit specific emission rate 60°C. Production date <2000 TriBDE TV set 0.2 ng Area specific (BDE18) housing m-2 h-1 emission rate at

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23°C. Production date <1979 Printed 1.9 ng h-1 Unit: printed circuit board unit-1 circuit board. Unit specific emission rate 60°C. Production date <2000 TetraBDE TV set 6.6 ng Area specific (BDE47) housing m-2 h-1 emission rate at 23°C. Production date <1979 Printed 14.2 ng h-1 Unit: printed circuit board unit-1 circuit board. Unit specific emission rate 60°C. Production date <2000 TetraBDE TV set 0.5 ng Area specific (BDE66) housing m-2 h-1 emission rate at 23°C. Production date <1979 Printed 0.4 ng h-1 Unit: printed circuit board unit-1 circuit board. Unit specific emission rate 60°C. Production date <2000 PentaBDE TV set 0.5 ng Area specific (BDE100) housing m-2 h-1 emission rate at 23°C. Production date <1979 Printed 1.3 ng h-1 Unit: printed circuit board unit-1 circuit board. Unit specific emission rate 60°C. Production date <2000 PentaBDE TV set 1.7 ng Area specific (BDE99) housing m-2 h-1 emission rate at 23°C. Production date <1979 Printed 2.6 ng h-1 Unit: printed circuit board unit-1 circuit board. Unit specific emission rate 60°C. Production date <2000 PentaBDE TV set n.d. ng Area specific (BDE85) housing m-2 h-1 emission rate at 23°C. Production date <1979 Printed 0.1 ng h-1 Unit: printed circuit board unit-1 circuit board. Unit specific emission rate 60°C. Production date <2000 HexaBDE TV set 0.2 ng Area specific (BDE154) housing m-2 h-1 emission rate at

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23°C. Production date <1979 Printed 0.1 ng h-1 Unit: printed circuit board unit-1 circuit board. Unit specific emission rate 60°C. Production date <2000 HexaBDE TV set 1 ng Area specific (BDE153) housing m-2 h-1 emission rate at 23°C. Production date <1979 Printed 0.04 ng h-1 Unit: printed circuit board unit-1 circuit board. Unit specific emission rate 60°C. Production date <2000 ΣHeptaBDE TV set 4.5 ng Area specific housing m-2 h-1 emission rate at 23°C. Production date <1979 Printed n.d. ng h-1 Unit: printed circuit board unit-1 circuit board. Unit specific emission rate 60°C. Production date <2000 ΣOctaBDE TV set 1.5 ng Area specific housing m-2 h-1 emission rate at 23°C. Production date <1979 Printed n.d. ng h-1 Unit: printed circuit board unit-1 circuit board. Unit specific emission rate 60°C. Production date <2000 ΣNonaBDE TV set 0.8 ng Area specific housing m-2 h-1 emission rate at 23°C. Production date <1979 Printed n.d ng h-1 Unit: printed circuit board unit-1 circuit board. Unit specific emission rate 60°C. Production date <2000 ΣDecaBDE TV set 0.3 ng Area specific housing m-2 h-1 emission rate at 23°C. Production date <1979 Printed n.d ng h-1 Unit: printed circuit board unit-1 circuit board. Unit specific emission rate 60°C. Production date <2000 TCEP Monitors <5-34 ng h-1 Unit: monitors. (Rauert et unit-1 al., 2014) TCIPP <5-2465

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TDCIPP Air + <5 Unit specific chamber emission rate TNBP 10-18 walls TPHP 23-133 TBP Computer Solid n.d. μg/m2 Migration rates. (Saito et monitor extraction /h Median and range al., 2007) disk (max-min). TV set n.d. (n.d.-0.17) TCPP Computer n.d. Computer monitor monitors: manufactured TV set 0.42 (n.d.-1.7) between 1996 and 2002 (2 Japanese TCEP Computer n.d. companies and 3 monitor US companies, TV set 1.4 (n.d. 13.0) made in Korea, Thailand or TBEB Computer n.d. Japan). monitor TV set n.d. (n.d.-0.32) TV sets: manufactured TDCPP Computer n.d. (n.d.-0.28) between 1989 and monitor 2001 (average 1995) by six TV set n.d. Japanese TPhP Computer 0.69 (n.d.-20.7) companies made in monitor Korea or Japan).

TV set 0.33 (n.d.-6.7) Higher levels in older TV sets and TCP Computer n.d. (n.d.-5.9) computer monitor monitors. TV set n.d.

BDE-47 Computer n.d. monitor TV set n.d. (n.d.-0.74) BDE-209 TV casing Artificial 1.52E-01 – ug/c Migration rate (Ionas et saliva 1.86e-01 m2/hr from (EPA, 2019) al., 2016)

(n.d = not detected)

There are also several other studies which have drawn links between the presence and use of electronic devices and levels of flame retardants in humans and the environment. Yang et al. (2018) found that handheld electronic devices, notably cell phones, may be sources of organophosphate ester (OPE) flame retardant human exposure through hand-to-mouth and/or dermal uptake. OPE levels in the urine of the subjects were related to levels in handwipes taken from the electronic devices, with the levels in the handwipes from cell phones the strongest explanatory variable. The electronic devices included cell phones, home phones, tablets, laptop computers, desktop computers, televisions and stereos. Prior to sampling the devices, surface dust was removed so that the case itself was sampled. The following OPEs were detected in >80% of the samples: TCEP, ΣTCPPs, TDCIPP, TPHP, EHDPP, TBOEP. Age, hours of operation of electronics, and use of the standby function were also positively associated with OPE levels in 50 households in the Netherlands (Sugeng et al., 2018). Frequent vacuuming and dusting reduced OPE levels in dust, and the addition of an electronic device in the house purchased before 2008 increased BDE209 levels in house dust significantly and by 66%.

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3.3 Furnishings and upholstery

Plastic is also commonly used in furnishings and upholstery, such as in mattresses, wall coverings and foam. The emission rate of chemical additives (flame retardants) are summarised in Table 3. TCPP was the chemical additive studied the most often, and emission rates have been measured from a range of products. Kemmlein et al. (2003) found the highest TCPP emission rate from rough, stored assembly foam, and the lowest in mattresses. In the same study, emissions of HBCD were higher from a larger sample of polystyrene, and an order of magnitude higher in extruded polystyrene than expandable. Ni, et al. (2007) found that higher concentrations of TCPP in wallpaper coverings, and higher temperatures, significantly increased the emission rate of TCPP.

Table 3.

Emission rates, emission factors or emission coefficients found in literature for furnishings/upholstery Chemical Material from Material Emission rate/ Unit Notes Reference name to factor/coefficient TCPP Insulating Air 0.21 μg(m-2h-1) Area-specific air- (Kemmlein board (80gl-1) flow emission et al., (2001) rate 2003) Date of Assembly 70 production of foam (rough, product in new) (2000) brackets in Assembly 50 “material from” foam column. (smooth, new) (2000) Upholstery 36 stool (2002) Mattress 0.012 (2000) Insulating 0.60 board (30gl-1) (2001) Assembly 140 foam (rough, stored) Assembly 50 foam (smooth, stored) Upholstery 77 foam (2000) HBCD Expandable Chamber 4 ng(m-2h-1) Total content on polystyrene walls chamber walls. (0.02m3) Date of (2001) production of product in Expandable 1 brackets in polystyrene “material from” (0.001m3) column. (2001) Extruded 29 polystyrene

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(0.02m3) (2001) Extruded 0.1 polystyrene (0.001m3) (2001) 1% TCPP Wallpaper Air Mean 262.3 (SD μg(m2h-1) 25°C (Ni et al., materials 29.3) 2007) 3% TCPP Mean 452.6 (SD 60.6) 5% TCPP Mean 644.8 (SD 94.2) 10% TCPP Mean 1119.1 (SD 1119.1) 20% TCPP Wallpaper Air Mean 2166.8 (SD 25°C materials 2166.8) 5% TCPP 1135.7 40°C 5% TCPP 2841.2 60°C TVOCs Polyurethane Air- 5-66 (23°C) μg/(m2h) Specific emission (Järnström insulation Tenax 48-148 (40°C, rate. et al., 2009) (foam) TA tubes after 60 min) Main compounds SVOCs Polyurethane 5-66 (23°C) identified at insulation 1-76 (40°C, after 23°C: Decanal, 2- (foam) 60 min) methyl- 2ñpentenal, tetradecane

Main compounds identified at 40°C: Cyclohexamine, 2-methyl- 2 ñpentenal, tetradecane , tris (1,3- dichloroisopropyl) phosphate TVOCs Expanded 153-408 (23°C) Specific emission polystyrene 193-410 (40°C, rate. after 60 min) Main compounds SVOCs Expanded 1-7 (23°C) identified at polystyrene 1-6 (40°C, after 23°C and 40°C: 60 min) Ethylbenzene, styrene, phenylethanone, xylenes TCPP Furniture Artificial 1.07E+01 – ug/cm2/hr Migration rate (Ghanem, foam saliva 9.24E+00 Concentration of 2015) chemical in material ranged from 52000-85000 ppm

(n.d = not detected)

In Uhde et al. (2001), specific emission rates were not calculated, and thus were not included in Table 3. However, the levels of various phthalates were measured after placing PVC wall

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Migration of chemical additives from plastic products | M-1906 coverings, containing 30% esters, in a test chamber for a 14 day period under standard room conditions (23°C). Emissions were higher in phthalates with lower boiling points than higher. During a 14-day test period, both the chamber air concentrations and the condensation on a cooled plate (fogging) were determined. In the chamber air, maximum concentrations of 5.1 mg/m3 for DBP, 2.08 mg/m3 for DPP and 0.94 mg/m3 for DEHP were found. After 14 days of exposure, up to 60.4 μg DEHP and 17.7 μg DPP could be quantified on the cooled plates. The amounts of DBP and DIBP were significantly lower than the other measured phthalates. A simple exposure calculation indicated no specific risk of an increased phthalate exposure in rooms with PVC wall coverings.

Liang and Xu (2014) estimated emissions of DEHA and DINCH from crib mattress covers at different temperatures using a specially designed chamber, finding higher emissions at higher temperatures. Following this, the authors validated an emission model for predicting concentrations in indoor air. Results showed a concentration of 0.7 μg/m3 in indoor air for DINCH and 1.05 μg/m3 for DEHA.

The VTT technical research centre of Finland detected Tris (2- chloroisopropyl) phosphate (TCCP) from air samples taken from the polyurethane insulation (foam type) at 24 µg/m2h after 120 minutes at 40°C (Järnström et al., 2009). No other flame retardants were detected as from the air from furnishing and upholstery, but they did detect 72 ng of hexabromocyclododecane (HBCD) from the rinsing samples of the chamber used for measuring expanded polystyrene (EPS) insulation.

4. Conclusion

4.1 Knowledge gaps

The literature review revealed several important knowledge gaps that should be addressed in future research.

1. “Real-life” migration datasets: The studies summarised above give the measured release of chemical additives from plastic products under normal conditions, such as would be found within the home. However, when conducting the literature search, such “real-life” migration datasets were in the minority. Many papers have focused on release at landfill sites (e.g. Kim et al., 2006; Kang et al., 2016; Dietsche et al., 2017), and measured experiments have thus been conducted to replicate these conditions, i.e. under different pHs and high temperatures (e.g. Chen et al., 2019; Noguchi and Yamasaki, 2020). With the scope of this project being on release within the home under the product’s normal use, there was a lack of suitable measured datasets. Other papers have linked amounts found in dust or air in the home to certain products, but with no emission calculations conducted.

2. Product specifications were missing from the papers. Many state that they measured from “computer monitors”, “cell phones” or “TV casing”, but only in Kemmlein et al. 2003 and Saito et al. 2007 were the manufacturing dates of the products disclosed. Saito et al. 2007 additionally stated the location of the product manufacturing, but

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more detailed information on the brand or type was not stated. The storage life of products will also have an impact. This makes it challenging to replicate the studies in a future migration experiment and necessitates a content analysis prior to the emission experiments.

4.2 The next steps

The way forward for this project is complex for several reasons. Firstly, it is challenging to know exactly which plastic products contain which chemical additives. The plastic additives sector does not know exactly where the products end up (e.g. plastic pellets marketed in bulk). Secondly, any commissioned real-life measurements cannot be directly compared to the PLASI release potentials, and it would not be possible to validate the ranking measures with measurements as very different things are measured. Our final aim is to identify chemical additives that should undergo regulatory scrutiny under REACH and CLP.

1. Possible collaboration with ETH Zurich group: A group is working on identifying which chemical additives are most likely to be emitted from plastics and can cause the greatest hazard to humans and environment through both literature searches and experimental work. This group could be consulted when choosing which chemicals and products to measure release/migration from.

2. Choose chemical additives: It has been suggested by members of the reference group to choose a combination of chemical additives with different release potentials. This will enable a wide scope for a more useful supplement to the PLASI results. To exaggerate the release potential differences picked up by real life studies, it is suggested to consider the extremes and then parts of the middle section substances (i.e. substances with predicted high and middle scoring release potentials). However, it has been indicated that the chemical additives do not necessarily need to be PLASI- ranked chemicals. Any potential candidate for testing can be characterised for its release-potential with the PLASI method.

We will also consider choosing chemicals based on the relevant regulatory actions that are in process, for example the restriction of PFAS, and the pending restriction of the organophosphate flame retardants (TCEP, TCPP and TCDP) in furniture foam and textiles. Brominated and chlorinated flame retardants are also of especial interest, and potentially TBBPA (CAS 79-94-7) and BMP (CAS 3296-90-0). Alternatives to dechlorane plus would also relevant, as well as potentially some PFAS. We will also consider choosing chemical additives that have been found in environmental screening and are listed in PLASI.

We will furthermore consult ECHA’s Substances of Concern in Products (SCIP) database for advice on choosing chemical additives.

3. Choose product types: Possible products for analysis include electrical products (e.g. electronic leads and cables), furniture foam (e.g. PUR ) and building materials made of plastic. A content analysis should be conducted to confirm presence of the chosen chemical additives in various product types before commencement of the migration study. This can potentially be completed at a low cost he by using non-

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destructive methods, e.g. Gallen et al. (2014) found that surface wipes of products successfully identified the presence of brominated flame retardants, which were later confirmed by destructive chemical testing. This content analysis could potentially be completed by ETH Zurich.

4. Commission migration study: Once chemicals and products have been chosen, an experiment can be commissioned to measure the release of the chemical additives from plastic products. We have been advised by the reference group to, ideally, run the following tests: 1) emission to solution of ethanol/water (taken as basis for dermal exposure in PLASI); 2) emission to water (taken as reference for saliva and environment in PLASI); 3) emission to sweat (to simulate dermal exposure and potentially validate assumptions of using ethanol/water solution as reference for dermal exposure, see test 1); 4) emission to air via chamber test. The number/type of tests should depend on the product types chosen and be reflective of their use. Existing test protocols should be followed where available. We plan for the first phase of the project to be focused on electronic cables before moving on to other products.

5. Use results for further regulatory work: New migration datasets can assist in defending and/or refining the release potential measurements within models which were used in PLASI. This can also assist in identifying certain chemical additives that should undergo regulatory scrutiny under REACH and CLP.

The migration of chemical additives from plastics potentially represent a risk for both humans and the environment. By calculating the emission rate and exposure of particularly harmful additives, a strong case can be developed for the regulation of these chemicals under REACH and CLP with the aim to ensure safe use of chemicals.

We thank the reference group for valuable contributions in the project so far and look forward to the continuation of the project.

Members of the reference group: Name Affiliation Andreas Ahrens ECHA Stefano Frattini ECHA Henna Piha ECHA Astrid Heiland BfR Wouter ter Burg RIVM Cathrine Thomsen NIPH Valentina Bertato DG ENV

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