Identification of Organic Contaminants in Indoor Dust by Comprehensive Target, Suspect and Nontarget Screening Analysis

Identification of organic contaminants in indoor dust by comprehensive target, suspect and nontarget screening analysis

Report authors Responsible publisher Thanh Wang, Örebro University Örebro University Florian Dubocq, Örebro University Postal address School of Science and Technology Örebro University

S-701 82 Örebro SWEDEN Telephone 019-30 3462 Report title and subtitle Purchaser Identification of organic contaminants in indoor Swedish Environmental Protection Agency, dust by comprehensive target, suspect and Environmental Monitoring Unit nontarget screening analysis SE-106 48 Stockholm, Sweden Keywords for location (specify in Swedish) Örebro, Motala Keywords for subject (specify in Swedish) Inomhusdamm, organiska föroreningar, nontarget screening, förutsättningslös screening Period in which underlying data were collected 2019-2020

Sammanfattning I norra Europa tillbringar vi mer än 90% av vår tid i olika inomhusmiljöer och kemikalier som avges från byggmaterial och produkter kan vara viktiga exponeringsvägar för människor som vistas i dessa miljöer. Många industriella kemikalier används som tillsatser och dessa är vanligtvis inte kemiskt bundna till materialet och kan därför avges i inomhusmiljön över tid eller under användning. Inomhusdamm har påvisats vara en bra indikator för polära och icke-polära organiska föroreningar i inomhusmiljön. I denna studie insamlades damm på ytor från olika inomhusmiljöer såsom bostäder, kontor, förskolor, tryckeri, möbelaffär och elektronikbutik. De insamlade inomhusdammproverna extraherades med ultraljudsextraktion utan provupprening för att minimera förlust av ämnen under provberedningsproceduren. Extraktet delades upp och analyserades med både vätskekromatograf kopplad till högupplösande masspektrometer (LC-HRMS) och gaskromatograf kopplad till HRMS (GC-HRMS). En omfattande analystrategi med riktad analys av ett antal förvalda ämnen, en så kallad suspect screening och förutsättningslös analys genomfördes, vilket resulterade i detektion av mer än 260 ämnen i inomhusdamm. Dessa inkluderar kemikalier som används som flamskyddsmedel, mjukgörare, flytkristallmonomerer (liquid crystal monomers, LCMs), aktiva ingredienser i läkemedel och personvårdsprodukter, desinfektionsmedel, färgämnen, högfluorerade ämnen, UV-stabilisatorer, bekämpningsmedel, doftämnen och växtmetaboliter. Potentiella riskerna som är förknippade med inomhusdammsexponering av många av dessa kemikalierna samt kombinationseffekter är inte välkända. Majoriteten av den kemiska sammansättningen i inomhusdammproverna är fortfaranade inte klarlagt och många häsloskadliga föroreningar som kan finnas i proven kan fortfarande inte identifieras. Studier rekommenderas för att identifera fler ämnen genom förbättrade analysmetoder eller förfina identifieringsflöden genom att till exempel utöka så kallade suspect list med fler högkvalitativa HRMS-spektra av ämnen som ännu inte finns tillgängliga.

Summary In Northern Europe, we spend more than 90% of our time in different indoor settings, and chemicals released from building materials and products from these environments can be significant exposure routes to humans. Many industrial chemicals are used as additives and these are usually not chemically bound to the material and can therefore be released to the indoor environment over time or during application. There is an increasing interest to study the presence of organic contaminants in indoor environments, and indoor dust has mainly been investigated since this matrix has been shown to be a good indicator of indoor semivolatile, nonpolar and polar organic contaminants. In this study, we collected indoor dust from different indoor settings such as households, offices, preschools, printing workshop, furniture store and electronics store. The collected indoor dust samples were extracted using solid-liquid ultrasonication extraction and no sample clean-up was conducted to minimize loss of compounds during the sample preparation procedure. The extract was split and analyzed using both liquid chromatography coupled with high resolution mass spectrometry (LC-HRMS) and gas chromatography coupled with HRMS (GC- HRMS). A combination of target analysis of a preselected number of compounds as well as a wide- scope suspect screening (>10000 compounds with HRMS fragment spectrum) and nontarget strategies (mass defect plots) were conducted which resulted in more than 260 compounds being detected at a high identification confidence level among the indoor samples. These included chemicals that are used as flame retardants, plasticizers, liquid crystal monomers (LCMs), active ingredients in pharmaceuticals and personal care products (PCPs), disinfectants, dyes and paint pigments, per- and polyfluoroalkyl substances (PFAS), UV stabilizers, various additives, pesticides, fragrances and plant metabolites. The potential risks associated with indoor dust exposure of many of the detected chemicals are not well known, and there is even less knowledge about the combined toxicity effects of the chemical mixtures. Furthermore, most of the chemical composition in the indoor dust samples are still not identified and important chemicals that might pose health risks might be missed. Further studies are therefore recommended to develop even more comprehensive workflows to either prioritize identification by criteria such as risk scores or improved identification schemes by for example extending the list of suspects by generating more high quality HRMS spectra that are not yet openly available.

Table of Contents ...... 1 1. Frame of the study ...... 6 2. Background ...... 6 3. Collection of samples ...... 7 4. Chemical analysis ...... 11 4.1. Extraction procedure ...... 11 4.2. Chemical analysis ...... 11 5. Data analysis workflows ...... 12 5.1. Target analysis workflow ...... 12 5.2. Suspect screening and nontarget analysis workflow ...... 13 5.4. QA/QC ...... 13 5.5. Reporting identification confidence level ...... 14 6. Results and discussion ...... 16 Organic flame retardants ...... 18 Various additives to materials/products...... 19 Liquid crystal monomers (LCMs) ...... 22 Pharmaceuticals and personal care products (PPCP) ...... 22 Antiseptic and disinfectants: ...... 23 Dyestuff and paint pigments ...... 23 Per- and polyfluoroalkyl substances (PFAS) ...... 24 UV stabilizers ...... 24 Pesticides, fungicides and herbicides ...... 24 Fragrances ...... 25 Plant or fungal derived chemicals ...... 26 Tobacco smoke chemicals ...... 27 Chemicals only detected in NIST SRM sample...... 27 7. Main findings ...... 27 8. Conclusions and suggested future works ...... 28 9. Acknowledgements...... 29 10. References ...... 30 Appendix 1. Target compounds for GC-HRMS...... 35 Appendix 2. Target compounds using LC-HRMS in positive and negative modes...... 40 Appendix 3. List of detected compounds ...... 41

1. Frame of the study The objective of this screening analysis was to investigate the chemical composition of indoor dust in regard to organic contaminants that are both known and unknown, by implementing an iterative and comprehensive analytical workflow. Indoor dust samples were collected using a custom-made stainless-steel filter housing unit connected to a vacuum cleaner. Chemical analysis was conducted by both a liquid chromatograph (LC) coupled to high resolution mass spectrometer (HRMS) and a gas chromatograph (GC) coupled with a HRMS. Both techniques are complementary for detection of the wide polarity range of organic chemicals. A comprehensive workflow was developed and implemented which include target analysis (TA), suspect screening analysis (SSA) and nontarget screening analysis (NTA). These different analysis strategies allowed for quantification of known target compounds as well as screening of priority compounds and detection of unknown compounds of interest related to the study objectives. Part of the results from this current report has recently been published in an article by Dubocq et al. (2021). Additional retrospective analysis was conducted on the original raw data which significantly extended the number of identified organic compounds in the dust samples, thus demonstrating the usefulness of the comprehensive analytical workflow.

2. Background In Europe and North America, we spend more than 90% of our time in different indoor settings (Klepeis et al., 2001, Schweizer et al., 2006). Exposure to various chemicals that are present within these indoor microenvironments (homes, workplaces, schools, vehicles, and more) can be very significant non-dietary exposure pathways. There could be more than 6000 different anthropogenic chemicals in a typical indoor environment of which several hundred could be attributed to building materials (Swedish Chemicals Agency, 2015). Besides building products and materials, interior decoration, textiles, furniture, and consumer products such as toys, cosmetics, health care products and electronics also contain chemical additives that contribute to the indoor chemical burden. These additives include for example different manufactured chemicals such as stabilizers, plasticizers, flame retardants, colorants, fragrances, emulsifiers and binding agents, and some of these have been found to cause various adverse health effects (Wensing et al., 2005). New chemicals are also constantly introduced into the market due to the increasing demand for greater functionality of materials as well as replacement for regulated chemicals (Gustavsson et al., 2017). As many additives are not chemically bound to the material, they can be emitted to the indoor environment over time and thus increasing the risk of exposure to the occupants. A recent survey estimated that 20% of the Swedish population have experienced negative health symptoms related to the indoor environment, which might partly be due to chemical exposure (The Public Health Agency of Sweden, 2017). The indoor occurrence and exposure of volatile organic compounds (VOCs), metals, radon, microbiota and physical parameters have been extensively studied, and inhalation of air is considered a major non-dietary human exposure pathway (Weschler, 2009). However, semivolatile organic compounds (SVOCs) and non-volatile organic compounds (NVOCs) are on the other hand much less studied, mainly due to their low concentrations and very challenging chemical analysis. The indoor exposure of these compounds is generally by ingestion of dust and dermal absorption through contact with contaminated material (Weschler and Nazaroff, 2008, Little et al., 2012). Furthermore, many of these are also endocrine

6 disruptors that can cause adverse health effects even at very low concentrations (Bergman et al., 2012). Indoor dust can be an important indicator of human exposure to organic contaminants in the indoor environment (de Boer et al., 2016). This matrix consists of a mixture of materials of biological origin (such as fungal spores, pollen, insect parts, skin fragments), indoor materials (e.g. fragments from plastic flooring, paints, furnishing, wall cover), natural and synthetic fibers (e.g., from plants or textile) and particulate matter from both indoor and outdoor sources. Indoor dust can therefore be regarded as a repository for SVOCs and NVOCs, and therefore a good indicator of human exposure to these compounds in indoor microenvironments (Butte and Heinzow, 2002). Over the past decades, organic contaminants of a wide range of molecular structures and physical-chemical properties have been detected in dust; from polar and non-volatile ionic compounds such as some pesticides, bisphenols and per- and polyfluoroalkyl substances (PFASs) to less polar and semivolatile compounds such as phthalates, brominated flame retardants (BFRs) and organophosphate esters (OPEs) (Mercier et al., 2011, Moschet et al., 2018, Rager et al., 2016, Persson et al., 2018b, Persson et al., 2019, Lucattini et al., 2018, Mitro et al., 2016, Rostkowski et al., 2019b). With the rapid advance of HRMS instruments and data processing techniques, there are now numerous studies that further explore the extensive chemical composition of indoor dust by performing so called suspect screening analysis (SSA) and nontarget screening analysis (NTA). For example, Rager et al. (2016) used liquid chromatography coupled with a HRMS (LC-HRMS) and detected thousands of molecular features in household dust but could only positively identify a small fraction of these by matching against reference databases and authentic standards. Moschet et al. (2018) compared the advantages and drawbacks of LC-HRMS and gas chromatography (GC) coupled with HRMS of indoor dust samples and found that both approaches were complementary to screen for chemicals of diverse physical-chemical properties. In a recent interlaboratory comparison study on SSA/NTA methods of a composite indoor dust sample, around 2350 organic compounds were detected at various levels of confidence (Rostkowski et al., 2019a). Interestingly, only 37% of these compounds were reported by more than one participating laboratory, meaning that 63% of the compounds were only detected by one laboratory even if all processed the same dust sample. One reason could be that the different laboratories used different instrumental methods (GC-MS, GCxGC-MS or LC-MS with different types of columns) and different data processing workflows which could significantly influence the identification process. This shows that SSA/NTA methods and results vary significantly between different laboratories. This current report describes the results from a comprehensive analytical workflow using ultrasonic solvent extraction of collected indoor dust samples and analyzed by both LC-HRMS and GC- HRMS. Target, suspect and nontarget analysis approaches were used to detect and identify a wide range of organic contaminant in these samples.

3. Collection of samples

Sampling sites A total of 26 dust samples from different indoor environments were included in this study (Table 1). These included offices (n=5; sample ID O1-O4), households (n=6; H1-H5, where five samples were collected from individual household and two were pooled samples from multiple households), preschools (n=10; P1-P6), various indoor working environments such as a printing workshop (n =

2, PW), an IT help desk department (n=1; IT), an interior and furniture shop (n = 1, IF) and an electronic store (n = 1; E). All indoor dust samples were collected in 2019 around the Örebro region in Sweden, except for H5 which was collected in 2016. Field blank samples were also collected at selected sites. Samples collected at the same site but at different occasions share the same initials but are differentiated by the last letter (e.g. O1a and O1b). Field blanks code were suffixed with “fb” at the end.

Sampling procedure Sampling of indoor dust was performed using a custom-made stainless steel housing unit containing a stainless-steel filter (mesh size: 500 μm) mounted on top of a pre-burned glass fiber filter (0.7 µm) to conveniently separate hair and larger objects from the dust. The unit was connected to an industrial vacuum cleaner (Alto Aero 21 Inox, Nilfisk, Sweden). This housing unit was designed to minimize potential contamination from the sampling equipment and from the field. Sampling was conducted on horizontal surfaces above the floor and the collected amount were between 33 mg and 110 mg. After the sampling, the GFF filter was placed in a pre-cleaned glass petri dish with a lid, covered with aluminum foil and stored in an airtight zip-lock bag. The samples were carefully transported to the laboratory within the same day and stored in a -20 °C freezer. Field blank samples were collected by placing a clean GFF filter in the stainless-steel housing unit at the sampling site and keeping the mouth away from surfaces while turning on the vacuum cleaner for five seconds. The blank filter samples were then treated in the same way the dust filter samples. The stainless-steel housing unit was carefully rinsed with ethanol between each sampling. The pooled household sample H5 was collected directly from vacuum cleaner bags from several households and sieved through a 500 μm stainless steel mesh, in order to obtain sufficient amount for method testing and subsequent analysis. An indoor dust standard reference material (NIST SRM 2585) was also included in the analysis as a quality control and assurance since different concentration values of various organic contaminants is available for this material.

Table 1. Information on sampled indoor dust. Modified from Dubocq et al. (2021) Indoor Sample ID environment Dust weight (mg) Sample areas Description category Built in 2019, open office Open offices. O1a Office 56.1 concept, Nordic Swan First sampling environmental certification Built in 2019, open office Open offices. O1b Office 106.8 concept, Nordic Swan Second sampling environmental certification Built in 2008, no O2 Office 81.4 Four offices certification Build in 1999, no O3 Office 110.5 Five offices certification Field blank O3fb Office Built in 1999, no O4 Office 57.7 Four offices certification Bedroom, kitchen, Built in the 1950s, no H1 Household 100.5 living room, hall certification Living room, Built in 2008, no H2 Household 32.9 bathroom, two certification bedrooms Field blank H2fb Household All rooms in H3a Household 107.7 apartment. 1st Built 1908, no certification sampling. All rooms in Built in 1908, no H3b Household 64.6 apartment. 2nd certification sampling. Pooled sample H4 Household 108.8/107.2/101.1 from several houses Pooled sample H5 Household 108.8/100.9 from several houses All rooms. 1st Built in 1991, no P1a Preschool 103 sampling. certification All rooms. 2nd Built in 1991, no P1b Preschool 77.5 sampling. certification

Indoor Sample ID environment Dust weight (mg) Sample areas Description category Rooms: South Build in 2015, Passive P2a Preschool 101.7 1+2, North 1+2. house, Nordic Swan 1st sampling. environmental certification Rooms: South Build in 2015, Passive P2b Preschool 99.5 1+2, North 1+2. house, Nordic Swan 2nd sampling. environmental certification Rooms: South Build in 2015, Passive P2c Preschool 77.2 1+2, North 1+2. house, Nordic Swan 3rd sampling. environmental certification Built in 2016, small energy Dining room, art P3 Preschool 91 house, environmental studio, playrooms building silver certification Field blank P3fb Preschool All playrooms. 1st Built in 2015, small energy P4a Preschool 61.1 sampling. house, no certification All playrooms. 2nd Built in 2015, small energy P4b Preschool 72.9 sampling. house, no certification Built in 2015, small energy P5 Preschool 88.3 All playrooms house, no certification Built in 2015, conventional P6 Preschool 96.5 Green section house, no certification In a large room with printing Printing Built in 1999, no PWa 56.4 machines, inks, workshop certification glues etc. 1st sampling. In a large room with printing Printing Built in 1999, no PWb 55.5 machines, inks, workshop certification glues. 2nd sampling. Four offices with Built in 1999, no IT IT help desk 87.8 various computers certification and electronics Interior design Randomly around Built in 1922, no FS and furniture 107.9 the shop above certification store the floor FSfb Field blank

Indoor Sample ID environment Dust weight (mg) Sample areas Description category Electronic shop Randomly around ES and repair 97.9 the shop above Built 2017, no certification workshop the floor From vacuum Collected from several NIST certified cleaner bags of NIST SRM states in the US during N reference material: homes, cleaning 2585 1993-1994 (Poster et al., indoor dust services, motels, 2007) hotels

4. Chemical analysis

4.1. Extraction procedure Approximately 100 mg of dust samples were carefully removed from the filter and transferred into an 8 mL amber vial. In cases where lower sample weights were collected, then the whole sample was extracted. Thereafter, 3 mL of a mixture hexane:acetone (3:1) were added to the vial and extraction were proceeded by 30 sec of vortexing, 15 min of sonication and 5 min of centrifugation at 3500 rpm. The supernatant was transferred into another 8 mL amber vial and the extraction was repeated using 3 mL of acetone. Both supernatants were combined and evaporated using nitrogen flow until 1 mL. The extract was filtered through a 0.2 µm PTFE filter and transferred into a 2 mL amber vial. The extract was then split in half (0.5 mL for GC analysis and 0.5 mL for LC analysis). The LC extract was evaporated down to 0.1 mL before adding 0.4 mL of methanol, evaporated further until 0.25 mL and finally another 0.25 mL of water was added to reach a final volume of 0.5 mL with a mixture of 1:1 methanol:water. While adding water, there could be a formation of precipitate, and the LC extract was then centrifuged for 5 min at 3500 rpm and finally the supernatant was transferred into a total recovery LC vial for injection.

4.2. Chemical analysis

GC-HRMS analysis: A GC (DB5-MS column, 30 m x ID 0.25 mm x 0.25 µm thickness) coupled with an Orbitrap mass spectrometer (Q Exactive GC Orbitrap, Thermo scientific, Bremen, Germany) was used in EI mode (70 eV) and full scan mode (m/z range 54-800) with a mass resolution of 60 000 full width at half maximum (FWHM) at m/z 200. A temperature programming was used with the following conditions: start 70 °C hold 0 min, ramp 8 °C/min to 205 °C and hold for 2 min, ramp 4 °C/min to 325 °C and hold for 5 min) and the total run time was 47 min.

LC-HRMS analysis: An LC (Acquity UPLC BEH C18 column, 100 mm length x 2.1 mm ID, particle size 1.7 µm) coupled with a Waters G2-XS-QToF instrument (Milford, Massachusetts, USA) was used for LC analysis. Electrospray ionization in both positive and negative full scan mode was used. The scan range was m/z 50-1200 at resolution of 40 000 FWHM at m/z 564.2600 (ESI-) and 566.2766 (ESI+). A gradient mobile phase composition consisted of (A): 0.1 % formic acid in water and (B): 0.1 % formic acid in ACN (B), was used for for ESI+. For negative mode the mobile composition was E (A): H2O + 1 mM NH4F and (B): ACN. A data-independent acquisition method was used (MS ) in which the the collision energy in the collision cell alternated between low energy (3 eV) and high energy (ramp 20-40 eV).

5. Data analysis workflows Data preprocessing is an important aspect of the SSA and NTA workflow of raw data outputs from full scan HRMS. The main goal of data preprocessing is to extract signals that corresponds to individual chemical entities in the samples. Usually, the steps are as follow: - Peak picking: This involves the detection and extraction of chromatographic peaks at specific m/z values (called feature) within a defined mass tolerance (usually in ppm unit) as well as their respective retention time. - Alignment: Due to various reasons, the retention time often shifts slightly between different sample injections which can lead to problems during data analysis as identical compounds can become treated as different chemicals between samples. Retention time alignment can adjust the retention time shifts between injections to facilitate comparison between samples. Therefore, various algorithms are used to adjust the retention time shift between injections. - Deconvolution/Componentization: A compound can produce different features due to isotopologues, in-source fragmentation, collision-induced fragmentation and adduct formation. To reduce the complexity of the data, features that belong to the same compound are grouped into a one component, usually by algorithms that performs deconvolution or componentization based on the similarity of retention time as well as the chromatographic peak shape. - Filtration: Another step to reduce complexity of data is to reduce the number of features by different data filtering processes. These include for example cropping the retention time or m/z window, only keeping features that are above a certain signal-to-noise ratio as well as above a sample-to-blank signal threshold.

In this work, a primary data processing workflow was conducted combining target, suspect and nontarget screening analysis. We thereafter performed a retrospective analysis using the same dataset to increase the number of identified compounds.

5.1. Target analysis workflow Target analysis was performed for compounds listed in Appendix 1 using XCalibur version 4.1 and TraceFinder EFS version 4.1 (Thermo Fisher, Waltham, Massachusetts, USA) for the GC analysis and UNIFI version 1.9.3.071 (Waters, Milford, Massachusetts, USA) for the LC analysis. Internal standards were not added to the samples, but the reported concentrations for target compounds were

12 reported on a recovery corrected basis based on recovery tests (Dubocq et al., 2021). Quantification of the target compounds was conducted using a one-point calibration, and therefore the concentrations were considered to be semiquantitative.

5.2. Suspect screening and nontarget analysis workflow The LC data were converted to mzXML format using MSConvert GUI (64-bit, v3.0.19122) from the ProteoWizard platform (Chambers et al., 2012). They were thereafter uploaded to XCMS online (version 3.7.1, The Scripps Research Institute, La Jolla, USA) (Smith et al., 2006). For GC raw files, these were directly uploaded to XCMS online. Both LC and GC datasets were pre-processed by performing peak detection, filtering and alignment. Suspect screening analysis was conducted on the processed data by screening the detected features with a list from the NORMAN network of detected compounds in indoor dust (Haglund and Rostkowski, 2019, Rostkowski et al., 2019a). For detailed data preprocessing parameters, please see Dubocq et al. (2021). Furthermore, NTA workflow was conducted on the list of features from XCMS online, which included hierarchical cluster analysis (HCA) and mass defect plot analysis using Cl-H/Br-H (mass scale = 34/33.9610 or 78/77.9105) using Excel software (Microsoft, Redmond, USA). Additional statistical analysis was performed using R (4.0, R Core Team).

After the initial data processing, we further performed retrospective data analysis to extend the number of detected compounds in the same sample set. Two other software were performed in this workflow; MS-DIAL v4.48 (Tsugawa et al., 2015) for LC data, and XCMS (v3.12, within the R programming platform) together with CAMERA (v1.46) for GC data. Additional suspect screening list in the retrospective analysis included the LC spectral libraries from Massbank of North America (Mona, https://mona.fiehnlab.ucdavis.edu/downloads, downloaded 2021-02-03), Massbank of Europe (MassBank-consortium and its contributors, 2021) and the GC spectral libraries from NIST14 and the RECETOX Exposome HR-[EI+]-MS library (Price et al., 2021).

5.4. QA/QC Recovery tests were performed using sodium sulphate spiked with the compounds listed Appendix 1 and 2, at two concentration ranges, 9-271 pg/µL (low) and 0.99-6.04 ng/µL (high), to investigate the recoveries even for compounds that were close to the method detection limit (MDL). Further recovery tests were carried out by spiking the NIST 2585 SRM with the high concentration range target compounds (Table S5). During the analysis, additional QA/QC measures were included to ensure the robustness of the method. These included e.g. a quality control (QC) pooled sample (excluding field and extraction blanks), spiking selected samples with deuterated OPFR internal standards (IS, n = 7) and one 13C-labeled recovery standard (RS) before injection, inclusion of field and extraction blanks, dilution of selected samples, replicate sample processing, replicate sample injections, randomization of sample injection, injection of a standard mixture of isotopic labelled OPFRs, injection of alkane mixture for retention time index estimations (for GC) and injection of solvent blank injections (hexane for GC analysis, and 50:50 MeOH:H2O for LC analysis). The method quantification limit (MQL, based on 0.1 g of sample, Appendix 1, 2) was estimated for each compound from the average of ten standard mixtures by calculating the concentration matching for a peak height of 10 000 for GC analysis and a signal over noise (S/N) ratio of 10 for LC analysis. Furthermore, features were only kept if the intensity ratio of sample-to-blank was above 5. 13

5.5. Reporting identification confidence level The terminologies for detection, identification and annotation followed the proposed glossary set up by Oberacher et al. (2020). The confidence level for reporting the tentative or positive identification of the chemicals in LC mode followed the guideline suggested by Schymanski et al. (2014). However, this identification scheme cannot be directly implemented for GC-EI-HRMS, mainly since molecular ions are not always visible or at very low intensity. In this report, we therefore also implemented various criteria for reporting identification confidence levels (ICL) for GC-EI-HRMS according to below Table 2. It should be noted that this identification scheme for GC was mainly used within the context of this report to provide a certain harmonization of ICL for both LC and GC and might not necessarily be applied in other studies or compared with other results. Especially, a high ICL for GC-EI-HRMS was only assigned if the spectrum had a high match with spectral libraries and the monoisotopic ion was present in the spectrum, which limits the number of positive identifications but on the other hand increases the confidence of correct annotation.

The ICL was assigned to each detected chemical together with information about the detection method used for the chemical analysis: LC-HRMS in positive ESI mode (abbreviated as LC+), LC- HRMS in negative ESI mode (LC-) and GC-HRMS in EI mode (GC).

Table 2. Criteria for the identification confidence level. Identification Criteria Applied criteria confidence level (ICL) 1: Confirmed High match of MS, MS/MS LC: mass error of precursor and selected structure and retention time with fragment ions: <10 ppm. Retention time match reference standard <10 s.

GC: quantification and qualification ion mass error: <5 ppm. Retention time match: <2s. 2a: Probable Matching with mass spectral LC: precursor match <10 ppm AND at least 3 structure by libraries matching MS/MS peaks. library

GC: Spectral library match >600 AND retention index difference <50 AND monoisotopic peak of molecular ion visible with <5 ppm mass error. 2b: Probable High match with theoretical LC: precursor match <10 ppm AND at least 3 structure by m/z MS/MS peaks explained by common diagnostic ions fragmentation rules.

GC: Spectral library match >600 AND monoisotopic peak of molecular ion visible with <5 ppm mass error OR (retention index <70 AND 3 most abundant ions at <5 ppm mass error).

3: Tentative Evidence for possible LC: Same as 2b but possible positional isomers candidate structure but not sufficient to cannot be distinguished. distinguish between isomers. GC: No match with spectral library but In silico predicted fragments suspected monoisotopic peak match <5 ppm of parent or transformation mass error AND 3 diagnostic fragment ions at products. <5 ppm mass error. 4: Unequivocal Chemical formula can be LC: precursor match <10 ppm BUT MS/MS molecular assigned but not enough peaks are not informative. formula evidence for structural

assignment. GC: not used (no applicable criteria available).

5: Exact mass Exact mass of the feature can LC and GC: Specific m/z patterns such as be measured Cl/Br isotopic patterns, specific mass defects and homolog series patterns.

As one of the purposes of this report was to screen for indoor contaminants with a high level of confidence, we therefore only reported those chemicals that were detected with an ICL of 3 or above in this report. An example is given for the identification of caffeine (ICL: 2a, LC+, GC), indicating that it was identified by good matching with spectral library in LC-HRMS positive mode (mass error of precursor ion = 5 ppm and more than three matching fragmentation ions at <10 ppm mass error) as well as in GC-EI-HRMS (NIST spectral library match score: 610, retention index difference = 10, mass error between the measured accurate m/z and the theoretical m/z of monoisotopic peak of the molecular ion = 3 ppm). Thus, detection of caffeine by both LC and GC analysis can be at a very high confidence level even if a standard was not used to raise the ICL to 1.

6. Results and discussion A total of 262 compounds were detected in the indoor dust samples with an identification confidence level (ICL) of at least 3. The full list can be found in Appendix 3. As seen in Figure 1, most of the chemicals were uniquely detected by one of the ionization methods, while only a few compounds could be detected by multiple methods. This shows that the different analytical methods are complementary in identifying organic contaminants.

Figure 1. Venn diagram showing detected compounds among the three different analysis methods (GC-EI- HRMS, LC-HRMS negative ESI mode, LC-HRMS positive ESI mode).

To provide a first general overview, hierarchical clustering analysis (HCA) was conducted by combining the scaled (normalized) intensities of detected compounds in all three detection modes (GC, LC-, LC+). It can be seen in Figure 2 that all replicates were nicely grouped together indicating that the sample preparation method and instrumental analysis was reproducible.

Figure 2. Hierarchical clustering analysis heatmap with dendrograms from intensities of all detected compounds in GC-EI, LC negative and LC positive modes. The intensities were scaled on the row direction (individual chemicals) to reduce the influence of differences in compound intensities as well as allowing comparison between different detection modes. The Euclidean distance metrics and average linkage criterion were used for hierarchical clustering. The same compound could occur in multiple rows if they were detected in more than one detection method, and these were also clustered very closed to each other (not visible in this figure). White cells indicate very low relative intensities or not detected, while more intense red color indicate higher relative signal intensities. The relative positions of some selected chemicals are annotated in the heatmap.

The indoor dust reference standard NIST SRM (N_rep samples in Figure 2) mainly distinguished itself compared to the other samples by having high relative intensities of legacy POPs such as PCBs, PBDEs, BPA, pesticides, drugs of abuse (cocaine) as well as PFAS. The electronics store (ES) had a larger distance from the most other dust samples in the dendrogram, which was mainly due to higher relative intensities of TBBPA, tribromophenol and octabenzone which could be markers of chemical release from electronics. The interior and furniture shop (FS) had relative higher intensities of tolylfluanid, methylparaben, PCP, 8:2-FTSA, asperphenamate, TBP and both TDI isomers. Furthermore, dibutyl phthalate (DBP) were clustered close to the TDI isomers, indicating usage and release from the same sources, likely from polyurethane foams. The

17 polyethylene glycol homologs, PEG-6 to PEG18, were all grouped together, whereas lower (PEG-4 and PEG-5) and higher (PEG-19 and PEG-20) homologs were separately grouped. In order to provide a better overview of the results, the detected chemicals were grouped into their main functional uses and discussion was made on a selection of compounds (full list in Appendix 3). It should be noted that many chemicals have multifunctional and multipurpose uses in the industry and in products. In most cases, quantitative results were not available and comparison between samples were made based on the intensities of precursor ions (in LC) or selected diagnostic ions (in GC).

Organic flame retardants 1,2-Bis(2,4,6-tribromophenoxy)ethane (BTBPE, ICL: 2b, GC) is a replacement brominated flame retardant (BFR) for octaBDE in hard plastics used to house electronics and has been previously found in indoor dust (Ali et al., 2011). In this study, BTBPE was only found in one home setting (H2).

2,4,6-tribromophenol (TBP, ICL: 3, GC) is an intermediate in the production of flame retardants but is also used as a pesticide in a salt form. Higher relative intensities were found in the IT help desk (IT) and ES samples, indicating its association with use of electronics.

2-ethylhexyl diphenyl phosphate (EHDPP, ICL: 3, GC) is a plasticizer in plastics with flame proofing properties. It is used under different trade names such as Octicizer, Santicizer 141, Phosflex 362, and more. EHDPP was detected in all samples (df: 100%) and it has also been frequently detected in various indoor environments (Persson et al., 2018b).

Phenyl di(p-tolyl) phosphate (ICL: 3, GC) is structurally related to TCP, and has been found in most indoor dust samples. Two isomers were mainly found although in one sample (H3), five closely eluted peaks could be distinguished.

TBBPA (ICL: 1, LC-, GC) was higher in ES, which sells and repairs electronics, indicating potential higher occupational exposure to those working with electronics since TBBPA is a reactive flame retardant in printed circuit boards.

Tricresylphosphate (TCP, ICL: 3, GC) has ten possible structural isomers (De Nola et al., 2008), of which all ten could be distinguished in the chromatograms of H3 (Figure 3), which had the highest peak intensities among the indoor dust samples. The retention time order is usually ortho-, meta- and para-isomers (Solbu et al., 2007), although this cannot be confirmed without standards. The other samples with lower signal intensities mainly showed 2-3 isomeric peaks of TCP.

Figure 3. Extracted ion chromatograms (m/z range: 368.116 - 368.118) showing TCP isomers from a high intensity sample H3 (upper) and a low intensity sample O4 (lower).

Tris(2-butoxyethyl) phosphate (TBOEP, ICL: 2a, GC) is a very common flame retardant and plasticizer. It has previously been frequently detected in various indoor environments all around the world (Persson et al., 2018b, Cristale et al., 2018). It was also detected in all samples showing the ubiquitous contamination of this compound on the indoor environment.

Various additives in materials/products 1,2-Diphenoxyethane (ICL: 2a, GC) is mainly used as sensitizer in the production of thermal paper (thermal paper coating, thermal recording paper, thermal carbon paper, receipts, invoices, etc). Relatively higher peak intensities were found in samples from the printing workshop (PW) and from the furniture and electronics stores (FS and ES). This compound have been found to give active responses in bioassay tests such as ER-α, PXR and AhR (https://pubchem.ncbi.nlm.nih.gov/compound/7713#section=BioAssay-Results&fullscreen=true).

Toluene diisocyanate isomers, 2,6-TDI (ICL: 1, GC) and 2,4-TDI (ICL: 1, GC), were detected in almost all indoor dust samples (df 96% and 100% respectively). These were target compounds and recovery corrected concentrations ranged

Figure 4. Concentration of 2,4-TDI and 2,6-TDI in different indoor dust samples.

4-sec-Butyl-2,6-di-tert-butylphenol (ICL: 2b, GC) is used in building products and was mainly found in the newly built office O1 (both O1a and O1b).

Benzothiazoles are extensively used in industrial processes and household products. Several compounds within this chemical group was found in the samples: 2-(Methylmercapto)benzothiazole (MTBT, ICL: 2a, GC) was found in all samples. 2-Hydroxybenzothiazole (ICL: 2b, LC+), a closely related compound, was also found in all samples. The monoisotopic peak of the molecular ion was further found in GC (mass error <4 ppm), with similar peak intensity trend among the samples as for LC mode which further confirm the positive identification of this compound. Dicyclohexylamine (ICL: 2b, LC+) also have the same usage as the benzothiazoles (Brorström- Lundén et al., 2011) and was highest in O1, H5 and FS. Furthermore, the above compounds could also be impurities or transformation products of N,N- dicyclohexylbenzothiazole-2-sulfenamide (DBS) or cyclohexylbenzothiazyl sulfenamide (CBS) that are used as accelerator of vulcanization in rubber products, although these were not detected.

1,3-Diphenylguanidine (ICL: 2b, LC+) is another vulcanizing agent or accelerator, and was found in all samples, with highest peak intensities in the H1 and FS samples.

Bisphenol A (ICL: 1, LC-, GC) was only found in one sample from the printing workshop (PWa) and in the NIST SRM, as its usage has been phased out. However, its analogue bisphenol S (ICL: 1, GC) was found in 33% of the samples, mainly in occupational settings (offices and stores), at a range of 84-751 ng/g among the detected samples.

Melamine (ICL: 1, LC+, GC) is a very HPV chemical in the EU (100 000 - 1 000 000 tonnes per year) and was found in several samples (such as H2, H4, NIST). Sample H2 is a household that uses many melamine tableware, and contamination of melamine in indoor dust could be related to use of these products.

Tributyl citrate (TBC, ICL: 1, LC+), triethyl citrate (TEC, ICL: 2a, GC) and acetyl tributyl citrate (ATBC, ICL: 2b, LC+) are widely used as plasticizers (also in cosmetics and more), food additives, solvents and paint removers (Persson et al., 2018a). The target compound TBC showed a detection frequency of 41% in LC positive mode and maximum concentration of 95 ng/g, with relatively higher concentrations in offices and preschools. Furthermore, both TEC and ATBC could also be detected in all samples (df: 100%).

Tris(2-ethylhexyl) trimellitate (TOTM, ICL: 2a, GC) is a high production volume plasticizer which has recently been detected in indoor dust (Tang et al., 2020, Christia et al., 2019, Salthammer, 2020). In this report, TOTM was found in all samples. Highest intensities were found in samples from IT and offices (Figure 5).

Figure 5. Intensities of TOTM of the selected diagnostic ion (m/z 305.1389) using GC-EI-orbitrap. X-axis is in logarithmic scale.

Liquid crystal monomers (LCMs) Target analysis was performed for thirteen LCMs, although it should be noted that the sample extraction and preparation method was not optimized for this group of compounds (Dubocq et al., 2021). It can also be seen from the relatively low extraction efficiencies between 10-72%. Among the LCMs, LCM-3 had the highest detection frequency (df: 70%) and with a concentration range of 0-1586 ng/g. LCM-13 was detected in 26% of the samples, in an office (O1a, b: 301-490 ng/g), two preschools (P2a-c: 86-100 ng/g, and P3: 719 ng/g) and in the furniture store (FS: 62 ng/g). LCM-6 was only sporadically found in three samples (H3a, H4 and P2b). All of these detected LCMs are non-fluorinated analogues, and none were detected in the NIST SRM indicating their increased used in recent years.

Pharmaceuticals and personal care products (PPCP) Acetaminophen (ICL: 2a, GC, LC+, LC-) is a very common medicine to relieve pain and reduce fever and was mainly found in NIST SRM but also occurred in several home and office dusts at low peak intensities. It was the only compound detected in all three ionization methods.

Benzyl salicylate (ICL: 2a, GC) is commonly used as a fragrance additive or UV light absorber in cosmetics, personal care products, air fresheners and also a food additive. It was found in all samples.

Diclofenac (ICL: 1, LC-) is widely used as a nonsteroidal anti-inflammatory drug which can be taken by mouth, rectally, injected and applied in a cream to the skin. Positive identification was confirmed by authentic standard and higher relative levels were found in several preschool and office environments compared to the home settings (Figure 2). Detection in indoor dust could indicate application to skin and subsequent release of skin fragments that is a component of indoor dust.

Hydrocortisone (ICL: 2a, LC+) is a multifunctional drug and is commonly e.g. used as a topical cream to treat eczema and rashes. Relatively higher intensities were found in preschools and offices than home environments and other workspaces.

Methyl dehydroabietate (ICL: 2a, GC) is a emollient agent in cosmetics and skin care products. This compound was also found in all samples.

Polyethylene glycols (PEGs, 2a, LC+) is a wide group of dialkyl ethers with the general chemical formula H−(O−CH2−CH2)n−OH, where n denotes the number of repeating units. Different PEG formulations are available based on the average molecular weight of the PEG constituents. PEGs are widely used in industrial processes, in medicines, personal care products, and more. In this report, PEGs were found in all samples with n-values ranging from 4 to 20.

Salicylic acid (ICL, 2a, LC-) is a degradation product of acetylsalicylic acid (aspirin) but also used to treat skin conditions. It was found in most indoor samples and had highest peak intensities in O2 and V3 samples. 22

Antiseptic and disinfectants: Benzalkonium chloride (BAC-12, ICL: 3, LC+), is a group of cationic surfactants that have benzyldimethylammonium group attached to even-numbered alkyl chain of variable lengths. The C12 analog was found in most samples, with higher peak intensities in home and preschool settings, which might reflect they wide usage in textile detergent and softeners and antibacterial agents in sprays and hand wipes.

Triclocarban (ICL: 1, LC+) was commonly used antibacterial agent in personal care products but has now been phased out. It was only found in NIST and in H3.

Triclosan (ICL: 2a, GC) is a widely used bacteriocide and was found in many samples. Highest intensities were found in the NIST SRM and in H1 sample.

Dyestuff and paint pigments 2,6-Dibromo-4-nitroaniline (ICL: 3, GC) is found in dyestuff and was only in one sample (PWa).

C.I. Basic Red 9 (ICL: 2b, LC+, GC), is a dye used in textiles, leather, and printing inks. It is also suspected to be carcinogenic in animal experiments (NTP, 1986). It was not found in any home environments and highest intensities were found in samples O1, P4, P5 and ES.

C.I Disperse Red 60 (ICL: 3, LC+, GC) is used as dye in fabrics, plastics, and printing inks. It was found in all samples with highest intensities were found in O2, P4 and P3.

Two isomers of chloroaniline (ICL: 3, GC), three isomers of dichloroaniline (ICL: 3, GC) and three isomers of trichloroaniline (ICL: 3, GC), have been found in various indoor dust samples. These are broad use intermediate chemicals in the production of pesticides, drugs and dyestuffs. Similarly, two isomers of chloronitroaniline (ICL: 3, GC) were also found in the samples, with highest intensities in H3 and P3 samples.

Crystal violet (ICL: 2b, LC+) is used as a dye in textile, paper and inks for printing, pens, and inkjet printers. It was found in higher intensities in preschools, work environments and stores than homes.

Two isomers of dichlorophenyl isocyanate were found, of which 3,4-dichlorophenyl isocyanate (ICL: 3, GC) is a very high production volume chemical, used as e.g. an intermediate in the production of dyes. It has been found in WWTP effluents (Glassmeyer et al., 2005). Further identification of the specific isomers should be conducted with authentic standards.

Indigo (ICL: 2b, GC) is used as dye in textile and food items. It was found in most samples with no specific patterns in regard to the intensities among the different indoor sites.

Per- and polyfluoroalkyl substances (PFAS) Several peaks corresponding to PFAS were detected in the samples in LC negative mode (ICLs between 2 and 3). Perfluoroalkyl sulfonic acids (PFSA), PFBS, PFHxS, PFHpS, PFOS, PFNS, PFDS, N-EtFOSAA and N-EtFOSA were mainly detected in NIST but also occurred at low intensities in older buildings. Same trends were found for the perfluoroalkyl carboxylic acids (PFCA) such as PFHxA, PFHpA, PFOA, PFNA, PFDA and PFUnDA. 8:2-FTSA had a very high relative intensity in FS indicating usage of surface treatment agents on textiles or leather products in this store. Similarly, 6:2-FTSA (ICL: 2a) was also found in FS as well as in NIST SRM.

UV stabilizers 2-(2H-Benzotriazol-2-yl)-4,6-di-tert-pentylphenol (UV-328, ICL: 2a, GC) is used in plastic films such as food packaging, outdoor furniture and clear coat automotive finishes. It was detected in all indoor samples at signals clearly above blank levels, with highest intensities found in H1, O1, NIST SRM and O3.

7,9-Di-tert-butyl-1-oxaspiro(4,5)deca-6,9-diene-2,8-dione (ICL: 2a, GC), is a potential transformation product of Irganox 1010, which is added to polyethylene (PE) and cross-linked polyethylene (PEX) (Moldovan et al., 2018, Lützhøft et al., 2013, Lagacé et al., 2017). The highest intensities were mainly found at FS, PWb and O3.

Bumetrizole (also called UV-326, ICL: 2a, GC) is used as UV absorber in plastics and cosmetics. It was found in almost all samples and highest intensities were found in H1 (similar as UV-328), P6 and O1.

Octabenzone (ICL: 3, GC) is a UV absorber for plastics such as polyethylene, polypropylene and polyvinylchloride. It found at very high relative intensity in ES, with lower intensities in H1, NIST SRM and P5.

Octocrylene (ICL: 2a, GC) is used as a UV absorber in sunscreens and cosmetics and was found in all samples. A trend of higher peak intensities was found for preschools than the other indoor environments which could indicate the use of sunscreens on children during the time of sampling.

Pesticides, fungicides and herbicides Benzisothiazolinone (BIT, ICL: 2b, LC+) is an antimicrobial and fungicide and used as preservative in a wide range of products such as paints, adhesives, and cleaning products. It was mainly found in P2, O1 and P4 (Figure 2).

Dinoterb (ICL: 3, LC-) is an herbicide which has been banned in the EU but was detected in all samples, with good match with the reference spectrum. An isomer, Dinoseb (also banned) also give rise to similar spectra and thus lowering the confidence of positive identification. Low intensity peak of the precursor ion also occurred in the procedural blanks at the same retention time, thus further raise the possibility of a false positive. Standards are thus needed to confirm the identification of these two herbicides in the dust samples.

Fipronil (ICL: 2a, LC-, GC) was found to be highest in a composite house dust (H4a) and was highly correlated (R = 0.94) with its metabolite fipronil sulfone (ICL: 2a, LC-) among the indoor samples.

Methyl 4-hydroxy-3-bromobenzoate (ICL: 2b, GC) was mainly found in FS, and might be a biodegradation product of the herbicide bromoxynil.

Pentachlorophenol (ICL: 2a, GC) has been used in antifouling pain and wood preservative and was also found at higher relative intensity in FS.

Propetamphos (ICL: 2a, GC) is an organophosphate insecticide which was found in some samples and sample O3 had highest peak intensity, indicating usage as pest control in this office environment.

Propiconazole (ICL: 3, GC) a fungicide was found in several samples, especially in preschools. Two out of four theoretical isomers were detected in the GC analysis.

Terbutryn (ICL: 2a, LC+ and GC) was found in a few indoor dust samples (H2, P3, P6). The fact that it was detected using both LC and GC-HRMS suspect screening provides a high level of confidence. It is an herbicide used against weeds and other unwanted vegetation. It is unclear how this chemical, which is restricted in EU, is present as a contaminant in these indoor environments.

Tolylfluanid (ICL: 2a, GC) and dichlofluanid (ICL: 2a, GC) are broad-spectrum antifouling biocides (Cai et al., 2021). Tolylfluanid was found in FS, O4, H4, IT, PWa and P3 (ordered by the intensities), whereas dichlofluanid was mainly found in H3, H1, P3, P1 and FS (Figure 2).

Fragrances Amylcinnamaldehyde (ICL: 2a, GC) is used as a fragrance in cosmetic products and is suspected allergen (SCCS;, 2012). Highest intensity was found in the NIST SRM followed by significantly lower intensities in P1 and P2 samples.

Tonalide (ICL: 3, GC) and galaxolide (ICL: 3, GC) are both polycyclic musk isomers and frequently used as a fragrance in soaps and cosmetics. They are suspected endocrine disruptors and also previously found in indoor dust (Li et al., 2013, Mitro et al., 2016). Furthermore, a galaxolide

25 metabolite, galaxolidone (ICL: 2a, LC+), was also detected in most samples with highest intensities for samples NIST SRM, P1 and H3). This metabolite has also previously been found in indoor dust (Lu et al., 2011) as well as in wastewater treatment plant influent and effluents (Tasselli and Guzzella, 2020).

Chloroatranorin (ICL: 2a, LC-) is found in natural extracts such as oak moss absolute and widely used as fragrance in perfumes (Johansen et al., 2006, Johansen et al., 2003, EUROPEAN COMMISSION, 2004). Its degradation product chloroatranol (ICL: 3, LC-) as well as atranol (ICL: 2a, LC-), which is a degradation product of a similar compound atranorin, were also frequently detected in the samples. The intensities of chloroatrinorin and chloroatranol were moderately correlated among the samples (R = 0.72, Figure 6), and they were also relatively close to each other in the hierarchical cluster plot (Figure 2), further validating their identities as parent and transformation product.

Figure 6. Comparison of the intensities between chloroatranol and chloroatranorin among the indoor dust samples.

Hexyl cinnamal (ICL: 2a, GC) is an additive in perfumes and cosmetics. It is a potential contact allergen (Schnuch et al., 2007), and was found in all samples. Highest intensities were found in the NIST SRM and in several preschool samples.

Plant or fungal derived chemicals Asperphenamate (ICL: 2b, LC+) a plant and fungal metabolite was mainly found in FS, H3 and NIST SRM.

Methyl ester 7-oxodehydroabietic acid (ICL: 2a, GC) is a component in rosin, which is the solid form of conifer resins. Rosin has a wide variety of uses which includes printing inks, glazing agent, and for applications that requires increase of friction such as on bowed string instruments. It has been suspected to induce dermal allergic reaction in patch tests (Febriana et al., 2015). It was found in all samples, with highest intensities in ES, H3, IT and FS.

Dehydroabietinol (ICL: 3, GC) is also a component in rosin and had highest intensities in H4, P5 and FS. 26

Lichexanthone (ICL: 3, GC) has been isolated from lichens and plants. It was mainly found in H4 and H3 samples.

Tobacco smoke chemicals Nicotine (both R- and S- isomers, ICL: 2a, LC+, GC) together with the metabolites harman (ICL: 2a, LC+), norharman (ICL: 2a, LC+) and cotinine (ICL: 2a, LC+) were found in several indoor samples. The high correlation (>0.95) among all samples further confirms their identity.

Chemicals only detected in NIST SRM sample The NIST SRM is a composite indoor dust sample collected between 1993-1994 in the US (Poster et al., 2007). It can be used as comparison of different geographical location to our samples from Sweden as well as comparison of use of chemicals between different decades.

Cocaine (ICL: 2a, LC+, GC) and one of its main metabolite benzoylecgonine was detected in the NIST SRM sample but not in other samples. They were detected both in LC-HRMS positive mode and GC-HRMS gives high confidence of positive detection.

Phenothiazine (ICL: 2a, GC) could be a degradation product from derivatives that are used as medicine, dyes or pesticides (Ohlow and Moosmann, 2011).

Several pesticides such as chlorpyrifos (ICL: 2c, GC), diazinone (ICL: 2b, GC), cyfluthrin (ICL: 3, GC), propetamphos (ICL: 2a, GC) were also only found in the NIST SRM.

7. Main findings

The use of complementary LC- and GC-HRMS analytical methods has shown to be complementary in screening and detecting a wide variety of organic contaminants in indoor dust samples. We identified 262 compounds with ICL of at least 3. Some compounds were also detected in both LC and GC methods which provides a near unequivocal identification, even if standards were not used. The results show that the indoor environment is contaminated by numerous chemicals that are used in various products and building materials. Many previously known indoor contaminants were further confirmed to be present in all or most dust samples, such as OPFRs, BFRs and PFAS. We also found some analogs of a group of chemicals of emerging concerns, LCMs, especially the non- fluorinated LCM-3. Furthermore, the two isomers of toluene diisocyanate, 2,6-TDI and 2,4-TDI, were found in most samples and highly correlated with each other, indicating release from polyurethane foams in the indoor environments. Various alternative plasticizers that are replacing phthalates such as citrates (TBC, ATBC and TEC), EHDPP and tris(2-ethylhexyl) trimellitate (TOTM) have also been detected in most indoor samples indicating their high prevalence in the 27 indoor environment. Detection of various active ingredients in pharmaceuticals or skin care products such as acetaminophen, hydrocortisone, diclofenac as well as antibacterials (triclosan, triclocarban and benzalkonium chloride) show that the use or application of products containing these chemicals can contaminate the indoor environment. The fungicides benzisothiazolinone and propiconazole were detected in many preschools, which could increase the exposure risk for children in these environments. Some chemicals used as fragrances such as chloroatranorin and its transformation product chloroatranol are potent allergens and found in many indoor environments suggesting their widespread usage. Chemicals that are used as dye or paint pigments or intermediate chemicals to produce these colorants were found in most samples, with many being halogenated compounds. Furthermore, different UV stabilizers were found in indoor dust such as benzotriazoles and octocrylene and these compounds or their transformation products have been potential adverse effects on biota (Downs et al., 2021, Giraudo et al., 2017).

8. Conclusions and suggested future works

In this report, we have shown the capability of using comprehensive target, suspect and nontarget screening workflow to identify the chemical composition of indoor dust. Although more than 260 compounds were identified with a high confidence level, additional work should be performed to identify and prioritize chemicals among the >10 000 features detected in the indoor dust samples. Furthermore, a more comprehensive high resolution mass spectra database for both LC and GC compounds should be utilized to further extend the scope of suspect screening. In this aspect, open access spectral libraries such as MONA and the Massbank Europe are important databases, but the number of environmental contaminants in these databases are still limited. Additional efforts to expand the databases will certainly lead to the increase of identified compounds at high confidence level. Among the emerging contaminants we detected in this study, it is recommended to investigate several compounds or compound groups more in detail. These include the two TDI isomers due to their seemingly ubiquitous presence in the indoor environments since their technical product is used to product PUF that are ever present in the built environment. The indoor occurrence and fate of halogenated dyes and their potential intermediate production chemicals should also be investigated as the exposure potential could be high due to their occurrence in clothing and other textile material (Swedish Chemicals Agency, 2021). Highest intensities for many of these contaminants were also found in preschools which should be prioritized indoor settings if further investigation should be conducted for this group of contaminants. Their environmental release should also be investigated by for example monitoring their levels in wastewater treatment facilities since washing can be a potential source of release. Furthermore, chloroatrinorin and chloroatranol are present in natural oak moss extracts used in fragrances and are very potent contact allergens. However, their environmental occurrence and fate have not yet been investigated. Lastly, several LCMs were found in the indoor dust which could indicate emission from LCDs. The specific sources in the indoor environment as well as release and fate to the outdoor environment should also be investigated. Dust can be an important route of human exposure since we spend a majority of our time in indoor settings. Indoor dust can also be indicator of chemical release from built environment to the outdoor environment through ventilation and through wastewater. Future works are also recommended to identify indoor contaminants detected in this study in humans as well as environmental matrices such as wastewater and biota. To be able to assess potential risks, quantification of a wide scope of indoor contaminants is necessary. Risk assessment of exposure from indoor dust should also take

28 into account the potential chemical mixture effects; even if concentration of individual compounds might not be sufficient to induce adverse health effects, the additive or synergistic effects of the combination of chemicals can be very significant.

9. Acknowledgements We would like to thank Jakob Gustavsson, Anna Kärrman, Alina Koch and Linda Linderholm for their kind support and assistance in this study. Financial support was provided by the Swedish Environmental Protection Agency (Naturvårdsverket).

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Appendix 1. Target compounds for GC-HRMS. Compound Retenti CAS Quantifica Confirmat Confirmat Est on tion ion ion ion 1 ion ion 2 MLO time m/z m/z m/z Q (min) (ng/ g)

Triethyl phosphate d15 5.10 NA 103.0092 135.0656 167.1220 NA 5 5 5 Triethylphosphate (TEP) 5.31 78-40- 98.9842 155.0466 127.0154 0.01 0 4 2-6 m-toluene diisocyanate 8.99 26471 174.0421 145.0395 132.0444 0.30 (2-6 TDI) -62-5 2-4 m-toluene diisocyanate 9.08 26471 174.0421 145.0395 132.0444 0.40 (2-4 TDI) -62-5

Tripropyl phosphate d21 9.10 NA 103.0092 151.0938 199.1785 NA 5 9

Tributyl phosphate d27 13.08 NA 103.0092 167.1220 231.2349 NA 5 5 5 Tributylphosphate (TBP) 13.59 126- 98.9841 124.9999 211.1093 0.00 73-8 8 Trifluralin 13.88 1582- 264.0227 306.0695 0.03 09-8 alpha-HCH 14.27 319- 180.9372 216.9141 0.03 84-6 HCB 14.34 118- 283.8096 248.8408 216.8719 0.02 74-1

TCEP d12 14.83 NA 261.0598 213.0084 147.9973 NA 5 5 gamma-HCH 15.04 58-89- 180.9373 216.9141 0.04 9 beta-HCH 15.16 319- 180.9373 216.9141 0.03 85-7 2

TCIPP d18 15.17 NA 131.0374 103.0092 293.1162 NA 5 5 Tris(2-chloroethyl) 15.18 51805 248.9842 222.9690 204.9584 0.11 phosphate (TCEP) -45-9 Tris(2- 15.59 13674 201.0078 98.9842 277.0159 0.06 chloroisopropyl)phosphate -84-5 (TCIPP)

1-methoxy-4-(4- 15.88 97398 163.148 206.2028 177.1636 0.45 propylcyclohexyl)cyclohexa -80-6 ne (LCM-3) delta HCH 15.97 319- 180.9372 216.9141 0.05 86-8 epsilon HCH 16.17 15372 180.9372 216.9141 0.03 22 Bromocyclen 16.18 1715- 356.7986 271.8097 393.7647 0.07 40-8 PCB 28 16.70 7012- 255.9608 186.0230 0.01 37-5 1-(prop-1-enyl)-4-(4- 16.79 27924 205.1952 248.2501 123.1169 1.00 propylcyclohexyl)cyclohexa 6-65-0 ne (LCM-4) Heptachlor 17.00 76-44- 271.8097 236.8407 336.8487 0.05 8 PCB 52 17.56 35693 291.9188 219.9839 0.02 -99-3 1-ethoxy-2,3-difluoro-4-(4- 17.63 17435 282.1791 156.0381 169.0459 0.30 propylcyclohexyl)benzene 0-05-1 (LCM-5) 1,4,5,6,7,7-hexachloro- 17.92 115- 262.8565 260.8595 236.8409 0.20 8,9,10-trinorborn-5-ene-2,3- 27-5 dicarboxylic anhydride 4-methyl-4'-pentylbipheny 18.70 64835 181.1010 238.1717 165.0699 0.02 (LCM-6) -63-8 5 Isodrin 18.71 465- 192.9373 328.9034 363.8723 0.03 73-6 Heptachlor epoxide 19.02 1024- 352.8434 386.8046 316.8668 0.05 57-3 Trans-Chlordane 19.72 5103- 372.8253 374.8225 236.8407 0.03 74-2 o,p-DDE 19.85 3424- 245.9997 317.9343 0.00 82-6 9 PCB 101 19.98 37680 325.8799 290.9107 0.02 -73-2 Cis-Chlordane 20.11 5103- 372.8253 374.8225 236.8407 0.04 71-9 p,p'-DDE 20.87 72-55- 245.9997 317.9343 0.01 9

Dieldrin 20.95 60-57- 379.8682 344.8982 280.9265 1.3 1 o,p DDD 21.08 53-19- 235.0074 165.0697 199.0307 0.01 0 Endosulfan 22.01 115- 236.8407 338.8724 306.8825 0.18 29-7 BDE 28 22.14 41318 405.8023 245.9674 0.08 -75-6 o,p DDT - p,p' DDD 22.27 789- 235.0074 165.0697 199.0307 0.14 02-6 72-54- 8

TDCIPP d15 22.51 - 196.9802 103.0092 393.9775 NA 5 5 5 PCB 153 22.67 35065 289.9034 287.9064 291.9004 0.03 -27-1 1,3,5-tris(oxiranylmethyl)- 23.01 2451- 255.0851 143.0327 82.0288 40.2 1,3,5-triazine- 62-9 2,4,6(1H,3H,5H)-trione 4,4'- 23.01 101- 250.0736 208.0756 221.0709 0.80 Methylenebis(phenylisocya 68-8 nate) tris(1,3-dichloro-2- 23.03 13674 380.8965 208.9537 320.9192 0.34 propyl)phosphate (TDCIPP) -87-8 2,3,7,8- TCDF 23.29 51207 305.8977 303.9008 307.8947 0.02 -31-9 1-methyl-4-(4-(4- 23.31 15504 282.2343 157.1013 171.1169 0.95 vinylcyclohexyl)cyclohexyl) 1-85-3 benzene (LCM-10) p,p'-DDT 23.56 50-29- 235.0074 165.0697 0.07 3 2,3,7,8-TCDD 23.69 1746- 321.8926 319.8956 323.8900 0.04 01-6

Triphenyl phosphate d15 23.84 NA 341.1644 243.0989 223.0758 NA 5 5 5

Triphenyl phosphate 13C18 23.98 NA 343.1228 245.0764 227.0659 NA (MTPP) 5 6 Methoxychlor 24.14 72-43- 227.1066 212.083 274.0754 0.03 5 4-[difluoro(3,4,5- 24.18 30318 281.0949 252.0557 201.0510 0.05 trifluorophenoxy)methyl]- 6-20-1

3,5-difluoro-4'- propylbipheny (LCM-12) Triphenylphosphate (TPHP) 24.30 115- 326.0703 233.0364 215.0255 0.05 86-6 1-methyl-4-(4-(4- 25.28 84656 298.2656 118.0777 105.0700 0.35 propylcyclohexyl)cyclohexyl -75-7 )benzene (LCM-13) 1,2,3,7,8-PeCDF 25.89 57117 339.8587 341.8556 337.8618 0.03 -41-6 PCB 180 26.03 35065 393.8017 323.864 251.9294 0.04 -29-3 BDE 47 26.26 5436- 325.8758 485.7103 0.04 43-1 2,3,4,7,8-PeCDF 26.62 57117 339.8587 341.8556 337.8618 0.03 -31-4 1,2,3,7,8-PeCDD 26.85 40321 355.8535 357.8504 353.8566 0.05 -76-4 BDE 66 26.97 18908 325.8758 485.7103 0.04 4-61-5 Mirex 27.30 2385- 271.8095 236.8405 403.7440 0.03 85-5 1-ethyl-4-(4-(4- 28.61 84540 306.2345 193.1013 221.1327 0.10 propylcyclohexyl)phenyl)be -37-4 nzene (LCM-16) 1,2,3,4,7,8-HxCDF 29.02 70648 373.8197 375.8166 371.8227 0.04 -26-9 1,2,3,6,7,8-HxCDF 29.12 57117 373.8197 375.8166 371.8227 0.03 -44-9 1-ethoxy-2,3-difluoro-4-(4- 29.29 12356 364.2575 156.0382 184.0695 0.35 (4- 0-48-5 propylcyclohexyl)cyclohexyl )benzene (LCM-18) BDE 100 29.51 18908 403.7864 563.6217 0.07 4-64-8 4''-ethyl-2'-fluoro-4- propyl- 29.67 95759 289.1388 318.1779 274.1154 0.05 1,1':4',1''-terphenyl (LCM- -44-7 0 19) 2,3,4,6,7,8-HxCDF 29.69 60851 373.8197 375.8166 371.8227 0.04 -34-5 1,2,3,6,7,8-HxCDD 29.86 57653 389.8147 391.8117 387.8176 0.06 -85-7

1,2,3,4,7,8-HxCDD 29.93 39227 389.8147 391.8117 387.8176 0.05 -28-6 1,2,3,7,8,9-HxCDD 30.19 19408 389.8147 391.8117 387.8176 0.06 -74-3 4-ethoxy-2,3-difluoro-4'-(4- 30.35 18975 358.2104 232.0695 245.0774 0.15 propylcyclohexyl)biphenyl 0-98-9 (LCM-21) 1,2,3,7,8,9 HxCDF 30.43 72918 373.8197 375.8166 371.8227 0.05 -21-9 BDE 99 30.63 60348 403.7864 563.6217 0.07 -60-9 1,2,3,4,6,7,8- HpCDF 31.90 67562 409.7778 407.7808 405.7838 0.05 -39-4 BDE 85 32.42 18234 403.7864 563.6217 0.8 6-21-0 1,2,3,4,6,7,8-HpCDD 33.03 35822 423.7758 425.7729 0.09 -46-9 BDE 154 33.30 20712 483.6944 643.531 0.11 2-15-4 1,2,3,4,7,8,9-HpCDF 33.48 55673 409.7778 407.7808 405.7838 0.07 -89-7 BDE 153 34.82 68631 483.6949 643.531 0.1 -49-2 OCDD 35.99 3268- 459.7338 457.7369 461.7307 0.13 87-9 OCDF 36.11 39001 443.7388 441.7416 0.1 -02-0 3,4-difluoro-4'-[4'-propyl- 37.43 11999 396.2624 216.0745 203.0666 0.20 1,1'-bi(cyclohexyl)-4- 0-81-7 yl]biphenyl (LCM-31) BDE 183 38.77 20712 561.606 721.4430 0.22 2-16-5 3,4-difluoro-4'-[4'-pentyl- 41.01 13660 424.2942 216.0745 203.0666 0.20 1,1'-bi(cyclohexyl)-4- 9-96-6 yl]biphenyl (LCM-33)

Appendix 2. Target compounds using LC-HRMS in positive and negative modes. Compound Retenti CAS Quantificat Confirmati Confirmati Estimat on time numb ion ion on ion 1 on ion 2 ed (min) er m/z m/z m/z MLOQ (ng/g) 4-tert-butylcatechol 8.37 98- 165.0921 149.0608 108.0217 2.3 29-3 BPA 8.71 80- 227.1072 212.0837 133.0653 5.1 05-7 Bithionol 12.35 97- 352.8770 191.9209 160.9566 0.7 18-7 Melamine 0.82 108- 127.0727 85.0509 6.3 78-1 BPS 5.46 80- 251.0373 156.9954 93.0335 7.1 09-1

Triethyl phosphate d15 5.92 NA 198.1727 NA

TCEP d12 7.93 NA 297.0370 NA Pimozide 9.51 2062- 462.2357 328.1871 201.1022 8.9 78-4 Tripropyl phosphate 9.76 NA 246.2574 NA d21

TCIPP d18 10.47 NA 345.1216 NA

TDCIPP d15 12.42 NA 443.9859 NA Diphenyl(2,4,6- 12.71 7598 349.1352 147.0804 119.0855 140 trimethylbenzoyl)phos 0-60- phine oxide 8 Triphenyl phosphate 12.8 NA 342.1728 NA d15 Triphenyl phosphate 12.92 NA 345.1390 NA 13C18 (MTPP)

Tributyl phosphate d27 12.99 NA 294.3420 NA Tributyl citrate (TBC) 14.35 77- 361.2221 185.0808 129.0182 36.3 94-1

Appendix 3. List of detected compounds ID method refers to suspect screening analysis (SSA) or target analysis (TA). Monoisotopic mass is the exact mass of the neutral monoisotopic peak. Analysis method refers to the chromatographic and ionization methods used; EI (GC-EI-HRMS), LC neg (LC-ESI-HRMS negative mode) and LC pos (LC-ESI-HRMS positive mode). Information for precursor mass is only shown for compounds detected in LC mode.

Common_na Formula Mon CAS ID_m Ionis ICL Prec Prec_Mass InChI me oiso_ etho ation ursor (mass_err_ Mass d _mo _ion ppm) de (2Z)-4,6- C16H12 300. NA SSA ESI 2a M-H 299.056 InChI=1S/C16 dihydroxy-2- O6 0634 neg (2 ppm) H12O6/c1-21- [(3-hydroxy- 12-3-2-8(4- 4- 10(12)18)5- methoxyphe 14-16(20)15- nyl)methylid 11(19)6- ene]-1- 9(17)7- benzofuran- 13(15)22- 3-one 14/h2-7,17- 19H,1H3/b14- 5- (2Z)-4,6- C17H14 330. NA SSA ESI 2a M-H 329.0653 InChI=1S/C17 dihydroxy-2- O7 074 neg (2 ppm) H14O7/c1-22- [(4-hydroxy- 12-3-8(4- 3,5- 13(23- dimethoxyp 2)16(12)20)5- henyl)methy 14-17(21)15- lidene]-1- 10(19)6- benzofuran- 9(18)7- 3-one 11(15)24- 14/h3-7,18- 20H,1- 2H3/b14-5- 1- C17H14 234. 607-58- SSA EI 2a InChI=1S/C17 (Benzyloxy)n O 1045 9 H14O/c1-2-7- aphthalene 14(8-3-1)13- 18-17-12-6- 10-15-9-4-5- 11- 16(15)17/h1- 12H,13H2 1,2- C14H14 214. 104-66- SSA EI 2a InChI=1S/C14 Diphenoxyet O2 0994 5 H14O2/c1-3-7- hane 13(8-4-1)15- 11-12-16-14- 9-5-2-6-10- 14/h1-10H,11- 12H2

1,3- C7H5NS 135. 272-16- SSA EI 2a InChI=1S/C7H Benzothiazol 0143 2 5NS/c1-2-4-7- e 6(3-1)8-5-9- 7/h1-5H 1,3- C16H16 208. 7614- SSA EI 3 InChI=1S/C16 diphenylbut 1252 93-9 H16/c1-14(16- ene 10-6-3-7-11- 16)12-13-15- 8-4-2-5-9- 15/h2- 14H,1H3/b13- 12+ 1,3- C13H13 211. 102-06- SSA ESI 2b M+H 212.1166 InChI=1S/C13 Diphenylgua N3 1109 7 pos (10 ppm) H13N3/c14- nidine 13(15-11-7-3- 1-4-8-11)16- 12-9-5-2-6-10- 12/h1- 10H,(H3,14,15 ,16) 10,18- C18H26 242. 32624- SSA EI 3 InChI=1S/C18 Bisnorabieta 2035 67-2 H26/c1- -8,11,13- 12(2)14-7-10- triene 17-15(11- 14)8-9-16- 13(3)5-4-6- 18(16)17/h7,1 0-13,16,18H,4- 6,8-9H2,1-3H3 1-Naphthyl C20H14 270. 607-52- SSA EI 3 InChI=1S/C20 ether O 1045 3 H14O/c1-3-11- 17-15(7-1)9-5- 13-19(17)21- 20-14-6-10- 16-8-2-4-12- 18(16)20/h1- 14H 1-Phenoxy- C9H12O 152. 770-35- SSA EI 2a InChI=1S/C9H 2-propanol 2 0837 4 12O2/c1- 8(10)7-11-9-5- 3-2-4-6-9/h2- 6,8,10H,7H2,1 H3 2,3,4- C6H4Cl3 194. 634-67- SSA EI 3 InChI=1S/C6H Trichloroanil N 9409 3 4Cl3N/c7-3-1- ine 2- 4(10)6(9)5(3)8 /h1-2H,10H2 2,4,6- C6H3Br 327. 118-79- SSA EI 3 InChI=1S/C6H Tribromoph 3O 7734 6 3Br3O/c7-3-1- enol

4(8)6(10)5(9)2 -3/h1-2,10H

2,4,6- C10H12 164. 480-63- SSA EI 2a InChI=1S/C10 Trimethylbe O2 0837 7 H12O2/c1-6-4- nzoic acid 7(2)9(10(11)12 )8(3)5-6/h4- 5H,1- 3H3,(H,11,12) 2,4-bis(1- C24H26 330. 2772- SSA EI 2b InChI=1S/C24 methyl-1- O 1984 45-4 H26O/c1- phenylethyl) 23(2,18-11-7- phenol 5-8-12-18)20- 15-16- 22(25)21(17- 20)24(3,4)19- 13-9-6-10-14- 19/h5- 17,25H,1-4H3 2,4- C8H10O 186. 88-61-9 SSA ESI 2a M-H 185.0279 InChI=1S/C8H Dimethylben 3S 0351 neg (4 ppm) 10O3S/c1-6-3- zenesulfonic 4-8(7(2)5- acid 6)12(9,10)11/ h3-5H,1- 2H3,(H,9,10,1 1) 2,4-TDI C9H6N2 174. 584-84- TA EI 1 InChI=1S/C9H O2 0429 9 6N2O2/c1-7-2- 3-8(10-5-12)4- 9(7)11-6- 13/h2-4H,1H3 2,5-Di-tert- C16H26 250. 79-74-3 SSA EI 2a InChI=1S/C16 pentylhydro O2 1933 H26O2/c1-7- quinone 15(3,4)11-9- 14(18)12(10- 13(11)17)16(5, 6)8-2/h9- 10,17-18H,7- 8H2,1-6H3 2,6- C6H4Br 293. 827-94- SSA EI 3 InChI=1S/C6H Dibromo-4- 2N2O2 8639 1 4Br2N2O2/c7- nitroaniline 4-1- 3(10(11)12)2- 5(8)6(4)9/h1- 2H,9H2 2,6-TDI C9H6N2 174. 91-08-7 TA EI 1 InChI=1S/C9H O2 0429 6N2O2/c1-7- 8(10-5-12)3-2- 4-9(7)11-6- 13/h2-4H,1H3 2,6-Xylidine C8H11N 121. 87-62-7 SSA ESI 3 M+H 122.0974 InChI=1S/C8H 0891 pos (3 ppm) 11N/c1-6-4-3- 43

5- 7(2)8(6)9/h3- 5H,9H2,1-2H3 2- C15H22 250. NA SSA ESI 2a M-H 249.1504 InChI=1S/C15 [(1S,2S,4aR,8 O3 1569 neg (5 ppm) H22O3/c1-9-5- aS)-1- 4-7-15(3)8-6- hydroxy-4a- 11(10(2)14(17) methyl-8- 18)13(16)12(9) methylidene 15/h11- - 13,16H,1-2,4- 1,2,3,4,5,6,7, 8H2,3H3,(H,17 8a- ,18)/t11-,12+, octahydrona 13-,15+/m0/s1 phthalen-2- yl]prop-2- enoic acid 2- C7H5NO 214. 941-57- SSA ESI 2a M-H 213.9646 InChI=1S/C7H Benzothiazol 3S2 9711 1 neg (6 ppm) 5NO3S2/c9- esulfonic 13(10,11)7-8- acid 5-3-1-2-4- 6(5)12-7/h1- 4H,(H,9,10,11) 2-Bromo-4- C6H3Br 215. NA SSA ESI 3 M-H 214.9222 1S/C6H4BrNO nitrophenola NO3 9296 neg (2 ppm) 3/c7-5-3- te 4(8(10)11)1-2- 6(5)9/h1- 3,9H/p-1 2-Chloro-4,6- C6H4Cl 216. 3531- SSA EI 2a InChI=1S/C6H dinitroanilin N3O4 989 19-9 4ClN3O4/c7-4- e 1-3(9(11)12)2- 5(6(4)8)10(13) 14/h1-2H,8H2 2- C18H30 326. 27176- SSA EI 3 InChI=1S/C18 Dodecylbenz O3S 1916 87-0 H30O3S/c1-2- enesulfonic 3-4-5-6-7-8-9- acid 10-11-14-17- 15-12-13-16- 18(17)22(19,2 0)21/h12- 13,15-16H,2- 11,14H2,1H3,( H,19,20,21) 2-Ethylhexyl C20H27 362. 1241- SSA EI 3 InChI=1S/C20 diphenyl O4P 1647 94-7 H27O4P/c1-3- phosphate 5-12-18(4- 2)17-22- 25(21,23-19- 13-8-6-9-14- 19)24-20-15- 10-7-11-16- 20/h6-11,13-

16,18H,3- 5,12,17H2,1- 2H3 2- C14H8O 224. 605-32- SSA ESI 2a M-H 223.0413 InChI=1S/C14 Hydroxyanth 3 0473 3 neg (8 ppm) H8O3/c15-8-5- raquinone 6-11-12(7- 8)14(17)10-4- 2-1-3- 9(10)13(11)16 /h1-7,15H 2- C7H5NO 151. 934-34- SSA ESI 2b M+H 152.0156 InChI=1S/C7H Hydroxyben S 0092 9 pos (9 ppm) 5NOS/c9-7-8- zothiazole 5-3-1-2-4- 6(5)10-7/h1- 4H,(H,8,9) 2- C10H8O 208. 120-18- SSA ESI 2a M-H 207.0132 InChI=1S/C10 Naphthalene 3S 0194 3 neg (8 ppm) H8O3S/c11- sulfonic acid 14(12,13)10-6- 5-8-3-1-2-4- 9(8)7-10/h1- 7H,(H,11,12,1 3) 3,4- C7H3Cl2 186. 102-36- SSA EI 3 InChI=1S/C7H Dichlorophe NO 9592 3 3Cl2NO/c8-6- nyl 2-1-5(10-4- isocyanate 11)3-7(6)9/h1- 3H 3,5,6- C5H2NO 196. 6515- NTA, ESI 1 M-H 195.9127 1S/C5H2Cl3N Trichloro-2- Cl3 9202 38-4 TA neg (2 ppm) O/c6-2-1- pyridinol 3(7)5(10)9- 4(2)8/h1H,(H, 9,10) 3,5- C6H5Cl2 160. 626-43- SSA EI 3 InChI=1S/C6H Dichloroanili N 9799 7 5Cl2N/c7-4-1- ne 5(8)3-6(9)2- 4/h1-3H,9H2 3- C26H30 486. 53899- SSA ESI 2a M-H 485.1814 InChI=1S/C26 Hydroxyphys O9 189 46-0 neg (0 ppm) H30O9/c1-3-5- odic acid 7-9-15(27)11- 14-12- 18(29)22(30)2 4- 20(14)26(33)3 4-19-13- 17(28)21(25(3 1)32)16(23(19) 35-24)10-8-6- 4-2/h12- 13,28-30H,3- 11H2,1- 2H3,(H,31,32) 45

4,6- C27H44 384. 14214- SSA EI 2b InChI=1S/C27 cholestadien O 3392 69-8 H44O/c1- ol 18(2)7-6-8- 19(3)23-11- 12-24-22-10- 9-20-17- 21(28)13-15- 26(20,4)25(22) 14-16- 27(23,24)5/h9 -10,17-19,21- 25,28H,6-8,11- 16H2,1- 5H3/t19-,21+, 22+,23-,24+,2 5+,26+,27- /m1/s1 4',7- C17H14 298. 5128- SSA EI 2b InChI=1S/C17 Dimethylapi O5 0841 44-9 H14O5/c1-20- genin 11-5-3-10(4-6- 11)15-9- 14(19)17- 13(18)7- 12(21-2)8- 16(17)22- 15/h3- 9,18H,1-2H3 4-chloro-2- C6H5Cl 172. 89-63-4 SSA EI 3 InChI=1S/C6H nitroaniline N2O2 004 5ClN2O2/c7-4- 1-2-5(8)6(3- 4)9(10)11/h1- 3H,8H2 4- C6H6Cl 127. 106-47- SSA ESI 3 M-H 126.0098 InChI=1S/C6H Chloroanilin N 0189 8 neg (10 ppm) 6ClN/c7-5-1-3- e 6(8)4-2-5/h1- 4H,8H2 4- C6H6Cl 127. 106-47- SSA EI 3 InChI=1S/C6H Chloroanilin N 0189 8 6ClN/c7-5-1-3- e 6(8)4-2-5/h1- 4H,8H2 4- C15H16 212. 599-64- SSA EI 3 InChI=1S/C15 Cumylpheno O 1201 4 H16O/c1- l 15(2,12-6-4-3- 5-7-12)13-8- 10-14(16)11- 9-13/h3- 11,16H,1-2H3 4- C7H6O2 122. 123-08- SSA ESI 2a M-H 121.0293 InChI=1S/C7H Hydroxyben 0368 0 neg (2 ppm) 6O2/c8-5-6-1- zaldehyde 3-7(9)4-2- 6/h1-5,9H

4- C7H6O3 138. 456-23- SSA ESI 2a M-H 137.0234 InChI=1S/C7H Hydroxyben 0317 5 neg (3 ppm) 6O3/c8-6-3-1- zoate 5(2-4- 6)7(9)10/h1- 4,8H,(H,9,10)/ p-1 4- C6H5NO 139. 100-02- SSA ESI 2a M-H 138.0197 InChI=1S/C6H Nitrophenol 3 0269 7 neg (4 ppm) 5NO3/c8-6-3- 1-5(2-4- 6)7(9)10/h1- 4,8H 4-Sec-Butyl- C18H30 262. 17540- SSA EI 2b InChI=1S/C18 2,6-di-tert- O 2297 75-9 H30O/c1-9- butylphenol 12(2)13-10- 14(17(3,4)5)16 (19)15(11- 13)18(6,7)8/h 10- 12,19H,9H2,1- 8H3 4-tert- C10H14 166. 98-29-3 TA ESI 1 M-H 165.0921 1S/C10H14O2 butylcatecho O2 0994 neg (3 ppm) /c1-10(2,3)7- l 4-5- 8(11)9(12)6- 7/h4-6,11- 12H,1-3H3 5,7- C17H14 298. NA SSA ESI 3 M+H 299.0926 InChI=1S/C17 Dimethoxy- O5 0841 pos (2 ppm) H14O5/c1-20- 3- 11-8-12(21- hydroxyflavo 2)14-13(9- ne 11)22- 17(16(19)15(1 4)18)10-6-4-3- 5-7-10/h3- 9,19H,1-2H3 6:2 FTSA C8H5F1 427. 27619- SSA ESI 3 M-H 426.9692 InChI=1S/C8H 3O3S 9752 97-2 neg (4 ppm) 5F13O3S/c9- 3(10,1-2- 25(22,23)24)4( 11,12)5(13,14) 6(15,16)7(17,1 8)8(19,20)21/ h1- 2H2,(H,22,23, 24) 7,9-Di-tert- C17H24 276. 82304- SSA EI 2a InChI=1S/C17 butyl-1- O3 1725 66-3 H24O3/c1- oxaspiro(4,5 15(2,3)11-9- )deca-6,9- 17(8-7- diene-2,8- 13(18)20- dione 17)10-

12(14(11)19)1 6(4,5)6/h9- 10H,7-8H2,1- 6H3 7- C27H44 400. 566-28- SSA ESI 2a M+H 401.3453 InChI=1S/C27 Oxocholeste O2 3341 9 pos (8 ppm) H44O2/c1- rol 17(2)7-6-8- 18(3)21-9-10- 22-25-23(12- 14- 27(21,22)5)26( 4)13-11- 20(28)15- 19(26)16- 24(25)29/h16- 18,20- 23,25,28H,6- 15H2,1- 5H3/t18-,20+, 21-,22+,23+,2 5+,26+,27- /m1/s1 8:2 FTSA C10H5F 527. 39108- SSA ESI 2a M-H 526.9622 InChI=1S/C10 17O3S 9688 34-4 neg (2 ppm) H5F17O3S/c11 -3(12,1-2- 31(28,29)30)4( 13,14)5(15,16) 6(17,18)7(19,2 0)8(21,22)9(23 ,24)10(25,26)2 7/h1- 2H2,(H,28,29, 30) Acacetin C16H12 284. 480-44- SSA ESI 2a M-H 283.0616 InChI=1S/C16 O5 0685 4 neg (3 ppm) H12O5/c1-20- 11-4-2-9(3-5- 11)14-8- 13(19)16- 12(18)6- 10(17)7- 15(16)21- 14/h2-8,17- 18H,1H3 Acacetin C16H12 284. 480-44- SSA ESI 2a M+H 285.0771 InChI=1S/C16 O5 0685 4 pos (3 ppm) H12O5/c1-20- 11-4-2-9(3-5- 11)14-8- 13(19)16- 12(18)6- 10(17)7- 15(16)21-

14/h2-8,17- 18H,1H3

Acetaminop C8H9NO 151. 103-90- SSA ESI 2a M-H 150.0565 InChI=1S/C8H hen 2 0633 2 neg (6 ppm) 9NO2/c1- 6(10)9-7-2-4- 8(11)5-3-7/h2- 5,11H,1H3,(H, 9,10) Acetaminop C8H9NO 151. 103-90- SSA ESI 2a M+H 152.0713 InChI=1S/C8H hen 2 0633 2 pos (1 ppm) 9NO2/c1- 6(10)9-7-2-4- 8(11)5-3-7/h2- 5,11H,1H3,(H, 9,10) Acetaminop C8H9NO 151. 103-90- SSA EI 2a InChI=1S/C8H hen 2 0633 2 9NO2/c1- 6(10)9-7-2-4- 8(11)5-3-7/h2- 5,11H,1H3,(H, 9,10) Aerugidiol C15H22 250. 116425- SSA ESI 3 M+H 233.1549 InChI=1S/C15 O3 1569 35-5 pos -H2O (3 ppm) H22O3/c1- 9(2)11-8-13- 14(4,17)5-6- 15(13,18)10(3) 7- 12(11)16/h7,1 3,17-18H,5- 6,8H2,1- 4H3/t13-,14+, 15+/m1/s1 Amylcinnam C14H18 202. 122-40- SSA EI 2a InChI=1S/C14 aldehyde O 1358 7 H18O/c1-2-3- 5-10-14(12- 15)11-13-8-6- 4-7-9-13/h4,6- 9,11-12H,2- 3,5,10H2,1H3/ b14-11- Androstane C19H32 260. 24887- SSA EI 3 InChI=1S/C19 2504 75-0 H32/c1-18-11- 5-7-16(18)15- 9-8-14-6-3-4- 12- 19(14,2)17(15) 10-13-18/h14- 17H,3-13H2,1- 2H3/t14?,15-, 16-,17-,18-,19- /m0/s1 49

Anthracene, C18H22 238. NA SSA EI 3 InChI=1S/C18 9-butyl- 1722 H22/c1-2-3- 1,2,3,4- 10-18-16-11- tetrahydro- 6-4-8- 14(16)13-15- 9-5-7-12- 17(15)18/h4,6, 8,11,13H,2- 3,5,7,9- 10,12H2,1H3 Apigenin C15H10 270. 520-36- SSA ESI 2a M-H 269.046 (4 InChI=1S/C15 O5 0528 5 neg ppm) H10O5/c16-9- 3-1-8(2-4- 9)13-7- 12(19)15- 11(18)5- 10(17)6- 14(15)20- 13/h1-7,16- 18H Apigenin C15H10 270. 520-36- SSA ESI 2a M+H 271.0602 InChI=1S/C15 O5 0528 5 pos (2 ppm) H10O5/c16-9- 3-1-8(2-4- 9)13-7- 12(19)15- 11(18)5- 10(17)6- 14(15)20- 13/h1-7,16- 18H Apigenin-7- C21H20 432. 578-74- SSA ESI 2a M-H 431.0961 InChI=1S/C21 O-glucoside O10 1056 5 neg (4 ppm) H20O10/c22- 8-16- 18(26)19(27)2 0(28)21(31- 16)29-11-5- 12(24)17- 13(25)7- 14(30- 15(17)6-11)9- 1-3-10(23)4-2- 9/h1-7,16,18- 24,26- 28H,8H2/t16-, 18-,19+,20-,21 -/m1/s1 Aspartame C14H18 294. 22839- SSA ESI 2b M+H 295.1282 InChI=1S/C14 N2O5 1216 47-0 pos (4 ppm) H18N2O5/c1- 21- 14(20)11(7-9- 5-3-2-4-6-

9)16- 13(19)10(15)8- 12(17)18/h2- 6,10-11H,7- 8,15H2,1H3,(H ,16,19)(H,17,1 8)/t10-,11- /m0/s1 Asperphena C32H30 506. 63631- SSA ESI 2b M+H 507.2281 InChI=1S/C32 mate N2O4 2206 36-7 pos (1 ppm) H30N2O4/c35 -30(26-17-9-3- 10-18-26)33- 28(21-24-13- 5-1-6-14- 24)23-38- 32(37)29(22- 25-15-7-2-8- 16-25)34- 31(36)27-19- 11-4-12-20- 27/h1-20,28- 29H,21- 23H2,(H,33,35 )(H,34,36)/t28 -,29-/m0/s1 ATBC C20H34 402. 77-90-7 SSA ESI 2b M+H 403.232 (3 InChI=1S/C20 O8 2254 pos ppm) H34O8/c1-5-8- 11-25- 17(22)14- 20(28- 16(4)21,19(24) 27-13-10-7- 3)15- 18(23)26-12- 9-6-2/h5- 15H2,1-4H3 ATBC C20H34 402. 77-90-7 SSA EI 2a InChI=1S/C20 O8 2254 H34O8/c1-5-8- 11-25- 17(22)14- 20(28- 16(4)21,19(24) 27-13-10-7- 3)15- 18(23)26-12- 9-6-2/h5- 15H2,1-4H3 Atranol C8H8O3 152. 526-37- SSA ESI 2a M-H 151.0403 InChI=1S/C8H 0473 4 neg (5 ppm) 8O3/c1-5-2- 7(10)6(4-

9)8(11)3-5/h2- 4,10-11H,1H3 Avocadene C19H36 328. 24607- SSA ESI 2a M-H 327.253 (2 InChI=1S/C19 1-acetate O4 2614 09-8 neg ppm) H36O4/c1-3-4- 5-6-7-8-9-10- 11-12-13-14- 18(21)15- 19(22)16-23- 17(2)20/h3,18 -19,21- 22H,1,4- 16H2,2H3 BAC-C12 C21H38 304. 8001- SSA ESI 2b M+ 304.2981 InChI=1S/C21 N 3004 54-5 pos (8 ppm) H38N/c1-4-5- 6-7-8-9-10-11- 12-16-19- 22(2,3)20-21- 17-14-13-15- 18-21/h13- 15,17-18H,4- 12,16,19- 20H2,1- 3H3/q+1 BBP C19H20 312. 85-68-7 SSA ESI 3 M+H 313.1416 InChI=1S/C19 O4 1362 pos (8 ppm) H20O4/c1-2-3- 13-22- 18(20)16-11- 7-8-12- 17(16)19(21)2 3-14-15-9-5-4- 6-10-15/h4- 12H,2-3,13- 14H2,1H3 BBP C19H20 312. 85-68-7 SSA EI 3 InChI=1S/C19 O4 1362 H20O4/c1-2-3- 13-22- 18(20)16-11- 7-8-12- 17(16)19(21)2 3-14-15-9-5-4- 6-10-15/h4- 12H,2-3,13- 14H2,1H3 BDE 47 C12H6B 481. 5436- TA EI 1 InChI=1S/C12 r4O 7152 43-1 H6Br4O/c13- 7-1-3- 11(9(15)5- 7)17-12-4-2- 8(14)6- 10(12)16/h1- 6H

BDE 99 C12H5B 559. 60348- TA EI 1 InChI=1S/C12 r5O 6257 60-9 H5Br5O/c13- 6-1-2- 11(9(16)3- 6)18-12-5- 8(15)7(14)4- 10(12)17/h1- 5H Benzo[a]dib C16H10 234. 239-35- SSA EI 3 InChI=1S/C16 enzothiophe S 0503 0 H10S/c1-2-6- ne 12-11(5-1)9- 10-14-13-7-3- 4-8-15(13)17- 16(12)14/h1- 10H Benzoylecgo C16H19 289. 519-09- SSA ESI 2b M+H 290.1388 InChI=1S/C16 nine NO4 1314 5 pos (2 ppm) H19NO4/c1- 17-11-7-8- 12(17)14(15(1 8)19)13(9- 11)21- 16(20)10-5-3- 2-4-6-10/h2- 6,11-14H,7- 9H2,1H3,(H,18 ,19)/t11-,12+, 13-,14+/m0/s1 Benzyl C14H12 212. 120-51- SSA EI 2a InChI=1S/C14 Benzoate O2 0837 4 H12O2/c15- 14(13-9-5-2-6- 10-13)16-11- 12-7-3-1-4-8- 12/h1- 10H,11H2 Benzyl C14H12 228. 118-58- SSA EI 2a InChI=1S/C14 salicylate O3 0786 1 H12O3/c15- 13-9-5-4-8- 12(13)14(16)1 7-10-11-6-2-1- 3-7-11/h1- 9,15H,10H2 BHT-OH C15H24 236. 10396- SSA EI 2b InChI=1S/C15 O2 1776 80-2 H24O2/c1- 13(2,3)10-8- 15(7,17)9- 11(12(10)16)1 4(4,5)6/h8- 9,17H,1-7H3 BIT C7H5NO 151. 2634- SSA ESI 2b M+H 152.0175 InChI=1S/C7H S 0092 33-5 pos (3 ppm) 5NOS/c9-7-5- 3-1-2-4-

6(5)10-8-7/h1- 4H,(H,8,9) BPA C15H16 228. 80-05-7 TA ESI 1 M-H 227.1072 1S/C15H16O2 O2 115 neg (0 ppm) /c1-15(2,11-3- 7-13(16)8-4- 11)12-5-9- 14(17)10-6- 12/h3-10,16- 17H,1-2H3 BPA C15H16 228. 80-05-7 SSA EI 2a InChI=1S/C15 O2 115 H16O2/c1- 15(2,11-3-7- 13(16)8-4- 11)12-5-9- 14(17)10-6- 12/h3-10,16- 17H,1-2H3 BPS C12H10 250. 80-09-1 SSA ESI 2a M-H 249.024 (7 InChI=1S/C12 O4S 03 neg ppm) H10O4S/c13- 9-1-5-11(6-2- 9)17(15,16)12- 7-3-10(14)4-8- 12/h1-8,13- 14H BPS C12H10 250. 80-09-1 TA ESI 1 M+H 251.0373 1S/C12H10O4 O4S 03 pos (2 ppm) S/c13-9-1-5- 11(6-2- 9)17(15,16)12- 7-3-10(14)4-8- 12/h1-8,13- 14H Br-BPA C15H15 306. 6073- SSA ESI 2 M-H 305.0164 1S/C15H15Br BrO2 0255 11-6 neg (4 ppm) O2/c1- 15(2,10-3-6- 12(17)7-4- 10)11-5-8- 14(18)13(16)9- 11/h3-9,17- 18H,1-2H3 Brucine C23H26 394. 357-57- SSA ESI 2b M+H 395.196 (3 InChI=1S/C23 N2O4 1893 3 pos ppm) H26N2O4/c1- 27-16-8-14- 15(9- 17(16)28- 2)25- 20(26)10-18- 21-13-7-19- 23(14,22(21)2 5)4-5- 24(19)11- 12(13)3-6-29-

18/h3,8- 9,13,18-19,21- 22H,4-7,10- 11H2,1- 2H3/t13-,18-,1 9-,21-,22-,23+ /m0/s1 BTBPE C14H8B 681. 37853- SSA EI 2b InChI=1S/C14 r6O2 5624 59-1 H8Br6O2/c15- 7-3- 9(17)13(10(18) 4-7)21-1-2-22- 14-11(19)5- 8(16)6- 12(14)20/h3- 6H,1-2H2 Bumetrizole C17H18 315. 3896- SSA EI 2a InChI=1S/C17 ClN3O 1138 11-5 H18ClN3O/c1- 10-7- 12(17(2,3)4)16 (22)15(8- 10)21-19-13- 6-5-11(18)9- 14(13)20- 21/h5- 9,22H,1-4H3 C.I Disperse C20H13 331. 17418- SSA EI 3 InChI=1S/C20 Red 60 NO4 0845 58-5 H13NO4/c21- 18-15(25-11- 6-2-1-3-7- 11)10- 14(22)16- 17(18)20(24)1 3-9-5-4-8- 12(13)19(16)2 3/h1- 10,22H,21H2 C.I Disperse C20H13 331. 17418- SSA ESI 3 M+H 332.0918 InChI=1S/C20 Red 60 NO4 0845 58-5 pos (1 ppm) H13NO4/c21- 18-15(25-11- 6-2-1-3-7- 11)10- 14(22)16- 17(18)20(24)1 3-9-5-4-8- 12(13)19(16)2 3/h1- 10,22H,21H2 C.I. Basic C19H17 287. 479-73- SSA ESI 2b M+H 288.1498 InChI=1S/C19 Red 9 N3 1422 2 pos (1 ppm) H17N3/c20- 16-7-1-13(2-8-

16)19(14-3-9- 17(21)10-4- 14)15-5-11- 18(22)12-6- 15/h1- 12,20H,21- 22H2 C.I. Basic C19H17 287. 479-73- SSA EI 3 InChI=1S/C19 Red 9 N3 1422 2 H17N3/c20- 16-7-1-13(2-8- 16)19(14-3-9- 17(21)10-4- 14)15-5-11- 18(22)12-6- 15/h1- 12,20H,21- 22H2 Caffeine C8H10N 194. 58-08-2 SSA ESI 2b M+H 195.0868 InChI=1S/C8H 4O2 0804 pos (7 ppm) 10N4O2/c1- 10-4-9-6- 5(10)7(13)12(3 )8(14)11(6)2/h 4H,1-3H3 Caffeine C8H10N 194. 58-08-2 SSA EI 2a InChI=1S/C8H 4O2 0804 10N4O2/c1- 10-4-9-6- 5(10)7(13)12(3 )8(14)11(6)2/h 4H,1-3H3 Chloroatran C8H7Cl 186. 57074- SSA ESI 3 M-H 185.0002 InChI=1S/C8H ol O3 0084 21-2 neg (2 ppm) 7ClO3/c1-4-2- 6(11)5(3- 10)8(12)7(4)9/ h2-3,11- 12H,1H3 Chloroatran C19H17 408. 479-16- SSA ESI 2a M-H 407.0548 InChI=1S/C19 orin ClO8 0612 3 neg (4 ppm) H17ClO8/c1-7- 5- 11(8(2)15(22)1 2(7)18(25)27- 4)28- 19(26)13- 9(3)14(20)17(2 4)10(6- 21)16(13)23/h 5-6,22-24H,1- 4H3 Chlorpyrifos C9H11Cl 348. 2921- SSA EI 2a InChI=1S/C9H 3NO3PS 9263 88-2 11Cl3NO3PS/c 1-3-14- 17(18,15-4-

2)16-9-7(11)5- 6(10)8(12)13- 9/h5H,3- 4H2,1-2H3 Cholesterol C27H46 386. 57-88-5 SSA EI 2a InChI=1S/C27 O 3549 H46O/c1- 18(2)7-6-8- 19(3)23-11- 12-24-22-10- 9-20-17- 21(28)13-15- 26(20,4)25(22) 14-16- 27(23,24)5/h9, 18-19,21- 25,28H,6-8,10- 17H2,1- 5H3/t19-,21+, 22+,23-,24+,2 5+,26+,27- /m1/s1 Cocaine C17H21 303. 50-36-2 SSA ESI 2b M+H 304.1578 InChI=1S/C17 NO4 1471 pos (9 ppm) H21NO4/c1- 18-12-8-9- 13(18)15(17(2 0)21-2)14(10- 12)22- 16(19)11-6-4- 3-5-7-11/h3- 7,12-15H,8- 10H2,1- 2H3/t12-,13+, 14-,15+/m0/s1 Cocaine C17H21 303. 50-36-2 SSA EI 2a InChI=1S/C17 NO4 1471 H21NO4/c1- 18-12-8-9- 13(18)15(17(2 0)21-2)14(10- 12)22- 16(19)11-6-4- 3-5-7-11/h3- 7,12-15H,8- 10H2,1-2H3 Coronene C24H12 300. 191-07- SSA EI 2b InChI=1S/C24 0939 1 H12/c1-2-14- 5-6-16-9-11- 18-12-10-17- 8-7-15-4-3- 13(1)19- 20(14)22(16)2

4(18)23(17)21( 15)19/h1-12H

Cotinine C10H12 176. 486-56- SSA ESI 2b M+H 177.103 (1 InChI=1S/C10 N2O 095 6 pos ppm) H12N2O/c1- 12-9(4-5- 10(12)13)8-3- 2-6-11-7-8/h2- 3,6-7,9H,4- 5H2,1H3/t9- /m0/s1 Coumaric C9H8O3 164. 4501- SSA ESI 2b M+H 147.0441 InChI=1S/C9H acid 0473 31-9 pos -H2O (4 ppm) 8O3/c10-8-4- 1-7(2-5-8)3-6- 9(11)12/h1- 6,10H,(H,11,1 2)/b6-3- Crystal violet C25H30 372. 7438- SSA ESI 2b M+ 372.242 (5 InChI=1S/C25 N3 244 46-2 pos ppm) H30N3/c1- 26(2)22-13-7- 19(8-14- 22)25(20-9- 15-23(16-10- 20)27(3)4)21- 11-17-24(18- 12- 21)28(5)6/h7- 18H,1- 6H3/q+1 Cyfluthrin C22H18 433. 68359- SSA EI 3 InChI=1S/C22 Cl2FNO 0648 37-5 H18Cl2FNO3/c 3 1-22(2)15(11- 19(23)24)20(2 2)21(27)29- 18(12-26)13- 8-9- 16(25)17(10- 13)28-14-6-4- 3-5-7-14/h3- 11,15,18,20H, 1-2H3 DBP C16H22 278. 84-74-2 SSA ESI 2a M-H 277.1454 InChI=1S/C16 O4 1518 neg (5 ppm) H22O4/c1-3-5- 11-19- 15(17)13-9-7- 8-10- 14(13)16(18)2 0-12-6-4-2/h7- 10H,3-6,11- 12H2,1-2H3

DBP C16H22 278. 84-74-2 SSA ESI 3 M+H 279.1591 InChI=1S/C16 O4 1518 pos (2 ppm) H22O4/c1-3-5- 11-19- 15(17)13-9-7- 8-10- 14(13)16(18)2 0-12-6-4-2/h7- 10H,3-6,11- 12H2,1-2H3 Dehydroabie C20H28 300. 1740- SSA EI 2a InChI=1S/C20 tic acid O2 2089 19-8 H28O2/c1- 13(2)14-6-8- 16-15(12- 14)7-9-17- 19(16,3)10-5- 11- 20(17,4)18(21) 22/h6,8,12- 13,17H,5,7,9- 11H2,1- 4H3,(H,21,22)/ t17-,19-,20- /m1/s1 Dehydroabie C20H30 286. 3772- SSA EI 3 InChI=1S/C20 tinol O 2297 55-2 H30O/c1- 14(2)15-6-8- 17-16(12- 15)7-9-18- 19(3,13-21)10- 5-11- 20(17,18)4/h6, 8,12,14,18,21 H,5,7,9- 11,13H2,1- 4H3 Delphinidin C15H11 303. 528-53- SSA ESI 2a M- 301.0364 InChI=1S/C15 O7 0505 0 neg 2H (5 ppm) H10O7/c16-7- 3-9(17)8-5- 12(20)15(22- 13(8)4-7)6-1- 10(18)14(21)1 1(19)2-6/h1- 5H,(H5-,16,17, 18,19,20,21)/p +1

DEP C12H14 222. 84-66-2 SSA ESI 2a M-H 221.0803 InChI=1S/C12 O4 0892 neg (5 ppm) H14O4/c1-3- 15-11(13)9-7- 5-6-8- 10(9)12(14)16-

4-2/h5-8H,3- 4H2,1-2H3

DEP C12H14 222. 84-66-2 SSA EI 3 InChI=1S/C12 O4 0892 H14O4/c1-3- 15-11(13)9-7- 5-6-8- 10(9)12(14)16- 4-2/h5-8H,3- 4H2,1-2H3 Diazinone C12H21 304. 333-41- SSA EI 2b InChI=1S/C12 N2O3PS 1011 5 H21N2O3PS/c 1-6-15- 18(19,16-7- 2)17-11-8- 10(5)13- 12(14- 11)9(3)4/h8- 9H,6-7H2,1- 5H3 Dibenzylami C14H15 197. 103-49- SSA ESI 2b M+H 198.1281 InChI=1S/C14 ne N 1204 1 pos (1 ppm) H15N/c1-3-7- 13(8-4-1)11- 15-12-14-9-5- 2-6-10-14/h1- 10,15H,11- 12H2 Dichlofluani C9H11Cl 331. 1085- SSA EI 2a InChI=1S/C9H d 2FN2O2 9623 98-9 11Cl2FN2O2S2 S2 /c1- 13(2)18(15,16) 14(17- 9(10,11)12)8- 6-4-3-5-7- 8/h3-7H,1-2H3 Dichlorophe C13H10 268. 97-23-4 SSA ESI 2a M-H 266.9973 InChI=1S/C13 n Cl2O2 0058 neg (3 ppm) H10Cl2O2/c14 -10-1-3- 12(16)8(6- 10)5-9-7- 11(15)2-4- 13(9)17/h1- 4,6-7,16- 17H,5H2 Diclofenac C14H11 295. 15307- NTA, ESI 1 M-H 294.0096 1S/C14H11Cl2 Cl2NO2 0167 86-5 TA neg (3 ppm) NO2/c15-10-5- 3-6- 11(16)14(10)1 7-12-7-2-1-4- 9(12)8- 13(18)19/h1-

7,17H,8H2,(H, 18,19)

Dicyclohexyl C12H23 181. 101-83- SSA ESI 2b M+H 182.1906 InChI=1S/C12 amine N 183 7 pos (2 ppm) H23N/c1-3-7- 11(8-4-1)13- 12-9-5-2-6-10- 12/h11-13H,1- 10H2 Didymin C28H34 594. 14259- SSA ESI 2a M-H 593.1855 InChI=1S/C28 O14 1949 47-3 neg (3 ppm) H34O14/c1- 11- 21(31)23(33)2 5(35)27(39- 11)38-10-19- 22(32)24(34)2 6(36)28(42- 19)40-14-7- 15(29)20- 16(30)9- 17(41- 18(20)8- 14)12-3-5- 13(37-2)6-4- 12/h3- 8,11,17,19,21- 29,31-36H,9- 10H2,1- 2H3/t11-,17-,1 9+,21-,22+,23 +,24-,25+,26+, 27+,28+/m0/s 1 Dihydrokae C15H12 288. 5150- SSA ESI 3 M-H 287.057 (5 InChI=1S/C15 mpferol O6 0634 32-3 neg ppm) H12O6/c16-8- 3-1-7(2-4- 8)15- 14(20)13(19)1 2-10(18)5- 9(17)6- 11(12)21- 15/h1-6,14- 18,20H Dinitrobrom C6H3Br 261. 2316- SSA ESI 3 M-H 260.9135 InChI=1S/C6H ophenol N2O5 9225 50-9 neg (5 ppm) 3BrN2O5/c7- 4-1- 3(8(11)12)2- 5(6(4)10)9(13) 14/h1-2,10H Dinoterb/Di C10H12 240. 1420- SSA ESI 3 M-H 239.0677 InChI=1S/C10 noseb N2O5 0746 07-1 neg (4 ppm) H12N2O5/c1- 61

10(2,3)7-4- 6(11(14)15)5- 8(9(7)13)12(16 )17/h4- 5,13H,1-3H3 Dioctyl C24H38 390. 117-84- SSA ESI 3 M+H 391.2841 InChI=1S/C24 Phthalate O4 277 0 pos (2 ppm) H38O4/c1-3-5- 7-9-11-15-19- 27-23(25)21- 17-13-14-18- 22(21)24(26)2 8-20-16-12- 10-8-6-4- 2/h13-14,17- 18H,3-12,15- 16,19-20H2,1- 2H3 Diosmetin C16H12 300. 520-34- SSA ESI 3 M+H 301.0699 InChI=1S/C16 O6 0634 3 pos (5 ppm) H12O6/c1-21- 13-3-2-8(4- 10(13)18)14- 7-12(20)16- 11(19)5- 9(17)6- 15(16)22- 14/h2-7,17- 19H,1H3 Divaricatic C21H24 388. 491-62- SSA ESI 2a M-H 387.145 (2 InChI=1S/C21 acid O7 1522 3 neg ppm) H24O7/c1-4-6- 12-9-15(11- 16(22)18(12)2 0(24)25)28- 21(26)19- 13(7-5-2)8- 14(27-3)10- 17(19)23/h8- 11,22-23H,4- 7H2,1- 3H3,(H,24,25) Dodecanoic C12H24 200. 143-07- SSA EI 2a InChI=1S/C12 acid O2 1776 7 H24O2/c1-2-3- 4-5-6-7-8-9- 10-11- 12(13)14/h2- 11H2,1H3,(H,1 3,14)

Enoxolone C30H46 470. 471-53- SSA ESI 2b M+H 471.3471 InChI=1S/C30 O4 3396 4 pos (1 ppm) H46O4/c1- 25(2)21-8-11- 30(7)23(28(21, 5)10-9- 22(25)32)20(3 1)16-18-19- 17- 27(4,24(33)34) 13-12- 26(19,3)14-15- 29(18,30)6/h1 6,19,21- 23,32H,8- 15,17H2,1- 7H3,(H,33,34)/ t19-,21?,22-,2 3+,26+,27-,28- ,29+,30+/m0/s 1 Ethylparabe C9H10O 166. 120-47- SSA ESI 2a M-H 165.0555 InChI=1S/C9H n 3 063 8 neg (2 ppm) 10O3/c1-2-12- 9(11)7-3-5- 8(10)6-4-7/h3- 6,10H,2H2,1H 3 Eupatilin C18H16 344. 22368- SSA ESI 2a M-H 343.0825 InChI=1S/C18 O7 0896 21-4 neg (2 ppm) H16O7/c1-22- 12-5-4-9(6- 14(12)23- 2)13-7- 10(19)16- 15(25-13)8- 11(20)18(24- 3)17(16)21/h4 -8,20-21H,1- 3H3 Exemestane C20H24 296. 107868- SSA ESI 2b M+H 297.184 (5 InChI=1S/C20 O2 1776 30-4 pos ppm) H24O2/c1-12- 10-14-15-4-5- 18(22)20(15,3) 9-7- 16(14)19(2)8- 6-13(21)11- 17(12)19/h6,8, 11,14-16H,1,4- 5,7,9-10H2,2- 3H3/t14-,15-,1 6-,19+,20- /m0/s1

Fipronil C12H4Cl 435. 120068- SSA ESI 2a M-H 434.9329 InChI=1S/C12 2F6N4O 9387 37-3 neg (5 ppm) H4Cl2F6N4OS/ S c13-5-1- 4(11(15,16)17) 2-6(14)8(5)24- 10(22)9(7(3- 21)23- 24)26(25)12(1 8,19)20/h1- 2H,22H2 Fipronil C12H4Cl 435. 120068- SSA EI 2a InChI=1S/C12 2F6N4O 9387 37-3 H4Cl2F6N4OS/ S c13-5-1- 4(11(15,16)17) 2-6(14)8(5)24- 10(22)9(7(3- 21)23- 24)26(25)12(1 8,19)20/h1- 2H,22H2 Fludioxonil C12H6F 248. 131341- SSA ESI 2a M-H 247.0329 InChI=1S/C12 2N2O2 0397 86-1 neg (4 ppm) H6F2N2O2/c1 3-12(14)17- 10-3-1-2- 8(11(10)18- 12)9-6-16-5- 7(9)4-15/h1- 3,5-6,16H Fluoranthen C16H10 202. 206-44- SSA EI 2a InChI=1S/C16 e 0783 0 H10/c1-2-8- 13-12(7-1)14- 9-3-5-11-6-4- 10- 15(13)16(11)1 4/h1-10H Flutamide C11H11 276. 13311- SSA ESI 2a M+H 277.0772 InChI=1S/C11 F3N2O3 0722 84-7 pos (10 ppm) H11F3N2O3/c 1- 6(2)10(17)15- 7-3-4- 9(16(18)19)8(5 - 7)11(12,13)14 /h3-6H,1- 2H3,(H,15,17) Galaxolide C18H26 258. 1222- SSA EI 3 InChI=1S/C18 O 1984 05-5 H26O/c1-11-9- 19-10-13-7- 15-16(8- 14(11)13)18(5, 6)12(2)17(15,3

)4/h7-8,11- 12H,9-10H2,1- 6H3 Galaxolidon C18H24 272. 256393- SSA ESI 2a M+H 273.1855 InChI=1S/C18 e O2 1776 37-0 pos (0 ppm) H24O2/c1-10- 9-20- 16(19)13-8- 15-14(7- 12(10)13)17(3, 4)11(2)18(15,5 )6/h7-8,10- 11H,9H2,1- 6H3 gamma- C28H42 410. 14101- SSA EI 3 InChI=1S/C28 Tocotrienol O2 3185 61-2 H42O2/c1- 20(2)11-8-12- 21(3)13-9-14- 22(4)15-10- 17-28(7)18- 16-25-19- 26(29)23(5)24( 6)27(25)30- 28/h11,13,15, 19,29H,8- 10,12,14,16- 18H2,1- 7H3/b21- 13+,22- 15+/t28- /m1/s1 Gangaleoidi C18H14 412. 55365- SSA ESI 2a M-H 411.0039 InChI=1S/C18 n Cl2O7 0117 63-4 neg (0 ppm) H14Cl2O7/c1- 6-11- 16(13(20)14(2 1)12(6)19)27- 15- 7(2)10(17(22)2 5-4)8(24-3)5- 9(15)26- 18(11)23/h5,2 1H,1-4H3 Gyrophoric C24H20 468. 548-89- SSA ESI 2a M-H 467.1014 InChI=1S/C24 acid O10 1056 0 neg (8 ppm) H20O10/c1- 10-4-13(25)7- 16(26)20(10)2 3(31)34-15-6- 12(3)21(18(28) 9- 15)24(32)33- 14-5- 11(2)19(22(29)

30)17(27)8- 14/h4-9,25- 28H,1- 3H3,(H,29,30) Harmane C12H10 182. 486-84- SSA ESI 2b M+H 183.0911 InChI=1S/C12 N2 0844 0 pos (6 ppm) H10N2/c1-8- 12-10(6-7-13- 8)9-4-2-3-5- 11(9)14- 12/h2- 7,14H,1H3 Hesperetin- C28H34 610. 520-26- SSA ESI 2a M+H 611.1995 InChI=1S/C28 7-O- O15 1898 3 pos (3 ppm) H34O15/c1- rutinoside 10- 21(32)23(34)2 5(36)27(40- 10)39-9-19- 22(33)24(35)2 6(37)28(43- 19)41-12-6- 14(30)20- 15(31)8- 17(42- 18(20)7- 12)11-3-4- 16(38- 2)13(29)5- 11/h3- 7,10,17,19,21- 30,32-37H,8- 9H2,1- 2H3/t10?,17-, 19?,21?,22?,2 3?,24?,25?,26 ?,27?,28?/m0/ s1 Hexachlorod C10H16 441. NA SSA ESI 3 M-H 440.8804 InChI=1S/C10 ecyl Cl6O4S 89 neg (4 ppm) H16Cl6O4S/c1 hydrogen 1- sulfate 8(10(15,16)20- 21(17,18)19)6- 4-2-1-3-5-7- 9(12,13)14/h8 H,1- 7H2,(H,17,18, 19) Hexadecana C16H33 255. 629-54- SSA EI 2a InChI=1S/C16 mide NO 2562 9 H33NO/c1-2- 3-4-5-6-7-8-9- 10-11-12-13- 14-15- 66

16(17)18/h2- 15H2,1H3,(H2, 17,18) Hexyl C15H20 216. 101-86- SSA EI 2a InChI=1S/C15 cinnamal O 1514 0 H20O/c1-2-3- 4-6-11-15(13- 16)12-14-9-7- 5-8-10- 14/h5,7-10,12- 13H,2- 4,6,11H2,1H3/ b15-12- Hibiscetin C22H24 432. 21634- SSA ESI 3 M+H 433.1487 InChI=1S/C22 heptamethyl O9 142 52-6 pos (3 ppm) H24O9/c1-24- ether 12-10-15(27- 4)20(29-6)21- 16(12)17(23)2 2(30-7)18(31- 21)11-8- 13(25- 2)19(28- 5)14(9-11)26- 3/h8-10H,1- 7H3 Hispidulin C16H12 300. 1447- SSA ESI 2a M-H 299.0573 InChI=1S/C16 O6 0634 88-7 neg (6 ppm) H12O6/c1-21- 16-11(19)7- 13- 14(15(16)20)1 0(18)6-12(22- 13)8-2-4- 9(17)5-3-8/h2- 7,17,19- 20H,1H3 Homosalate C16H22 262. 118-56- SSA EI 2b InChI=1S/C16 O3 1569 9 H22O3/c1-11- 8-12(10- 16(2,3)9- 11)19- 15(18)13-6-4- 5-7- 14(13)17/h4- 7,11-12,17H,8- 10H2,1-3H3 HO-PEG13- C26H54 590. 17598- SSA ESI 2a M+H 591.3576 InChI=1S/C26 OH O14 3514 96-8 pos (3 ppm) H54O14/c27- 1-3-29-5-7-31- 9-11-33-13- 15-35-17-19- 37-21-23-39- 25-26-40-24-

22-38-20-18- 36-16-14-34- 12-10-32-8-6- 30-4-2- 28/h27-28H,1- 26H2 HO-PEG14- C28H58 634. 118911 SSA ESI 2a M+H 635.3847 InChI=1S/C28 OH O15 3776 2-05-7 pos (1 ppm) H58O15/c29- 1-3-31-5-7-33- 9-11-35-13- 15-37-17-19- 39-21-23-41- 25-27-43-28- 26-42-24-22- 40-20-18-38- 16-14-36-12- 10-34-8-6-32- 4-2-30/h29- 30H,1-28H2 HO-PEG15- C30H62 678. 28821- SSA ESI 2a M+H 679.4137 InChI=1S/C30 OH O16 4038 35-4 pos (3 ppm) H62O16/c31- 1-3-33-5-7-35- 9-11-37-13- 15-39-17-19- 41-21-23-43- 25-27-45-29- 30-46-28-26- 44-24-22-42- 20-18-40-16- 14-38-12-10- 36-8-6-34-4-2- 32/h31-32H,1- 30H2 HO-PEG17- C34H70 766. 351342- SSA ESI 2a M+N 784.4928 InChI=1S/C34 OH O18 4562 04-6 pos H4 (3 ppm) H70O18/c35- 1-3-37-5-7-39- 9-11-41-13- 15-43-17-19- 45-21-23-47- 25-27-49-29- 31-51-33-34- 52-32-30-50- 28-26-48-24- 22-46-20-18- 44-16-14-42- 12-10-40-8-6- 38-4-2- 36/h35-36H,1- 34H2

HO-PEG18- C36H74 810. 4445- SSA ESI 2a M+N 828.5178 InChI=1S/C36 OH O19 4824 03-8 pos H4 (1 ppm) H74O19/c37- 1-3-39-5-7-41- 9-11-43-13- 15-45-17-19- 47-21-23-49- 25-27-51-29- 31-53-33-35- 55-36-34-54- 32-30-52-28- 26-50-24-22- 48-20-18-46- 16-14-44-12- 10-42-8-6-40- 4-2-38/h37- 38H,1-36H2 HO-PEG19- C38H78 854. 351342- SSA ESI 2a M+N 877.4967 InChI=1S/C38 OH O20 5086 07-9 pos a (2 ppm) H78O20/c39- 1-3-41-5-7-43- 9-11-45-13- 15-47-17-19- 49-21-23-51- 25-27-53-29- 31-55-33-35- 57-37-38-58- 36-34-56-32- 30-54-28-26- 52-24-22-50- 20-18-48-16- 14-46-12-10- 44-8-6-42-4-2- 40/h39-40H,1- 38H2 HO-PEG20- C40H82 898. 351342- SSA ESI 2a M+N 921.5263 InChI=1S/C40 OH O21 5349 08-0 pos a (2 ppm) H82O21/c41- 1-3-43-5-7-45- 9-11-47-13- 15-49-17-19- 51-21-23-53- 25-27-55-29- 31-57-33-35- 59-37-39-61- 40-38-60-36- 34-58-32-30- 56-28-26-54- 24-22-52-20- 18-50-16-14- 48-12-10-46- 8-6-44-4-2- 42/h41-42H,1- 40H2

HO-PEG4-OH C8H18O 194. 112-60- SSA ESI 2a M+H 195.1235 InChI=1S/C8H 5 1154 7 pos (1 ppm) 18O5/c9-1-3- 11-5-7-13-8-6- 12-4-2-10/h9- 10H,1-8H2 HO-PEG5-OH C10H22 238. 4792- SSA ESI 2a M+H 239.1471 InChI=1S/C10 O6 1416 15-8 pos (10 ppm) H22O6/c11-1- 3-13-5-7-15-9- 10-16-8-6-14- 4-2-12/h11- 12H,1-10H2 HO-PEG6-OH C12H26 282. 2615- SSA ESI 2a M+H 283.1766 InChI=1S/C12 O7 1679 15-8 pos (3 ppm) H26O7/c13-1- 3-15-5-7-17-9- 11-19-12-10- 18-8-6-16-4-2- 14/h13-14H,1- 12H2 HO-PEG9-OH C18H38 414. 3386- SSA ESI 2a M+H 415.2563 InChI=1S/C18 O10 2465 18-3 pos (5 ppm) H38O10/c19- 1-3-21-5-7-23- 9-11-25-13- 15-27-17-18- 28-16-14-26- 12-10-24-8-6- 22-4-2- 20/h19-20H,1- 18H2 Hydrocortiso C21H30 362. 50-23-7 SSA ESI 2a M+H 363.2151 InChI=1S/C21 ne O5 2093 pos (6 ppm) H30O5/c1-19- 7-5-13(23)9- 12(19)3-4-14- 15-6-8- 21(26,17(25)1 1- 22)20(15,2)10- 16(24)18(14)1 9/h9,14- 16,18,22,24,26 H,3-8,10- 11H2,1- 2H3/t14-,15-,1 6-,18+,19-,20-, 21-/m0/s1 Indarubicin C16H10 262. 479-41- SSA ESI 3 M+H 263.0816 InChI=1S/C16 N2O2 0742 4 pos (2 ppm) H10N2O2/c19 -15-10-6-2-4- 8-12(10)17- 14(15)13-9-5- 1-3-7-11(9)18-

16(13)20/h1- 8,18,20H

Indigo C16H10 262. 482-89- SSA EI 2b InChI=1S/C16 N2O2 0742 3 H10N2O2/c19 -15-9-5-1-3-7- 11(9)17- 13(15)14- 16(20)10-6-2- 4-8-12(10)18- 14/h1- 8,17,19H Indole-3- C9H7NO 145. 487-89- SSA ESI 2a M-H 144.0453 InChI=1S/C9H carboxyalde 0528 8 neg (3 ppm) 7NO/c11-6-7- hyde 5-10-9-4-2-1- 3-8(7)9/h1- 6,10H Isoconazole C18H14 413. 27523- NTA ESI 3 M+H 414.993 (2 1S/C18H14Cl4 Cl4N2O 986 40-6 pos ppm) N2O/c19-12-4- 5-13(17(22)8- 12)18(9-24-7- 6-23-11- 24)25-10-14- 15(20)2-1-3- 16(14)21/h1- 8,11,18H,9- 10H2 Isokaempfer C16H12 300. 1592- SSA ESI 2a M-H 299.0573 InChI=1S/C16 ide O6 0634 70-7 neg (6 ppm) H12O6/c1-21- 16-14(20)13- 11(19)6- 10(18)7- 12(13)22- 15(16)8-2-4- 9(17)5-3-8/h2- 7,17-19H,1H3 Isopropylph C21H21 368. 28108- SSA EI 2a InChI=1S/C21 enyl O4P 1177 99-8 H21O4P/c1- diphenyl 17(2)20-15-9- phosphate 10-16- 21(20)25- 26(22,23-18- 11-5-3-6-12- 18)24-19-13- 7-4-8-14- 19/h3-17H,1- 2H3 Lariciresinol C20H24 360. 27003- SSA ESI 2a M-H 359.1506 InChI=1S/C20 O6 1573 73-2 neg (3 ppm) H24O6/c1-24- 18-8-12(3-5- 16(18)22)7- 71

14-11-26- 20(15(14)10- 21)13-4-6- 17(23)19(9- 13)25-2/h3- 6,8-9,14- 15,20- 23H,7,10- 11H2,1- 2H3/t14-,15-,2 0+/m0/s1 Lauryl C12H26 266. 151-41- SSA ESI 2a M-H 265.1496 InChI=1S/C12 sulfate O4S 1552 7 neg (8 ppm) H26O4S/c1-2- 3-4-5-6-7-8-9- 10-11-12-16- 17(13,14)15/h 2- 12H2,1H3,(H,1 3,14,15) LCM-13 C22H34 298. 84656- TA EI 1 InChI=1S/C22 2661 75-7 H34/c1-3-4- 18-7-11- 20(12-8- 18)22-15-13- 21(14-16- 22)19-9-5- 17(2)6-10- 19/h5-6,9- 10,18,20- 22H,3-4,7- 8,11-16H2,1- 2H3 LCM-3 C16H30 238. 97398- TA EI 1 InChI=1S/C16 O 2297 80-6 H30O/c1-3-4- 13-5-7-14(8-6- 13)15-9-11- 16(17-2)12- 10-15/h13- 16H,3-12H2,1- 2H3 LCM-6 C18H22 238. 64835- TA EI 1 InChI=1S/C18 1722 63-8 H22/c1-3-4-5- 6-16-9-13- 18(14-10- 16)17-11-7- 15(2)8-12- 17/h7-14H,3- 6H2,1-2H3

Lecanoric C16H14 318. 480-56- SSA ESI 2a M-H 317.0665 InChI=1S/C16 Acid O7 074 8 neg (1 ppm) H14O7/c1-7-3- 9(17)5- 11(18)14(7)16( 22)23-10-4- 8(2)13(15(20)2 1)12(19)6- 10/h3-6,17- 19H,1- 2H3,(H,20,21) Lichexantho C16H14 286. 15222- SSA EI 3 InChI=1S/C16 ne O5 0841 53-4 H14O5/c1-8-4- 9(19-2)6-12- 14(8)16(18)15- 11(17)5- 10(20-3)7- 13(15)21- 12/h4- 7,17H,1-3H3 Matairesinol C20H22 358. 580-72- SSA EI 3 InChI=1S/C20 O6 1416 3 H22O6/c1-24- 18-9-12(3-5- 16(18)21)7- 14-11-26- 20(23)15(14)8- 13-4-6- 17(22)19(10- 13)25-2/h3- 6,9-10,14- 15,21-22H,7- 8,11H2,1- 2H3/t14-,15+/ m0/s1 Melamine C3H6N6 126. 108-78- TA ESI 1 M+H 127.0727 1S/C3H6N6/c4 0654 1 pos (4 ppm) -1-7-2(5)9- 3(6)8- 1/h(H6,4,5,6,7 ,8,9) Melamine C3H6N6 126. 108-78- SSA EI 2a 1S/C3H6N6/c4 0654 1 -1-7-2(5)9- 3(6)8- 1/h(H6,4,5,6,7 ,8,9) Melibiose C12H22 342. 585-99- SSA ESI 2b M+N 365.1057 InChI=1S/C12 O11 1162 9 pos a (1 ppm) H22O11/c13- 1-3- 5(14)8(17)10(1 9)12(23-3)21- 2-4- 6(15)7(16)9(18 )11(20)22-

4/h3-20H,1- 2H2/t3-,4-,5+, 6-,7+,8+,9-,10- ,11?,12+/m1/s 1 Methyl 4- C8H7Br 229. 106291- SSA EI 2b InChI=1S/C8H bromo-3- O3 9579 80-9 7BrO3/c1-12- hydroxybenz 8(11)5-2-3- oate 6(9)7(10)4- 5/h2- 4,10H,1H3 Methyl C21H30 314. 1235- SSA EI 2a InChI=1S/C21 dehydroabie O2 2246 74-1 H30O2/c1- tate 14(2)15-7-9- 17-16(13- 15)8-10-18- 20(17,3)11-6- 12- 21(18,4)19(22) 23-5/h7,9,13- 14,18H,6,8,10- 12H2,1-5H3 methyl ester C21H28 328. NA SSA EI 2a InChI=1S/C21 7- O3 2038 H28O3/c1- Oxodehydro 13(2)14-7-8- abietic acid 16-15(11- 14)17(22)12- 18-20(16,3)9- 6-10- 21(18,4)19(23) 24-5/h7- 8,11,13,18H,6, 9-10,12H2,1- 5H3 Methyl C10H10 210. 34874- SSA EI 2a InChI=1S/C10 haematomm O5 0528 90-3 H10O5/c1-5-3- ate 7(12)6(4- 11)9(13)8(5)10 (14)15-2/h3- 4,12-13H,1- 2H3 Methyl C17H34 270. 112-39- SSA EI 2a InChI=1S/C17 palmitate O2 2559 0 H34O2/c1-3-4- 5-6-7-8-9-10- 11-12-13-14- 15-16- 17(18)19- 2/h3-16H2,1- 2H3 Methyl C19H38 298. 112-61- SSA EI 2a InChI=1S/C19 stearate O2 2872 8 H38O2/c1-3-4-

5-6-7-8-9-10- 11-12-13-14- 15-16-17-18- 19(20)21- 2/h3-18H2,1- 2H3 Methylparab C8H8O3 152. 99-76-3 SSA EI 2 InChI=1S/C8H en 0473 8O3/c1-11- 8(10)6-2-4- 7(9)5-3-6/h2- 5,9H,1H3 MTBT C8H7NS 181. 615-22- SSA EI 2a InChI=1S/C8H 2 002 5 7NS2/c1-10-8- 9-6-4-2-3-5- 7(6)11-8/h2- 5H,1H3 Narirutin C27H32 580. 14259- SSA ESI 2a M-H 579.1713 CC1C(C(C(C(O O14 1792 46-2 neg (0 ppm) 1)OCC2C(C(C( C(O2)OC3=CC( =C4C(=O)CC(O C4=C3)C5=CC= C(C=C5)O)O)O )O)O)O)O)O N-EtFOSA C10H6F 526. 4151- SSA ESI 2a M-H 525.9793 InChI=1S/C10 17NO2S 9848 50-2 neg (4 ppm) H6F17NO2S/c 1-2-28- 31(29,30)10(2 6,27)8(21,22)6 (17,18)4(13,14 )3(11,12)5(15, 16)7(19,20)9(2 3,24)25/h28H, 2H2,1H3 N-EtFOSAA C12H8F 584. 2991- SSA ESI 2a M-H 583.9858 InChI=1S/C12 17NO4S 9903 50-6 neg (6 ppm) H8F17NO4S/c 1-2-30(3- 4(31)32)35(33, 34)12(28,29)1 0(23,24)8(19,2 0)6(15,16)5(13 ,14)7(17,18)9( 21,22)11(25,2 6)27/h2- 3H2,1H3,(H,31 ,32) N- C6H10N 142. 59702- SSA EI 3 InChI=1S/C6H Ethylpiperazi 2O2 0742 31-7 10N2O2/c1-2- ne-2,3-dione 8-4-3-7- 5(9)6(8)10/h2- 4H2,1H3,(H,7, 9)

n-Hexyl C13H18 222. 6259- SSA EI 2a InChI=1S/C13 salicylate O3 1256 76-3 H18O3/c1-2-3- 4-7-10-16- 13(15)11-8-5- 6-9- 12(11)14/h5- 6,8-9,14H,2- 4,7,10H2,1H3 Nicotine C10H14 162. 23950- SSA EI 3 InChI=1S/C10 N2 1157 04-1 H14N2/c1-12- 8-4-6-10(12)9- 5-2-3-7-11- 9/h2- 3,5,7,10H,4,6, 8H2,1H3 Nicotine (R- C10H14 162. 25162- SSA ESI 3 M+H 163.1239 InChI=1S/C10 isomer) N2 1157 00-9 pos (2 ppm) H14N2/c1-12- 7-3-5-10(12)9- 4-2-6-11-8- 9/h2,4,6,8,10H ,3,5,7H2,1H3/t 10-/m1/s1 Nicotine (S- C10H14 162. 54-11-5 SSA ESI 3 M+H 163.124 (3 InChI=1S/C10 isomer) N2 1157 pos ppm) H14N2/c1-12- 7-3-5-10(12)9- 4-2-6-11-8- 9/h2,4,6,8,10H ,3,5,7H2,1H3/t 10-/m0/s1 N- C8H9NO 135. 93-61-8 SSA EI 3 InChI=1S/C8H Methylform 0684 9NO/c1-9(7- anilide 10)8-5-3-2-4- 6-8/h2-7H,1H3 Nobiletin C21H22 402. 478-01- SSA ESI 2b M+H 403.1403 InChI=1S/C21 O8 1315 3 pos (2 ppm) H22O8/c1-23- 13-8-7-11(9- 15(13)24- 2)14-10- 12(22)16- 17(25- 3)19(26- 4)21(28- 6)20(27- 5)18(16)29- 14/h7-10H,1- 6H3 Nobiletin C21H22 402. 478-01- SSA EI 3 InChI=1S/C21 O8 1315 3 H22O8/c1-23- 13-8-7-11(9- 15(13)24- 2)14-10-

12(22)16- 17(25- 3)19(26- 4)21(28- 6)20(27- 5)18(16)29- 14/h7-10H,1- 6H3 Norgestrel C21H28 312. 797-63- SSA ESI 2b M-H 311.2016 InChI=1S/C21 O2 2089 7 neg (1 ppm) H28O2/c1-3- 20-11-9-17- 16-8-6- 15(22)13- 14(16)5-7- 18(17)19(20)1 0-12- 21(20,23)4- 2/h2,13,16- 19,23H,3,5- 12H2,1H3/t16- ,17+,18+,19-,2 0-,21-/m0/s1 Norharman C11H8N 168. 244-63- SSA ESI 2b M+H 169.0749 InChI=1S/C11 2 0687 3 pos (10 ppm) H8N2/c1-2-4- 10-8(3-1)9-5- 6-12-7- 11(9)13- 10/h1-7,13H Norstictic C18H12 372. 571-67- SSA ESI 2a M-H 371.0425 InChI=1S/C18 acid O9 0481 5 neg (6 ppm) H12O9/c1-5-3- 8(20)7(4- 19)14- 9(5)16(22)26- 13- 6(2)12(21)10- 11(15(13)25- 14)18(24)27- 17(10)23/h3- 4,18,20- 21,24H,1-2H3 o,p-DDE C14H8Cl 315. 3424- TA EI 1 InChI=1S/C14 4 938 82-6 H8Cl4/c15-10- 7-5-9(6-8- 10)13(14(17)1 8)11-3-1-2-4- 12(11)16/h1- 8H o- C6H6Cl 127. 95-51-2 SSA EI 3 InChI=1S/C6H Chloroanilin N 0189 6ClN/c7-5-3-1- e 2-4-6(5)8/h1- 4H,8H2

Octabenzon C21H26 326. 1843- SSA EI 3 InChI=1S/C21 e O3 1882 05-6 H26O3/c1-2-3- 4-5-6-10-15- 24-18-13-14- 19(20(22)16- 18)21(23)17- 11-8-7-9-12- 17/h7-9,11- 14,16,22H,2- 6,10,15H2,1H3 Octadecanoi C18H36 284. 57-11-4 SSA EI 2a InChI=1S/C18 c acid O2 2715 H36O2/c1-2-3- 4-5-6-7-8-9- 10-11-12-13- 14-15-16-17- 18(19)20/h2- 17H2,1H3,(H,1 9,20) Octocrylene C24H27 361. 6197- SSA EI 2b InChI=1S/C24 NO2 2042 30-4 H27NO2/c1-3- 5-12-19(4- 2)18-27- 24(26)22(17- 25)23(20-13- 8-6-9-14- 20)21-15-10- 7-11-16- 21/h6-11,13- 16,19H,3- 5,12,18H2,1- 2H3 OH-PEG10- C20H42 458. 5579- SSA ESI 2a M+H 459.2806 InChI=1S/C20 OH O11 2727 66-8 pos (0 ppm) H42O11/c21- 1-3-23-5-7-25- 9-11-27-13- 15-29-17-19- 31-20-18-30- 16-14-28-12- 10-26-8-6-24- 4-2-22/h21- 22H,1-20H2 OH-PEG11- C22H46 502. 6809- SSA ESI 2a M+H 503.3088 InChI=1S/C22 OH O12 2989 70-7 pos (4 ppm) H46O12/c23- 1-3-25-5-7-27- 9-11-29-13- 15-31-17-19- 33-21-22-34- 20-18-32-16- 14-30-12-10- 28-8-6-26-4-2-

24/h23-24H,1- 22H2

OH-PEG12- C24H50 546. 6790- SSA ESI 2a M+H 547.3312 InChI=1S/C24 OH O13 3251 09-6 pos (3 ppm) H50O13/c25- 1-3-27-5-7-29- 9-11-31-13- 15-33-17-19- 35-21-23-37- 24-22-36-20- 18-34-16-14- 32-12-10-30- 8-6-28-4-2- 26/h25-26H,1- 24H2 OH-PEG16- C32H66 722. 6812- SSA ESI 2a M+H 723.4372 InChI=1S/C32 OH O17 43 36-8 pos (1 ppm) H66O17/c33- 1-3-35-5-7-37- 9-11-39-13- 15-41-17-19- 43-21-23-45- 25-27-47-29- 31-49-32-30- 48-28-26-46- 24-22-44-20- 18-42-16-14- 40-12-10-38- 8-6-36-4-2- 34/h33-34H,1- 32H2 OH-PEG7-OH C14H30 326. 5617- SSA ESI 2a M+H 327.202 (0 InChI=1S/C14 O8 1941 32-3 pos ppm) H30O8/c15-1- 3-17-5-7-19-9- 11-21-13-14- 22-12-10-20- 8-6-18-4-2- 16/h15-16H,1- 14H2 OH-PEG8-OH C16H34 370. 5117- SSA ESI 2a M+H 371.228 (0 InChI=1S/C16 O9 2203 19-1 pos ppm) H34O9/c17-1- 3-19-5-7-21-9- 11-23-13-15- 25-16-14-24- 12-10-22-8-6- 20-4-2- 18/h17-18H,1- 16H2 Oleanitrile C18H33 263. 112-91- SSA EI 2b InChI=1S/C18 N 2613 4 H33N/c1-2-3- 4-5-6-7-8-9- 10-11-12-13- 79

14-15-16-17- 18-19/h9- 10H,2-8,11- 17H2,1H3/b10 -9- Olivetoric C26H32 472. 491-47- SSA ESI 2a M-H 471.2026 InChI=1S/C26 acid O8 2097 4 neg (2 ppm) H32O8/c1-3-5- 7-9-16-13- 20(15- 22(30)23(16)2 5(31)32)34- 26(33)24- 17(12- 19(28)14- 21(24)29)11- 18(27)10-8-6- 4-2/h12- 15,28-30H,3- 11H2,1- 2H3,(H,31,32) p,p'-DDE C14H8Cl 315. 72-55-9 TA EI 1 InChI=1S/C14 4 938 H8Cl4/c15-11- 5-1-9(2-6- 11)13(14(17)1 8)10-3-7- 12(16)8-4- 10/h1-8H p,p'-DDT C14H9Cl 351. 50-29-3 TA EI 1 InChI=1S/C14 5 9147 H9Cl5/c15-11- 5-1-9(2-6- 11)13(14(17,1 8)19)10-3-7- 12(16)8-4- 10/h1-8,13H Palmidrol C18H37 299. 544-31- SSA EI 3 InChI=1S/C18 NO2 2824 0 H37NO2/c1-2- 3-4-5-6-7-8-9- 10-11-12-13- 14-15- 18(21)19-16- 17-20/h20H,2- 17H2,1H3,(H,1 9,21) PCB 101 C12H5Cl 323. 37680- TA EI 1 InChI=1S/C12 5 8834 73-2 H5Cl5/c13-6- 1-2-9(14)7(3- 6)8-4- 11(16)12(17)5- 10(8)15/h1-5H PCB 153 C12H4Cl 357. 35065- TA EI 1 InChI=1S/C12 6 8444 27-1 H4Cl6/c13-7-

3- 11(17)9(15)1- 5(7)6-2- 10(16)12(18)4- 8(6)14/h1-4H PCB 28 C12H7Cl 255. 7012- TA EI 1 InChI=1S/C12 3 9613 37-5 H7Cl3/c13-9- 3-1-8(2-4- 9)11-6-5- 10(14)7- 12(11)15/h1- 7H PCB 52 C12H6Cl 289. 35693- TA EI 1 InChI=1S/C12 4 9224 99-3 H6Cl4/c13-7- 1-3-11(15)9(5- 7)10-6-8(14)2- 4- 12(10)16/h1- 6H PCP C6HCl5 263. 87-86-5 SSA EI 2a InChI=1S/C6H O 847 Cl5O/c7-1- 2(8)4(10)6(12) 5(11)3(1)9/h1 2H Permethrine C21H20 390. 52645- SSA EI 3 InChI=1S/C21 Cl2O3 079 53-1 H20Cl2O3/c1- 21(2)17(12- 18(22)23)19(2 1)20(24)25- 13-14-7-6-10- 16(11-14)26- 15-8-4-3-5-9- 15/h3- 12,17,19H,13H 2,1-2H3 PFBS C4HF9O 299. 375-73- SSA ESI 2b M-H 298.945 (8 InChI=1S/C4HF 3S 9503 5 neg ppm) 9O3S/c5- 1(6,3(9,10)11) 2(7,8)4(12,13) 17(14,15)16/h (H,14,15,16) PFDA C10HF1 513. 335-76- SSA ESI 2a M-H 512.9601 InChI=1S/C10 9O2 9673 2 neg (1 ppm) HF19O2/c11- 2(12,1(30)31)3 (13,14)4(15,16 )5(17,18)6(19, 20)7(21,22)8(2 3,24)9(25,26)1 0(27,28)29/h( H,30,31)

PFDS C10HF2 599. 335-77- SSA ESI 2a M-H 598.9249 InChI=1S/C10 1O3S 9311 3 neg (3 ppm) HF21O3S/c11- 1(12,3(15,16)5 (19,20)7(23,24 )9(27,28)29)2( 13,14)4(17,18) 6(21,22)8(25,2 6)10(30,31)35( 32,33)34/h(H, 32,33,34) PFHpA C7HF13 363. 375-85- SSA ESI 2b M-H 362.9702 InChI=1S/C7HF O2 9769 9 neg (3 ppm) 13O2/c8- 2(9,1(21)22)3( 10,11)4(12,13) 5(14,15)6(16,1 7)7(18,19)20/ h(H,21,22) PFHpS C7HF15 449. 375-92- SSA ESI 2a M-H 448.9343 InChI=1S/C7HF O3S 9407 8 neg (3 ppm) 15O3S/c8- 1(9,2(10,11)4( 14,15)6(18,19) 20)3(12,13)5(1 6,17)7(21,22)2 6(23,24)25/h( H,23,24,25) PFHxA C6HF11 313. 307-24- SSA ESI 2b M-H 312.9731 InChI=1S/C6HF O2 9801 4 neg (3 ppm) 11O2/c7- 2(8,1(18)19)3( 9,10)4(11,12)5 (13,14)6(15,16 )17/h(H,18,19) PFHxS C6HF13 399. 355-46- SSA ESI 2a M-H 398.9351 InChI=1S/C6HF O3S 9439 4 neg (2 ppm) 13O3S/c7- 1(8,3(11,12)5( 15,16)17)2(9,1 0)4(13,14)6(18 ,19)23(20,21)2 2/h(H,20,21,2 2) PFNA C9HF17 463. 375-95- SSA ESI 2b M-H 462.9625 InChI=1S/C9HF O2 9705 1 neg (0 ppm) 17O2/c10- 2(11,1(27)28)3 (12,13)4(14,15 )5(16,17)6(18, 19)7(20,21)8(2 2,23)9(24,25)2 6/h(H,27,28) PFNS C9HF19 549. 68259- SSA ESI 2a M-H 548.9251 InChI=1S/C9HF O3S 9343 12-1 neg (3 ppm) 19O3S/c10- 1(11,2(12,13)4 (16,17)6(20,21

)8(24,25)26)3( 14,15)5(18,19) 7(22,23)9(27,2 8)32(29,30)31 /h(H,29,30,31) PFOA C8HF15 413. 335-67- SSA ESI 2b M-H 412.967 (3 InChI=1S/C8HF O2 9737 1 neg ppm) 15O2/c9- 2(10,1(24)25)3 (11,12)4(13,14 )5(15,16)6(17, 18)7(19,20)8(2 1,22)23/h(H,2 4,25) PFOS C8HF17 499. 1763- SSA ESI 2a M-H 498.9297 InChI=1S/C8HF O3S 9375 23-1 neg (0 ppm) 17O3S/c9- 1(10,3(13,14)5 (17,18)7(21,22 )23)2(11,12)4( 15,16)6(19,20) 8(24,25)29(26, 27)28/h(H,26, 27,28) PFUnDA C11HF2 563. 2058- SSA ESI 2a M-H 562.9595 InChI=1S/C11 1O2 9641 94-8 neg (6 ppm) HF21O2/c12- 2(13,1(33)34)3 (14,15)4(16,17 )5(18,19)6(20, 21)7(22,23)8(2 4,25)9(26,27)1 0(28,29)11(30, 31)32/h(H,33, 34) Phenothiazi C12H9N 199. 92-84-2 SSA EI 2a InChI=1S/C12 ne S 0456 H9NS/c1-3-7- 11-9(5-1)13- 10-6-2-4-8- 12(10)14- 11/h1-8,13H Phenyl di(p- C20H19 354. 34909- SSA EI 3 InChI=1S/C20 tolyl) O4P 1021 69-8 H19O4P/c1- phosphate 16-8-12- 19(13-9- 16)23- 25(21,22-18-6- 4-3-5-7-18)24- 20-14-10- 17(2)11-15- 20/h3-15H,1- 2H3 Phenylacetic C8H8O2 136. 103-82- SSA ESI 2a M-H 135.0452 InChI=1S/C8H acid 0524 2 neg (4 ppm) 8O2/c9-

8(10)6-7-4-2- 1-3-5-7/h1- 5H,6H2,(H,9,1 0) Physodalic C20H16 416. 90689- SSA ESI 2a M-H 415.0671 InChI=1S/C20 acid O10 0743 60-4 neg (1 ppm) H16O10/c1-7- 4-12(23)10(5- 21)17- 13(7)20(27)30- 18-11(6-28- 9(3)22)15(24)1 4(19(25)26)8(2 )16(18)29- 17/h4-5,23- 24H,6H2,1- 3H3,(H,25,26) Physodic C26H30 470. 84-24-2 SSA ESI 2a M-H 469.1875 InChI=1S/C26 acid O8 1941 neg (3 ppm) H30O8/c1-3-5- 7-9-16(27)11- 15-12- 17(28)13-20- 22(15)26(32)3 4-21-14- 19(29)23(25(3 0)31)18(24(21) 33-20)10-8-6- 4-2/h12- 14,28-29H,3- 11H2,1- 2H3,(H,30,31) Pimozide C28H29 461. 2062- TA ESI 1 M+H 462.2357 1S/C28H29F2 F2N3O 2279 78-4 pos (0 ppm) N3O/c29-22- 11-7-20(8-12- 22)25(21-9- 13-23(30)14- 10-21)4-3-17- 32-18-15- 24(16-19- 32)33-27-6-2- 1-5-26(27)31- 28(33)34/h1- 2,5-14,24- 25H,3-4,15- 19H2,(H,31,34 ) Piperine C17H19 285. 94-62-2 SSA ESI 3 M+H 286.144 (1 InChI=1S/C17 (isomer) NO3 1365 pos ppm) H19NO3/c19- 17(18-10-4-1- 5-11-18)7-3-2- 6-14-8-9-15- 16(12-14)21-

13-20-15/h2- 3,6-9,12H,1,4- 5,10- 11,13H2/b6- 2+,7-3+ Piperine C17H19 285. 94-62-2 SSA ESI 3 M+H 286.144 (1 InChI=1S/C17 (isomer) NO3 1365 pos ppm) H19NO3/c19- 17(18-10-4-1- 5-11-18)7-3-2- 6-14-8-9-15- 16(12-14)21- 13-20-15/h2- 3,6-9,12H,1,4- 5,10- 11,13H2/b6- 2+,7-3+ Piperine C17H19 285. 94-62-2 SSA ESI 3 M+H 286.1442 InChI=1S/C17 (isomer) NO3 1365 pos (0 ppm) H19NO3/c19- 17(18-10-4-1- 5-11-18)7-3-2- 6-14-8-9-15- 16(12-14)21- 13-20-15/h2- 3,6-9,12H,1,4- 5,10- 11,13H2/b6- 2+,7-3+ Propetamph C10H20 281. 31218- SSA EI 2a InChI=1S/C10 os NO4PS 0851 83-4 H20NO4PS/c1- 6-11-16(17,13- 5)15-9(4)7- 10(12)14- 8(2)3/h7- 8H,6H2,1- 5H3,(H,11,17)/ b9-7+ Propiconazol C15H17 341. 60207- SSA EI 3 InChI=1S/C15 e Cl2N3O 0698 90-1 H17Cl2N3O2/c 2 1-2-3-12-7-21- 15(22-12,8-20- 10-18-9-19- 20)13-5-4- 11(16)6- 14(13)17/h4- 6,9-10,12H,2- 3,7-8H2,1H3 p-Toluene C7H8O3 172. 104-15- SSA ESI 2a M-H 171.0126 InChI=1S/C7H sulfonate S 0194 4 neg (6 ppm) 8O3S/c1-6-2- 4-7(5-3- 6)11(8,9)10/h 2-

5H,1H3,(H,8,9, 10)

Pyrene C16H10 202. 129-00- SSA EI 3 InChI=1S/C16 0783 0 H10/c1-3-11- 7-9-13-5-2-6- 14-10-8-12(4- 1)15(11)16(13) 14/h1-10H Quercetin C15H10 302. 117-39- SSA ESI 2a M-H 301.0354 InChI=1S/C15 O7 0427 5 neg (2 ppm) H10O7/c16-7- 4-10(19)12- 11(5-7)22- 15(14(21)13(1 2)20)6-1-2- 8(17)9(18)3- 6/h1-5,16- 19,21H Salazinic C18H12 388. 521-39- SSA ESI 2a M-H 387.0353 InChI=1S/C18 acid O10 043 1 neg (0 ppm) H12O10/c1-5- 2-8(21)6(3- 19)13- 9(5)16(23)27- 14-7(4- 20)12(22)10- 11(15(14)26- 13)18(25)28- 17(10)24/h2- 3,18,20- 22,25H,4H2,1 H3 Salicylic acid C7H6O3 138. 69-72-7 SSA ESI 2a M-H 137.0237 InChI=1S/C7H 0317 neg (1 ppm) 6O3/c8-6-4-2- 1-3- 5(6)7(9)10/h1- 4,8H,(H,9,10) Santin C18H16 344. 27782- SSA ESI 3 M-H 343.0814 InChI=1S/C18 O7 0896 63-4 neg (1 ppm) H16O7/c1-22- 10-6-4-9(5-7- 10)16-18(24- 3)15(21)13- 12(25-16)8- 11(19)17(23- 2)14(13)20/h4 -8,19-20H,1- 3H3 Santin C18H16 344. 27782- SSA ESI 3 M+H 345.0969 InChI=1S/C18 O7 0896 63-4 pos (2 ppm) H16O7/c1-22- 10-6-4-9(5-7- 10)16-18(24- 3)15(21)13- 12(25-16)8-

11(19)17(23- 2)14(13)20/h4 -8,19-20H,1- 3H3 Sebacic acid C10H18 202. 111-20- SSA ESI 2a M-H 201.1135 InChI=1S/C10 O4 1205 6 neg (4 ppm) H18O4/c11- 9(12)7-5-3-1- 2-4-6-8- 10(13)14/h1- 8H2,(H,11,12)( H,13,14) Spiraeoside C21H20 464. 20229- SSA ESI 3 M-H 463.0888 InChI=1S/C21 O12 0955 56-5 neg (3 ppm) H20O12/c22- 6-13- 15(26)17(28)1 9(30)21(33- 13)32-11-2-1- 7(3- 9(11)24)20- 18(29)16(27)1 4-10(25)4- 8(23)5- 12(14)31- 20/h1- 5,13,15,17,19, 21-26,28- 30H,6H2 Squalene C30H50 410. 111-02- SSA EI 2b InChI=1S/C30 3913 4 H50/c1- 25(2)15-11- 19-29(7)23- 13-21- 27(5)17-9-10- 18-28(6)22- 14-24- 30(8)20-12- 16- 26(3)4/h15- 18,23-24H,9- 14,19-22H2,1- 8H3/b27- 17+,28- 18+,29- 23+,30-24+ Stictic acid C19H14 386. 549-06- SSA ESI 2a M-H 385.0548 InChI=1S/C19 O9 0638 4 neg (3 ppm) H14O9/c1-6-4- 9(25-3)8(5- 20)15- 10(6)17(22)27- 14- 7(2)13(21)11-

12(16(14)26- 15)19(24)28- 18(11)23/h4- 5,19,21,24H,1- 3H3 Tadalafil C22H19 389. 171596- SSA ESI 3 M-H 388.1315 InChI=1S/C22 N3O4 1376 29-5 neg (5 ppm) H19N3O4/c1- 24-10- 19(26)25- 16(22(24)27)9- 14-13-4-2-3-5- 15(13)23- 20(14)21(25)1 2-6-7-17-18(8- 12)29-11-28- 17/h2- 8,16,21,23H,9- 11H2,1H3/t16- ,21-/m1/s1 Tadalafil C22H19 389. 171596- SSA ESI 3 M+H 390.144 (4 InChI=1S/C22 N3O4 1376 29-5 pos ppm) H19N3O4/c1- 24-10- 19(26)25- 16(22(24)27)9- 14-13-4-2-3-5- 15(13)23- 20(14)21(25)1 2-6-7-17-18(8- 12)29-11-28- 17/h2- 8,16,21,23H,9- 11H2,1H3/t16- ,21-/m1/s1 Tangeritin C20H20 372. 481-53- SSA ESI 3 M+H 373.1267 InChI=1S/C20 O7 1209 8 pos (6 ppm) H20O7/c1-22- 12-8-6-11(7-9- 12)14-10- 13(21)15- 16(23- 2)18(24- 3)20(26- 5)19(25- 4)17(15)27- 14/h6-10H,1- 5H3 Tangeritin C20H20 372. 481-53- SSA ESI 3 M+H 373.1258 InChI=1S/C20 O7 1209 8 pos (8 ppm) H20O7/c1-22- 12-8-6-11(7-9- 12)14-10- 13(21)15- 16(23-

2)18(24- 3)20(26- 5)19(25- 4)17(15)27- 14/h6-10H,1- 5H3 TBBPA C15H12 539. 79-94-7 NTA, ESI 1 M-H 538.7501 1S/C15H12Br4 Br4O2 7571 TA neg (2 ppm) O2/c1-15(2,7- 3- 9(16)13(20)10( 17)4-7)8-5- 11(18)14(21)1 2(19)6-8/h3- 6,20-21H,1- 2H3 TBBPA C15H12 539. 79-94-7 SSA EI 2a InChI=1S/C15 Br4O2 7571 H12Br4O2/c1- 15(2,7-3- 9(16)13(20)10( 17)4-7)8-5- 11(18)14(21)1 2(19)6-8/h3- 6,20-21H,1- 2H3 TBC C18H32 360. 77-94-1 TA ESI 1 M+H 361.2221 1S/C18H32O7 O7 2148 pos (1 ppm) /c1-4-7-10-23- 15(19)13- 18(22,17(21)2 5-12-9-6-3)14- 16(20)24-11- 8-5-2/h22H,4- 14H2,1-3H3 TBEP C18H39 398. 78-51-3 SSA EI 2a InChI=1S/C18 O7P 2433 H39O7P/c1-4- 7-10-20-13- 16-23- 26(19,24-17- 14-21-11-8-5- 2)25-18-15- 22-12-9-6- 3/h4-18H2,1- 3H3 TBP C12H27 266. 126-73- SSA EI 1 InChI=1S/C12 O4P 1647 8 H27O4P/c1-4- 7-10-14- 17(13,15-11-8- 5-2)16-12-9-6- 3/h4-12H2,1- 3H3 TCEP C6H12Cl 283. 115-96- SSA EI 1 InChI=1S/C6H 3O4P 9539 8 12Cl3O4P/c7-

1-4-11- 14(10,12-5-2- 8)13-6-3-9/h1- 6H2 TCPP isomer C9H18Cl 326. 13674- SSA ESI 2b M+H 327.007 (5 InChI=1S/C9H 3O4P 0008 84-5 pos ppm) 18Cl3O4P/c1- 7(4-10)14- 17(13,15- 8(2)5-11)16- 9(3)6-12/h7- 9H,4-6H2,1- 3H3 TCPP isomer C9H18Cl 326. 13674- SSA ESI 2b M+H 327.0082 InChI=1S/C9H 3O4P 0008 84-5 pos (1 ppm) 18Cl3O4P/c1- 7(4-10)14- 17(13,15- 8(2)5-11)16- 9(3)6-12/h7- 9H,4-6H2,1- 3H3 TCPP isomer C9H18Cl 326. 13674- SSA ESI 2b M+H 327.0081 InChI=1S/C9H 3O4P 0008 84-5 pos (2 ppm) 18Cl3O4P/c1- 7(4-10)14- 17(13,15- 8(2)5-11)16- 9(3)6-12/h7- 9H,4-6H2,1- 3H3 TCPP isomer C9H18Cl 326. 13674- SSA EI 1 InChI=1S/C9H 3O4P 0008 84-5 18Cl3O4P/c1- 7(4-10)14- 17(13,15- 8(2)5-11)16- 9(3)6-12/h7- 9H,4-6H2,1- 3H3 TDCPP C9H15Cl 427. 13674- SSA EI 1 InChI=1S/C9H 6O4P 8839 87-8 15Cl6O4P/c10 -1-7(2-11)17- 20(16,18-8(3- 12)4-13)19- 9(5-14)6- 15/h7-9H,1- 6H2 TEC C12H20 276. 77-93-0 SSA EI 2a InChI=1S/C12 O7 1209 H20O7/c1-4- 17-9(13)7- 12(16,11(15)1 9-6-3)8- 10(14)18-5-

2/h16H,4- 8H2,1-3H3

TEP C6H15O 182. 78-40-0 SSA ESI 3 M+H 183.077 (9 InChI=1S/C6H 4P 0708 pos ppm) 15O4P/c1-4-8- 11(7,9-5-2)10- 6-3/h4-6H2,1- 3H3 Terbutryn C10H19 241. 886-50- SSA ESI 2a M+H 242.1423 InChI=1S/C10 N5S 1361 0 pos (7 ppm) H19N5S/c1-6- 11-7-12-8(15- 10(2,3)4)14- 9(13-7)16- 5/h6H2,1- 5H3,(H2,11,12 ,13,14,15) Terbutryn C10H19 241. 886-50- SSA EI 2b InChI=1S/C10 N5S 1361 0 H19N5S/c1-6- 11-7-12-8(15- 10(2,3)4)14- 9(13-7)16- 5/h6H2,1- 5H3,(H2,11,12 ,13,14,15) Tetradecano C14H28 228. 544-63- SSA EI 2a InChI=1S/C14 ic acid O2 2089 8 H28O2/c1-2-3- 4-5-6-7-8-9- 10-11-12-13- 14(15)16/h2- 13H2,1H3,(H,1 5,16) Tetramethyl C19H18 342. 1168- SSA ESI 3 M+H 343.1167 InChI=1S/C19 scutellarein O6 1103 42-9 pos (4 ppm) H18O6/c1-21- 12-7-5-11(6-8- 12)14-9- 13(20)17- 15(25-14)10- 16(22- 2)18(23- 3)19(17)24- 4/h5-10H,1- 4H3 Thiabendazo C10H7N 201. 148-79- SSA ESI 2b M-H 200.028 (1 InChI=1S/C10 le 3S 0361 8 neg ppm) H7N3S/c1-2-4- 8-7(3-1)12- 10(13-8)9-5- 14-6-11-9/h1- 6H,(H,12,13) Thiabendazo C10H7N 201. 148-79- SSA ESI 2b M+H 202.0426 InChI=1S/C10 le 3S 0361 8 pos (6 ppm) H7N3S/c1-2-4- 8-7(3-1)12- 91

10(13-8)9-5- 14-6-11-9/h1- 6H,(H,12,13) Tolylfluanid C10H13 345. 731-27- SSA EI 2a InChI=1S/C10 Cl2FN2 978 1 H13Cl2FN2O2 O2S2 S2/c1-8-4-6- 9(7-5-8)15(18- 10(11,12)13)1 9(16,17)14(2)3 /h4-7H,1-3H3 Tonalide C18H26 258. 21145- SSA EI 3 InChI=1S/C18 O 1984 77-7 H26O/c1-11-8- 16-15(9- 14(11)13(3)19) 17(4,5)10- 12(2)18(16,6)7 /h8- 9,12H,10H2,1- 7H3 TOTM C33H54 546. 3319- SSA EI 2a InChI=1S/C33 O6 392 31-1 H54O6/c1-7- 13-16-25(10- 4)22-37- 31(34)28-19- 20- 29(32(35)38- 23-26(11- 5)17-14-8- 2)30(21- 28)33(36)39- 24-27(12- 6)18-15-9- 3/h19-21,25- 27H,7-18,22- 24H2,1-6H3 TPO C22H21 348. 75980- TA ESI 1 M+H 349.1352 1S/C22H21O2 O2P 1279 60-8 pos (2 ppm) P/c1-16-14- 17(2)21(18(3)1 5- 16)22(23)25(2 4,19-10-6-4-7- 11-19)20-12- 8-5-9-13- 20/h4-15H,1- 3H3 TPP C18H15 326. 115-86- SSA ESI 1 M+H 327.0815 InChI=1S/C18 O4P 0708 6 pos (9 ppm) H15O4P/c19- 23(20-16-10- 4-1-5-11- 16,21-17-12-6- 2-7-13-17)22-

18-14-8-3-9- 15-18/h1-15H

TPPO C18H15 278. 791-28- SSA ESI 2a M+H 279.0952 InChI=1S/C18 OP 0861 6 pos (5 ppm) H15OP/c19- 20(16-10-4-1- 5-11-16,17-12- 6-2-7-13- 17)18-14-8-3- 9-15-18/h1- 15H trans-4- C9H8O3 164. 501-98- SSA ESI 2a M-H 163.039 (3 InChI=1S/C9H Coumaric 0473 4 neg ppm) 8O3/c10-8-4- acid 1-7(2-5-8)3-6- 9(11)12/h1- 6,10H,(H,11,1 2)/b6-3+ Triclocarban C13H9Cl 313. 101-20- SSA ESI 1 M-H 312.9717 InChI=1S/C13 3N2O 978 2 neg (5 ppm) H9Cl3N2O/c14 -8-1-3-9(4-2- 8)17- 13(19)18-10- 5-6- 11(15)12(16)7- 10/h1- 7H,(H2,17,18, 19) Triclocarban C13H9Cl 313. 101-20- SSA ESI 1 M+H 314.9865 InChI=1S/C13 3N2O 978 2 pos (2 ppm) H9Cl3N2O/c14 -8-1-3-9(4-2- 8)17- 13(19)18-10- 5-6- 11(15)12(16)7- 10/h1- 7H,(H2,17,18, 19) Triclosan C12H7Cl 287. 3380- SSA EI 2a InChI=1S/C12 3O2 9512 34-5 H7Cl3O2/c13- 7-1-3- 11(9(15)5- 7)17-12-4-2- 8(14)6- 10(12)16/h1- 6,16H Tricresylpho C21H21 368. 1330- SSA ESI 2b M+H 369.1262 InChI=1S/C21 sphate O4P 1177 78-5 pos (2 ppm) H21O4P/c1- 16-10-4-7-13- 19(16)23- 26(22,24-20- 14-8-5-11- 93

17(20)2)25- 21-15-9-6-12- 18(21)3/h4- 15H,1-3H3 UV-328 C22H29 351. 25973- SSA EI 2a InChI=1S/C22 N3O 2311 55-1 H29N3O/c1-7- 21(3,4)15-13- 16(22(5,6)8- 2)20(26)19(14- 15)25-23-17- 11-9-10-12- 18(17)24- 25/h9- 14,26H,7- 8H2,1-6H3 Vanillic acid C8H8O4 168. 121-34- SSA ESI 2a M-H 167.0358 InChI=1S/C8H 0423 6 neg (8 ppm) 8O4/c1-12-7- 4-5(8(10)11)2- 3-6(7)9/h2- 4,9H,1H3,(H,1 0,11) Vanillin C8H8O3 152. 121-33- SSA EI 3 InChI=1S/C8H 0473 5 8O3/c1-11-8- 4-6(5-9)2-3- 7(8)10/h2- 5,10H,1H3 Variolaric C16H10 314. 490-34- SSA ESI 2a M-H 313.036 (4 InChI=1S/C16 acid O7 0427 6 neg ppm) H10O7/c1-6-2- 8(17)4-9- 11(6)16(20)23- 10-3-7-5-21- 15(19)12(7)13( 18)14(10)22- 9/h2-4,17- 18H,5H2,1H3 Velutin C17H14 314. 25739- SSA ESI 3 M+H 315.0866 InChI=1S/C17 O6 079 41-7 pos (1 ppm) H14O6/c1-21- 10-6- 12(19)17- 13(20)8- 14(23- 16(17)7-10)9- 3-4- 11(18)15(5- 9)22-2/h3- 8,18-19H,1- 2H3