Occurrence of emerging persistent and mobile organic contaminants in European water samples

Accepted Manuscript Occurrence of emerging persistent and mobile organic contaminants in European water samples Stefanie Schulze, Daniel Zahn, Rosa Montes, Rosario Rodil, José Benito Quintana, Thomas P. Knepper, Thorsten Reemtsma, Urs Berger PII: S0043-1354(19)30036-3 DOI: https://doi.org/10.1016/j.watres.2019.01.008 Reference: WR 14374 To appear in: Water Research Received Date: 31 August 2018 Revised Date: 19 December 2018 Accepted Date: 12 January 2019 Please cite this article as: Schulze, S., Zahn, D., Montes, R., Rodil, R., Quintana, J.B., Knepper, T.P., Reemtsma, T., Berger, U., Occurrence of emerging persistent and mobile organic contaminants in European water samples, Water Research, https://doi.org/10.1016/j.watres.2019.01.008. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain. This is the postprint (accepted manuscript) version of the article published in Water Research. https://doi.org/10.1016/j.watres.2019.01.008 © 2019. This manuscript version is made available under the CC-BY-NC-ND 4.0 license http://creativecommons.org/licenses/by-nc-nd/4.0/ MANUS CRIP T ACCEP TED ACCEPTED MANUSCRIPT Graphical Abstract MANUS CRIP T ACCEP TED ACCEPTED MANUSCRIPT 1 Occurrence of emerging persistent and mobile organic contaminants in 1 European water samples 2 3 Stefanie Schulze 1 , Daniel Zahn 2 , Rosa Montes 3 , Rosario Rodil 3 , José Benito Quintana 3 , 4 Thomas P. Knepper 2 , Thorsten Reemtsma 1 , Urs Berger 1,* 5 6 1 Helmholtz Centre for Environmental Research – UFZ, Department of Analytical Chemistry, 7 Permoserstrasse 15, 04318 Leipzig, Germany 8 2 Hochschule Fresenius University of Applied Sciences, Institute for Analytical Research, 9 Limburger Strasse 2, 65510 Idstein, Germany 10 3 Universidade de Santiago de Compostela, Department of Analytical Chemistry, Nutrition 11 and Food Sciences, IIAA - Institute for Food Analysis and Research, Constantino Candeira 12 S/N, 15782 Santiago de Compostela, Spain 13 14 * Corresponding author e-mail, [email protected]; phone, +49 341 235 4654; fax, +49 341 15 235 450822 16 MANUS CRIP T ACCEP TED ACCEPTED MANUSCRIPT 2 Abstract 17 The release of persistent and mobile organic chemicals (PMOCs) into the aquatic 18 environment puts the quality of water resources at risk. PMOCs are challenging to analyze in 19 water samples, due to their high mobility. The aim of this study was to develop novel 20 analytical methods for PMOCs and to investigate their occurrence in surface and groundwater 21 samples. The target compounds were culled from a prioritized list of industrial chemicals that 22 were modeled to be persistent, mobile, and emitted into the environment. Analytical screening 23 methods based on mixed-mode liquid chromatography (LC), hydrophilic interaction LC, 24 reversed phase LC, or supercritical fluid chromatography in combination with mass 25 spectrometric detection were successfully developed for 57 target PMOCs and applied to 14 26 water samples from three European countries. A total of 43 PMOCs were detected in at least 27 one sample, among them 23 PMOCs that have not been reported before to occur in 28 environmental waters. The most prevalent of these novel PMOCs were methyl sulfate, 229 acrylamino-2-methylpropane sulfonate, benzyltrimethylammonium, benzyldimethylamine, 30 trifluoromethanesulfonic acid, 6-methyl-1,3,5-triazine-diamine, and 1,3-di-o-tolylguanidine 31 occurring in ≥50 % of the samples at estimated concentrations in the low ng L -1 up to µg L -1 32 range. The approach of focused prioritization combined with sensitive target chemical 33 analysis proved to be highly efficient in revealing a large suite of novel as well as scarcely 34 investigated PMOCs in surface and groundwater. 35 36 Keywords: Persistent and mobile organic chemicals, PMOC, water, occurrence, 37 chromatography 38 39 MANUS CRIP T ACCEP TED ACCEPTED MANUSCRIPT 3 1. Introduction 40 Persistent and mobile organic compounds (PMOCs, also referred to as PM substances) are 41 man-made, highly polar organic chemicals that only degrade very slowly (if at all) in the 42 environment and that show a low tendency to sorb to surfaces or to organic matter in soil and 43 sediments (Reemtsma et al. 2016). PMOCs can enrich in (semi-)closed water cycles, as the 44 only relevant process leading to decreasing concentrations in the aquatic environment is 45 dilution. Consequently, if PMOCs are emitted in significant quantities, they may threaten the 46 quality of surface water bodies, groundwater aquifers, and ultimately also our drinking water 47 resources (Reemtsma et al. 2016). Known examples of such PMOCs are melamine (Beltrán48 Martinavarro et al. 2013), saccharine, acesulfame (Buerge et al. 2009), and sulfanilic acid 49 (Holm et al. 1995). PMOCs are particularly critical if they also exhibit toxicological effects. 50 Such compounds are then denoted as PMT (persistent, mobile, and toxic) substances 51 (Neumann 2017). In Europe there is a currently ongoing discussion whether or not PMT 52 substances should be regulated under the European Union chemical regulation REACH 53 (European Parliament 2006) in a similar way as is the case for PBT (persistent, 54 bioaccumulative, and toxic) substances (Neumann and Schliebner 2017). 55 Whereas chemical analytical methods to detect and quantify PBT substances are well 56 established, PMOCs are much more challenging to analyze in environmental water samples. 57 This is due to their intrinsic property of high mobility, which makes PMOCs extremely 58 difficult to extract and enrich from water samples or to separate (retain) using routine liquid 59 chromatography techniques (Reemtsma et al. 2016). The most commonly applied separation 60 method for polar environmental contaminants is undoubtedly reversed phase liquid 61 chromatography (RPLC). However, in RPLC, PMOCs tend to elute with or close to the void 62 volume, together with most of the waterborne matrix constituents. Furthermore, they often 63 exhibit poor peak shape. This severely hampers unambiguous identification, sensitive 64 detection, and reliable quantification of PMOCs. Recently, alternative liquid chromatographic 65 MANUS CRIP T ACCEP TED ACCEPTED MANUSCRIPT 4 methods for separation of highly polar compounds such as PMOCs have been developed, 66 based on either hydrophilic interaction liquid chromatography (HILIC) (Mazzarino et al. 67 2011; Christophoridis et al. 2016; Zahn et al. 2016) or tri-functional mixed-mode liquid 68 chromatography (MMLC) separation columns (Montes et al. 2017). Furthermore, also 69 supercritical fluid chromatography (SFC) with hybrid or normal phase columns and a polar 70 modifier/co-solvent can be used as an orthogonal technique to RPLC (Parr et al. 2016; Bieber 71 et al. 2017). 72 A recent modeling study identified potential PMOCs as well as precursors to PMOCs among 73 the high production volume substances registered under REACH (Arp et al. 2017). Arp and 74 co-workers came up with a list of 2167 unique substance identities, whereof 1811 have been 75 modeled to be persistent and mobile in the aquatic environment (PMOC score of 4 to 5 in Arp 76 et al. 2017) and 356 have been modeled to be PMOC precursors (i.e. to have the potential to 77 be hydrolyzed to PMOCs with a PMOC score of 4 to 5). Building on this work, we estimated 78 the environmental emission potential of the 2167 substances (Schulze et al. 2018). This study 79 resulted in two consolidated lists, one for PMOCs that are expected to be emitted into the 80 environment (936 substances) and a corresponding list for PMOC precursors (174 substances) 81 (supplementary data in Schulze et al. 2018). Both lists are ranked according to the 82 environmental emission potential, i.e. the magnitude of expected emissions. However, the 83 ultimate proof that a substance is released into the environment in significant quantities and 84 possesses PMOC properties is its presence in environmental water samples far from potential 85 points of emissions. 86 The aim of the present study was thus to screen for PMOCs of concern in selected water 87 samples from three European countries. The target analytes were primarily chosen from the 88 list of 936 PMOCs prioritized with regard to expected emissions (Schulze et al. 2018). 89 Enrichment methods based on solid phase extraction or evaporation as well as instrumental 90 methods based on MMLC (Montes et al. 2017), HILIC (Zahn et al. submitted), or SFC were 91 MANUS CRIP T ACCEP TED ACCEPTED MANUSCRIPT 5 employed, as well as two RPLC-based separation methods. Target chemical analytical 92 methods were used (rather than HRMS-based suspect screening) for two reasons. 1) PMOCs 93 are not expected to be sufficiently retained on a generic RPLC-based separation column 94 (Reemtsma et al. 2016). 2) We intended to screen for the PMOCs in surface and groundwater, 95 rather than in WWTP effluent, to verify their persistence and mobility (i.e. their occurrence 96 far from primary environmental emission points), and thus we needed methods of utmost 97 sensitivity. The results of the present study should be used to validate the PMOC and 98 emission modeling (Arp et al. 2017; Schulze et al. 2018) and to obtain a first picture of the 99 potential magnitude of the problem of PMOCs in European water cycles. 100 101 2. Materials and methods 102 2.1 Target analytes 103 A total of 64 target analytes were selected for the present study. Table S1 in the 104 supplementary data shows the structures and CAS registry numbers of all analytes and lists 105 the suppliers and purities of the commercial standards. The majority of these analytes (54 106 substances) originated from the top 300 substances on the list of modeled PMOCs ranked 107 according to their expected emission potential (Table S1 in the supplementary data in Schulze 108 et al. 2018). The selection of the 54 target analytes was based on the prerequisites of 109 availability of chemical standards and amenability to at least one of the employed 110 instrumental methods (see section 2.4). Additionally, substances were excluded if they were 111 assessed to be non-persistent or volatile by expert judgement. The remaining ten target 112 analytes were ID-2, -22, -32, -37, -38, -41, -43, -49, -52, and -59 (Table S1). They were 113 chosen based on knowledge or suspicion of their occurrence in environmental water samples 114 (e.g. Stüber and Reemtsma 2004; Landesamt für Natur, Umwelt und Verbraucherschutz NRW 115 2015; Scheurer et al. 2016; Montes et al. 2017). 116 MANUS CRIP T ACCEP TED ACCEPTED MANUSCRIPT 6 ChemAxon (JChem for Office, JChem for Excel) was used to estimate substance properties, 117 as the studied chemicals are within its application domain (personal communication with D. 118 Szisz, ChemAxon). The majority of the selected analytes (44) are highly hydrophilic 119 compounds with a negative logD value at pH 7 (Table S1). Among the analytes there were 26 120 compounds possessing acidic properties, with either a carboxylic, sulfonic, sulfuric or 121 phosphonic acid moiety (strongest acidic pK a between -4.6 and 5.5) and 35 compounds 122 possessing basic properties (strongest basic pK a between 2.4 and 10.7) (ChemAxon). Stock 123 standard solutions of analytes were prepared in acetonitrile, acetonitrile:water (50:50) or 124 water (depending on solubility) at 1 mg mL -1 and stored at -20 °C. Aliquots of the stock 125 standard solutions were combined to obtain standard mixture solutions, which were 126 subsequently diluted with acetonitrile or water depending on the chromatographic system to 127 be used (see section 2.4). 128 2.2 Samples 129 The 14 water samples analyzed in the present study were grab samples obtained from 130 different locations in Germany (DE, country code used in sample names), Spain (ES), and 131 The Netherlands (NL). They consisted of surface water (SW, 7 samples), groundwater (GW, 132 4), bank filtrate (BF, 1), as well as reverse osmosis concentrate (ROC, 1) and permeate (ROP, 133 1) from a full-scale pilot plant for drinking water production. The samples were taken in 2016 134 and stored for up to six weeks at +4 °C in the dark until analysis. Details on all samples are 135 given in Table S2 and Figure S1 in the supplementary data. 136 2.3 Sample preparation 137 Chemical analysis of all samples was performed in parallel in three different labs with 138 complementary instrumental techniques. A number of sample preparation methods were used 139 in each lab, which are briefly described individually hereafter. In total 8 different sample 140 preparation techniques (denoted as Enrichment I-VIII) were developed, using spike and 141 recovery experiments at PMOC concentrations in the ng L -1 to µg L -1 range in surface and 142 MANUS CRIP T ACCEP TED ACCEPTED MANUSCRIPT 7 drinking water. Materials, chemicals, and instrumentation used in the different enrichments 143 are listed in Table S3 in the supplementary data. 144 Enrichment I. The water sample was filtered through a 0.45 µm cellulose filter and an aliquot 145 of 100 mL was submitted to a mixed-mode weak anion exchange (WAX) solid phase 146 extraction (SPE) cartridge. The cartridge was previously conditioned with 5 mL of 2 % formic 147 acid in methanol and 5 mL of Milli-Q water. After sample loading the cartridge was dried and 148 analytes were eluted with 10 mL of 5 % ammonia in methanol. The extract was evaporated to 149 dryness and the residues were reconstituted in 200 µL of Milli-Q water:acetonitrile (90:10). 150 Finally, the extract was filtered through a 0.22 µm PP filter. For more details see Montes et al. 151 (manuscript). 152 Enrichment II. Identical to Enrichment I but employing a mixed-mode weak cation exchange 153 (WCX) SPE cartridge previously conditioned with 5 mL of 5 % ammonia in methanol and 5 154 mL of Milli-Q water. Elution of the analytes was performed with 10 mL of 2 % formic acid in 155 methanol (Montes et al., manuscript). 156 Enrichment III. A multi-layer SPE cartridge (3 mL) was prepared by filling in (from bottom 157 to top) 60 mg (±5 mg) of graphitized carbon black (GCB), 60 mg (±5 mg) of WCX bulk 158 material, and 60 mg (±5 mg) of WAX bulk material, separated by polyethylene frits. The 159 cartridge was conditioned with 1 mL 5 % ammonia in methanol, 1 mL 2 % formic acid in 160 methanol, 1 mL methanol, and 3 mL deionized water. The water sample was filtered through a 161 glass fiber filter and the pH was adjusted to 5.5 ± 0.1 with formic acid or ammonium 162 hydroxide. An aliquot of 100 mL was passed through the cartridge. The cartridge was dried 163 and elution was performed with 3 mL 5 % ammonia in methanol, 3 mL 2 % formic acid in 164 methanol, and 1.5 mL methanol:dichloromethane (80:20). The combined extracts were 165 evaporated to dryness and the residues were reconstituted in 500 µL of acetonitrile:water 166 (95:5). Finally, the extract was filtered through a 0.2 µm cellulose syringe filter. For more 167 details see Köke et al. (2018). 168 MANUS CRIP T ACCEP TED ACCEPTED MANUSCRIPT 14 more than 24 of the investigated PMOCs (Figure S5), which demonstrates the 325 complementarity of the methods. Nevertheless, there were distinct differences in the 326 broadness of applicability. Enrichments III and IV (multi-layer SPE and evaporation, both in 327 combination with HILIC) and Enrichment VII (ENV+ SPE, in combination with RPLC or 328 SFC) were the enrichment methods capturing most PMOCs. Multi-layer SPE methods have 329 also earlier been used successfully in environmental water analysis for a variety of polar 330 micropollutants (Huntscha et al. 2012). On the other hand, Enrichment VI (MCX) was only 331 successful for few PMOCs in the present study. MCX is a strong reversed-phase mixed-mode 332 cation-exchange polymer. Some cationic analytes may have sorbed too strongly on this 333 polymer to be eluted with the chosen elution method. In terms of separation methods, 334 Chromatography C 2 (RPLC with Hypercarb column) showed a comparatively poor 335 performance. It worked well for standard chemicals, but many signals broadened significantly 336 in the presence of sample matrix, preventing this method from a broad applicability range 337 among the selected target PMOCs (Figure S5). 338 3.1.4 Procedural blanks and method detection limits 339 The estimated method detection limits (MDLs) for all PMOCs applying the developed 340 methods (i.e. combinations of enrichment and instrumental methods) are listed in Table S9. 341 They were generally in the low to sub ng L -1 range, but covered overall five orders of 342 magnitude (0.02 to 2000 ng L -1 ) for the different PMOCs and methods. Also for some 343 individual PMOCs the MDLs of different methods varied considerably. It is important to note 344 that the MDLs were not only dependent on the enrichment and separation methods, but also 345 on the employed MS instrument and on the presence (or absence) of procedural blank 346 contamination. A total of 29 investigated PMOCs seem to be widely dispersed water 347 pollutants or contaminants in lab consumables and equipment, as they were detected 348 repeatedly in procedural blank experiments, leading to correspondingly elevated MDLs. 349 These compounds were ID-2, -10, -14, -16, -17, -20, -21, -22, -23, -24, -25, -26, -32, -33, -34, 350 MANUS CRIP T ACCEP TED ACCEPTED MANUSCRIPT 15 -36, -37, -39, -40, -43, -44, -46, -47, -51, -52, -54, -58, -61, and -63. No effort was made in the 351 present study to elucidate or eliminate the source(s) of the procedural blank contaminations. 352 3.2 Detection frequencies in target screening of environmental water samples 353 All developed method combinations were applied to 14 water samples (section 2.2 and Table 354 S2) to screen for the 57 PMOCs amenable to at least one of the methods (see 3.1.3). The 355 samples comprised surface water, groundwater, and bank filtrate as well as reverse osmosis 356 concentrate and permeate. In total 43 PMOCs (75 % of the investigated substances) were 357 detected above their MDL in at least one sample with at least one of the applied methods 358 (Figure 1). Figure 1 shows the detection frequency for the individual PMOCs in the 14 359 samples including information on the number of underlying principally different separation 360 methods (Chromatography A-D). Of the 43 detected PMOCs, 21 were found in at least 50 % 361 of the samples and often at relatively high concentrations (Figure S6 and section 3.3 below). 362 Chromatography method-specific detection frequencies are listed in Table S10, underpinning 363 the complementarity of the employed separation methods in analysis of the target PMOCs. 364 The most important detected PMOCs are discussed in section 3.4 below. 365 3.3 Concentration estimates 366 Concentrations of the detected PMOCs in the water samples were estimated according to 367 section 2.5. They need to be considered as semi-quantitative estimates. Since extraction 368 recoveries and matrix effects (suppression more common than enhancement) were not taken 369 into account, it can be assumed that the estimated concentrations are mostly underestimations. 370 Figure 2 shows boxplots of estimated concentrations of selected PMOCs in the water samples. 371 The selection of PMOCs for Figure 2 was based on the quality criteria that the substance was 372 detected by more than one method and that the estimated concentrations by the different 373 methods for a given sample were consistent (i.e. typically within one order of magnitude, then 374 averaged over all methods in Figure 2). Furthermore, Figure S6 depicts the maximum 375 MANUS CRIP T ACCEP TED ACCEPTED MANUSCRIPT 16 estimated concentration (gray shade) for all detected PMOCs together with the frequency of 376 detection. 377 Some PMOCs were detected in the high ng L -1 up to µg L -1 range (Figure 2 and Figure S6). 378 Of the PMOCs shown in Figure 2, these were notably ID-13 (acesulfame), ID-25 (sulfanilic 379 acid), ID-26 (melamine), ID-33 (trifluoromethanesulfonic acid), ID-37 (cyanoguanidine), ID380 39 (p-toluenesulfonic acid), ID-40 (saccharine), ID-44 (dimethylbenzenesulfonic acid), and 381 ID-45(benzyldimethylamine). It is noteworthy that a high frequency of detection did not 382 necessarily go along with high concentrations. An example is ametryn (ID-61), which was 383 detected in 11 samples, but at a low maximum concentration (Figure 2). 384 3.4 Discussion of detected PMOCs 385 All of the 43 detected PMOCs were industrial chemicals registered under REACH with 386 calculated logD values at pH 7 ranging between -5.6 and 3.4 (average -1.9, ChemAxon). 387 Their uses cover many different fields of application, including coating products, inks and 388 paints, adhesives and sealants, water treatment products, leather and textile treatment 389 products, cosmetics and personal care products, vulcanization or polymerization processes, 390 and processing aids in other applications (Table 1). Also the tonnages manufactured in and/or 391 imported into the European Union vary widely. They range from single digit up to hundred 392 thousands of tons (Table 1, ECHA 2018). 393 The detected PMOCs were categorized according to two criteria: Frequency of detection and 394 level of awareness as environmental water pollutants (Figure 3 and Table 1). PMOCs that 395 were detected in at least half of the samples (≥7 samples) were placed in the category “high 396 frequency of detection”, other detected PMOCs were placed in the category “low frequency 397 of detection”. For the awareness criterion, three categories were made based on a literature 398 search using Google Scholar including the substance name (IUPAC or trivial name) and the 399 search terms ‘environment’, ‘surface water’, ‘groundwater’, or ‘drinking water’. The three 400 categories were “novel” PMOCs, i.e. substances that have not been reported as environmental 401 MANUS CRIP T ACCEP TED ACCEPTED MANUSCRIPT 17 water pollutants so far, “scarcely investigated” PMOCs, i.e. substances for which very few 402 reports on environmental occurrence exist (often only from industrial sites or waste water 403 treatment effluents), and “well-known” PMOCs, for which ample literature data exist. This 404 categorization allows a prioritization of the detected PMOCs for future investigations as 405 indicated in Figure 3, with PMOCs in the top left corner having the highest priority (priority 406 1), followed by PMOCs in the top middle (priority 2), PMOCs in the bottom left corner 407 (priority 3), and so forth. The PMOCs in the two top priority categories are shown with their 408 structures in Figure 3 and shortly discussed individually in the following sub-sections, while 409 all detected PMOCs are presented in Table 1. 410 3.4.1 Priority 1 PMOCs 411 Methyl sulfate (ID-14) as a relatively small surfactant was detected in surface and 412 groundwater samples primarily from The Netherlands at levels up to the high ng L -1 range. 413 The present study is the first report on the occurrence of methyl sulfate in the environment. 414 2-Acrylamino-2-methylpropane sulfonate (ID-16) was one of several sulfonic 415 acids/sulfonates frequently detected in the present study. This compound was typically found 416 in the range of 1-10 ng L -1 , but occasionally also exceeding 100 ng L -1 . ID-16 was detected in 417 every analyzed sample type. The occurrence of ID-16 in environmental waters is reported 418 here for the first time. 419 Benzyltrimethylammonium (ID-23), a permanently charged quaternary ammonium cation, 420 and benzyldimethylamine (ID-45) are two PMOCs with similar basic structures that were 421 frequently detected here for the first time. They were both primarily found in surface water, 422 but in single cases also in groundwater samples. ID-23 was detected in single digit ng L -1 423 concentrations while ID-45 occurred in up to several hundreds of ng L -1 . 424 Trifluoromethanesulfonic acid (TFMSA, ID-33) was found in all analyzed samples with the 425 exception of the reverse osmosis permeate and at levels up to the µg L -1 range (Figure 2). 426 TFMSA could be analyzed by all of the separation methods (Table S9), even though the 427 MANUS CRIP T ACCEP TED ACCEPTED MANUSCRIPT 18 retention in HILIC and RPLC was poor (Table S8). We have chosen to categorize TFMSA as 428 “novel” since we are the only ones so far who have reported on the occurrence of TFMSA in 429 environmental water samples (Zahn et al. 2016; Montes et al. 2017, in another context and in 430 other samples from the same larger collaborative study). TFMSA belongs to the group of 431 short-chain perfluoroalkane sulfonic acids. Other short-chain perfluoroalkyl acids, such as 432 trifluoroacetic acid, have already been found in drinking water (Mak et al. 2009; Janda et al. 433 2018). 434 6-Methyl-1,3,5-triazine-diamine (acetoguanamine, ID-42) was detected in all of the 7 435 surface water samples at concentrations typically around or below 10 ng L -1 (Figure 2). To the 436 best of our knowledge the presence of acetoguanamine in environmental water samples is 437 reported here for the first time. 438 1,3-Di-o-tolylguanidine (DTG, ID-58) was detected in all 14 analyzed samples (in 11 439 samples with at least two methods, Figure 1) at estimated concentrations typically around 10 440 ng L -1 (Figure 2). Likewise TFMSA (ID-33), so far only our reports exist on the presence of 441 DTG in surface water, groundwater, and drinking water (present study and Montes et al. 2017 442 with a different sample set). 443 3.4.2 Priority 2 PMOCs 444 Adamantan-1-amine (amantadine, ID-32) is a pharmaceutical used as antiviral (against 445 influenza A virus) and antiparkinsonian medication. Moreover, amantadine is also a chemical 446 registered under REACH because of its use as an intermediate in industrial processes (ECHA 447 2018). Also this PMOC was identified in every sample with the exception of the reverse 448 osmosis permeate. It has earlier been identified in German municipal effluent water (Möhle 449 and Metzger 2001). 450 All of the three guanidine derivatives that were analyzed (including DTG discussed above and 451 DPG discussed below) were detected in the majority of samples. Cyanoguanidine (CG, ID452 37) was detected in 8 of the analyzed water samples, i.e. in all 7 surface water samples and in 453 MANUS CRIP T ACCEP TED ACCEPTED MANUSCRIPT 19 one German groundwater sample (Figure 1) at concentrations exceeding 3000 ng L -1 (Figure 454 2). Few studies have previously reported the environmental occurrence of CG. Scheurer and 455 co-workers detected CG in German surface water in the mg L -1 range, with an industrial site 456 as a point source (Scheurer et al. 2016). In surface water samples in a coastal agricultural 457 catchment from New Zealand CG was quantified with a maximum concentration close to 1 458 mg L -1 (Smith and Schallenberg 2013). 459 p-Toluenesulfonic acid (ID-39) was detected in all 14 samples and at concentrations 460 exceeding 1000 ng L -1 . It has earlier been detected in drinking water in the United Kingdom 461 (Crathorne et al. 1984). 462 The two isomers of dimethylbenzenesulfonic acid (ID-44), i.e. xylenesulfonic acid and 2,3463 dimethylbenenzenesulfonic acid, were both detected in 13 samples (Figure 1). Only the 464 reverse osmosis permeate from the Netherlands showed levels <MDL. Betowski and co465 workers have earlier reported on the presence of xylenesulfonic acid in groundwater 466 (Betowski et al. 1996). 467 Two isomers of the compound toluenesulfonamide (ID-51) were detected in 12 out of 14 468 samples, with the exception of one groundwater sample and the reverse osmosis permeate. In 469 a study by Richter et al. (2017) with different types of water from Berlin ID-51 was found at 470 concentrations up to 50 µg L -1 in wastewater and 0.27 µg L -1 in drinking water. 471 Likewise DTG, 1,3-diphenylguanidine (DPG, ID-52) was detected in all 14 analyzed 472 samples, but at higher estimated concentrations up to 100 ng L -1 (Figure 2). In an earlier study 473 on drinking water in China DPG was found at levels up to 0.74 mg L -1 due to migration from 474 high density polyethylene pipes (Tang et al. 2015). 475 3.5 Evaluation of the prioritization and analytical strategy 476 While a number of prioritization approaches for chemicals (based on regulatory databases or 477 other available datasets) with respect to environmental and/or human exposure and risk have 478 been published (as reviewed in e.g. Muir and Howard 2006; Bu et al. 2013; Mitchell et al. 479 MANUS CRIP T ACCEP TED ACCEPTED MANUSCRIPT 20 2013), relatively few chemical analytical studies have been conducted taking direct advantage 480 of such prioritization exercises (McLachlan et al. 2014; Singer et al. 2016; Sjerps et al. 2016; 481 Montes et al. 2017; Gago-Ferrero et al. 2018). Nevertheless, monitoring is necessary to 482 validate the prioritization approaches. 483 The present chemical analytical study builds on a prioritized list of industrial chemicals that 484 have been modeled to be persistent, mobile, and to possess a high environmental emission 485 potential (Schulze et al. 2018). Additionally, we used targeted analytical methods with 486 generally very high sensitivity. Still, several target analytes were not detected in the analyzed 487 samples. This could be due to one or several of the following uncertainties of our overall 488 prioritization and analytical strategy. I) The modeling of especially persistence, but also 489 mobility and emission potential, is tainted with considerable uncertainties, as discussed in 490 detail in Arp et al. 2017 and in Schulze et al. 2018. II) For some of the target analytes 491 enrichment from water, chromatographic retention and/or peak shape, or ionization in ESI 492 was poor, hampering sensitive detection. III) The analyzed water samples were not 493 representative for all European countries or regions. Some PMOCs may have well defined 494 points of emission that were not covered by the sampling design. 495 Despite these uncertainties, our overall strategy was highly successful. Among the 54 target 496 PMOCs selected from the prioritized list in the supplementary data in Schulze et al. 2018 497 (section 2.1), 49 were amenable to at least one of the developed methods. Out of these 49 498 substances 35 PMOCs were found in surface and/or groundwater, among them 23 PMOCs 499 that have not been reported before to occur in environmental waters. The high detection rate 500 of 71 % (35/49) validates the good accuracy of the modeling and corroborates the strength of 501 the chosen approach, i.e. a focused prioritization combined with sensitive target analysis. 502 503 4 Conclusions 504 MANUS CRIP T ACCEP TED ACCEPTED MANUSCRIPT 21 The present study has validated and proven the strength of the chosen modeling and analytical 505 approach consisting of a focused prioritization combined with sensitive target chemical 506 analysis. The developed enrichment and chromatographic methods proved to be useful and 507 complementary for analysis of PMOCs in water samples. They can be used individually or in 508 combination with each other to further investigate the occurrence and fate of PMOCs in water 509 cycles. In the present study 75 % of the analyzed PMOCs were detected in selected water 510 samples from Germany, Spain and The Netherlands. This high rate of detection together with 511 the fact that more than 1000 PMOC candidates with an environmental emission potential were 512 identified only among the substances registered under REACH (Schulze et al. 2018) leads to 513 the conclusion that there are likely hundreds of so far undiscovered PMOCs present in 514 environmental waters, threatening the quality of drinking water resources. An important 515 follow-up study would thus be to use the list published by Schulze et al. (2018) in order to 516 better characterize the number and identity of PMOCs occurring in environmental waters. 517 Furthermore, the development of quantitative analytical methods for PMOCs would enable 518 more detailed fate studies of PMOCs, e.g. investigating the removal in different steps of 519 drinking water production. Finally, the toxicity of the most abundant of the identified PMOCs 520 (e.g. TFMSA, CG, and p-toluenesulfonic acid occurring in high ng L -1 up to µg L -1 521 concentrations) needs to be investigated as another important step in PMOC risk assessment. 522 In this respect, activities are ongoing by national and European authorities to classify 523 substances according to their persistence, mobility, and toxicity (PMT) properties (Neumann 524 and Schliebner 2017). The results of the present study inform such activities. 525 526 Acknowledgments 527 This work has been funded by the German BMBF (02WU1347A/B) and the Spanish 528 MINECO/AEI (JPIW2013-117) in the frame of the collaborative international consortium 529 (WATERJPI2013 – PROMOTE) of the Water Challenges for a Changing World Joint 530 MANUS CRIP T ACCEP TED ACCEPTED MANUSCRIPT 22 Programming Initiative (Water JPI) Pilot Call. RM, RR and JBQ also acknowledge Galician 531 Council of Culture, Education and Universities and FEDER/EDRF funding 532 (ED431C2017/36). The authors are thankful for the support in sample acquisition by 533 Hessenwasser GmbH & Co. KG (Darmstadt, Germany), Peter Seel (Hessian Agency for 534 Nature Conservation, Environment and Geology, Wiesbaden, Germany), Mónica Velo and 535 Raquel Piñeiro (Augas de Galicia, Santiago de Compostela, Spain), Oasen drinking water 536 (Gouda, the Netherlands), and Vittorio Albergamo (Institute for Biodiversity and Ecosystem 537 Dynamics, University of Amsterdam, The Netherlands). Finally, we would like to thank 538 Heidrun Paschke and Till Meier for technical help in the lab. 539 540 Appendix A. Supplementary data 541 Supplementary data related to this article can be found at … 542 543 References 544 Alonso, M. C.; Barcelo, D. 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Environ. Sci. Technol., 48, 7264–7271. 619 MANUS CRIP T ACCEP TED ACCEPTED MANUSCRIPT Figure 1. Detection frequencies of the target PMOCs in the 14 water samples. The gray shading shows the number of principally different separation methods (Chromatography A-D) with which the PMOCs were detected. MANUS CRIP T ACCEP TED ACCEPTED MANUSCRIPT Figure 2. Estimated concentrations of selected PMOCs in the water samples. The color shading indicates the detection frequency in the 14 samples. The horizontal line marks the median value, the box comprises the interquartile range (IQR), and the whiskers reach to the outmost measuring points that are within 1.5 times the IQR. Dots represent single high concentrations. ID-6: methacrylamido propyl trimethyl ammonium, ID-13: acesulfame, ID15: 1,4-diazabicyclo-[2.2.2]octane, ID-16: 2-acrylamino-2-methylpropane sulfonate, ID-23: benzyltrimethylammonium, ID-25: sulfanilic acid, ID-26: melamine, ID-29: N-(3- (dimethylamino)-propyl)methacrylamide, ID-32: adamantan-1-amine, ID-33: trifluoromethanesulfonic acid, ID-37: cyanoguanidine. ID-38: 2-amino-4,5dichlorobenzenesulfonic acid, ID-39: p-toluenesulfonic acid, ID-40: saccharine, ID-42: 6methyl-1,3,5,-triazine-diamine, ID-44: dimethylbenzenesulfonic acid, ID-45: benzyldimethylamine, ID-52: 1,3-diphenylguanidine, ID-57: bisphenol S, ID-58: 1,3-di-otolylguanidine, ID-61: ametryn. MANUS CRIP T ACCEP TED ACCEPTED MANUSCRIPT Figure 3. Classification of PMOCs in priority classes (1-6) according to their frequency of detection and level of awareness as environmental water pollutants. MANUS CRIP T ACCEP TED ACCEPTED MANUSCRIPT Highlights - Persistent and mobile organic chemicals (PMOCs) occur in drinking water resources - Innovative methods for analysis of PMOCs in water samples are presented - 57 PMOCs are selected and analyzed in 14 European water samples - 43 PMOCs (75 %) are detected, among them 23 for the first time - PMOC concentrations range up to µg L -1 in surface and groundwater S1 Supplementary Data Occurrence of emerging persistent and mobile organic contaminants in European water samples Stefanie Schulze1, Daniel Zahn2, Rosa Montes3, Rosario Rodil3, José Benito Quintana3, Thomas P. Knepper2, Thorsten Reemtsma1, Urs Berger1,* 1 Helmholtz Centre for Environmental Research – UFZ, Department of Analytical Chemistry, Permoserstrasse 15, 04318 Leipzig, Germany 2 Hochschule Fresenius University of Applied Sciences, Institute for Analytical Research, Limburger Strasse 2, 65510 Idstein, Germany 3 Universidade de Santiago de Compostela, Department of Analytical Chemistry, Nutrition and Food Sciences, IIAA - Institute for Food Analysis and Research, Constantino Candeira S/N, 15782 Santiago de Compostela, Spain * Corresponding author: Urs Berger, e-mail: [email protected]; phone: +49 341 235 4654; fax: +49 341 235 450822 S2 Table of contents Table S1. List of target PMOCs sorted by logD (pH 7.0) S3 Table S2. Sample description S10 Figure S1. Sampling regions S11 Table S3. Materials, chemicals and instrumentation for Enrichment I-VIII S12 Table S4. Chemicals and instrumentation for the instrumental methods Chromatography A-D S14 Figure S2. Gradient profiles of the mobile phases as a function of time S15 Table S5A. Chromatography A (MMLC-MS/MS) mass spectrometric parameters S16 Table S5B. Chromatography B (HILIC-MS/MS) mass spectrometric parameters S18 Table S5C. Chromatography C1/C2 (RPLC-MS/MS) mass spectrometric parameters S21 Table S5D. Chromatography D1/D2 (SFC-HRMS) mass spectrometric parameters S23 Method performance evaluation and semi-quantitative concentration estimates S24 Table S6. Retention time repeatability for the different chromatographic methods over a relevant sample batch bracketed between standards S24 Table S7. Instrumental detection limits for the target PMOCs given as injected quantities [ng] with the different instrumental methods S25 Table S8. Retention factor k’ of the target chemicals for the different chromatographic methods S27 Figure S3. Retention factors k‘ of all PMOCs for the different chromatographic method S28 Figure S4. Retention factors k’ versus logD for all PMOCs and all chromatographic methods S29 Figure S5. Number of PMOCs that were amenable to the different combinations of enrichment and instrumental methods S30 Table S9. Enrichment and instrumental methods that were successfully applied for analysis of the different PMOCs (indicated with a +) S31 Figure S6. Frequency of detection (including all methdos) and maximum estimated concentration of the detected PMOCs in the 14 water samples S34 Table S10. Chromatography method-specific detection frequencies (number of samples) of the detected PMOCs in the 14 water samples S35 S3 Table S1. List of target PMOCs sorted by logD (pH 7.0)1 Index CAS registry number Substance name logD (pH 7.0) 1 Structure (main structure at pH 7.0)1 Supplier Chemical standard grade ID-1 299-27-4 (Potassium) gluconate -6.68 HO OH OH OH OH O O Sigma Aldrich Pharmace utical secondary standard ID-2 140-31-8 2-Piperazin-1-ylethylamine -5.61 N N H 2 NH 3 Fluorochem ID-3 2855-13-2 Isophoronediamine -4.59 CH 3 H 3 C NH 3 H 3 C H 3 N abcr GmbH 99% ID-4 45021-77-0 (3-Acrylamidopropyl)- trimethylammonium (chloride) -4.13 H 3 C N CH 3 H 3 C N H O CH 2 Sigma Aldrich 75% ID-5 83016-70-0 N,N,N’-Trimethyl-N’-(2hydroxyethyl)-bis(2aminoethyl)ether -3.99 H 3 C N CH 3 O N CH 3 OH abcr GmbH 98% ID-6 51410-72-1 Methacrylamido propyl trimethyl ammonium (chloride) -3.74 H 3 C CH 2 O H NN CH 3 CH 3 H 3 C abcr GmbH 50% ID-7 3033-62-3 Bis(2-dimethylaminoethyl)ether -3.57 H 3 C N CH 3 O N CH 3 CH 3 Alfa Aesar 98% ID-8 81-04-9 1,5-Naphthalenedisulfonic acid -3.43 O SO O S O O O abcr GmbH ID-9 7365-45-9 2-[4-(2-hydroxyethyl)-1piperazinyl]ethanesulfonic acid -3.25 OH N NH SOO O Sigma Aldrich ≥ 99,5 % S4 ID-10 34730-59-1 (Sodium) 2-(2aminoethylamino)ethanesulfon ate -3.25 H 3 N NH S O OO Ark Pharm Fine Chemicals 40% ID-11 3030-47-5 1,1,4,7,7-Pentamethyldiethylenetriamine -3.20 H 3 C N CH 3 N CH 3 N CH 3 CH 3 Acros Organics ≥ 99,5 % ID-12 52556-42-0 3-Allyloxy-2-hydroxy-1propanesulfonic acid (sodium salt) -3.13 OH O CH2 S O O O Sigma Aldrich ID-13 55589-62-3 Acesulfame (K) -3.06 CH 3 O N S OO O Sigma Aldrich ≥ 99 % ID-14 512-42-5 (Sodium) methyl sulfate -2.84 H 3 C O S O OO Sigma Aldrich ID-15 280-57-9 1,4-diazabicyclo-[2.2.2]octane -2.83 N N Sigma Aldrich ≥ 99 % ID-16 5165-97-9 (Sodium) 2-acrylamino-2methylpropane sulfonate -2.71 CH3 H3C SO O O NH O H2C abcr GmbH ID-17 52722-86-8 4-Hydroxy-1-(2-hydroxyethyl)- 2,2,6,6,-tetramethylpiperidine -2.62 CH 3 H 3 C OH H 3 C H 3 C N HO abcr GmbH 98% ID-18 3039-83-6 (Sodium) vinylsulfonate -2.60 O S O O H2C abcr GmbH 25% ID-19 17636-10-1 3-Mercapto-1-propanesulfonic acid (sodium salt) -2.56 O S O O HS Sigma Aldrich 90 % (technical grade) ID-20 342573-755 (1-Ethyl-3-methylimidazolium) ethyl sulfate -2.48 CH 3 O S O OO Fluka Analytical ≥ 98,5 % S5 ID-21 1704-62-7 2-(2- (Dimethylamino)ethoxy)ethanol -2.41 H 3 C N CH 3 O OH Sigma Aldrich 98% ID-22 108-80-5 Cyanuric acid -2.39 O NH O N H O HN Sigma Aldrich analytical standard ID-23 56-93-9 Benzyltrimethylammonium (chloride) -2.24 H 3 C N H 3 C CH 3 Sigma Aldrich 97% ID-24 1561-92-8 2-Methyl-2-propene-1-sulfonic acid (sodium salt) -2.21 CH3 CH2 S O OO Sigma Aldrich 98% ID-25 121-47-1 121-57-3 Sulfanilic acid -2.04 NH 2 S O O O NH 2 S O O O Sigma Aldrich 99% ID-26 108-78-1 Melamine -2.02 NH 2 NH NH 2 NH 2 N N Sigma Aldrich analytical standard ID-27 1571-33-1 Phenylphosphonic acid -1.98 O PHO O Sigma Aldrich 98% ID-28 497-18-7 Carbodihydrazide -1.96 NH2 NH O NHH2N Sigma Aldrich 98% ID-29 5205-93-6 N-(3-(dimethylamino)- propyl)methacrylamide -1.85 H 3 C N CH 3 N H O CH 3 CH 2 Fluorochem ID-30 1071-93-8 Adipic acid dihydrazide -1.72 H 2 N H N O O N H NH 2 Fluorochem S6 ID-31 98-67-9 p-Phenolsulfonic acid hydrate -1.53 OH S O O O abcr GmbH 85% ID-32 768-94-5 Adamantan-1-amine -1.49 NH 3 Fluorochem ID-33 1493-13-6 Trifluoromethanesulfonic acid -1.23 SOO F FF O Sigma Aldrich ≥ 99 % ID-34 3965-55-7 Dimethyl 5-sulfoisophthalate (sodium salt) -1.22 CH 3 OO S O O O O O CH 3 Alfa Aesar 98% ID-35 7529-22-8 N-methylmorpholin-N-oxid -1.15 CH 3 N O O Sigma Aldrich 97% ID-36 622-40-2 2-(4-Morpholinyl)ethanol -1.13 OH NH O Sigma Aldrich 99% ID-37 461-58-5 Cyanoguanidine -1.03 N N H 2 N H 2 N Acros Organics 99.50% ID-38 6331-96-0 2-Amino-4,5Dichlorobenzenesulfonic acid -0.84 Cl Cl S O O OH NH 2 Fluorochem ID-39 104-15-4 p-Toluenesulfonic acid -0.71 CH 3 S O O O MP Biomedicals ≥ 99 % ID-40 81-07-2 Saccharine -0.49 O N S O O Sigma Aldrich ≥ 99% S13 V Materials and instrumentation: Weak anion exchanger (WAX), OASIS, 150 mg, 6 mL (Waters, Eschborn, Germany) Freestyle SPE unit (LCTech GmbH, Obertaufkirchen, Germany) Glas Fibre Filters Whatman (GE Healthcare, Freiburg, Germany) Chemicals: Methanol (Biosolve, Valkenswaard, Netherlands) Hydrochloric acid (Chemsolute, Th. Geyer, Berlin, Germany) Glycine, formic acid (Sigma Aldrich, Taufkirchen, Germany) Ammonium hydroxide (Fisher Scientific, Schwerte, Germany) VI Materials and instrumentation: Moderate cation exchanger (MCX), OASIS, 150 mg, 6 mL (Waters, Eschborn, Germany) Freestyle SPE unit (LCTech GmbH, Obertaufkirchen, Germany) Chemicals: Methanol (Biosolve, Valkenswaard, Netherlands) Hydrochloric acid (Chemsolute, Th. Geyer, Berlin, Germany) Glycine, formic acid (Sigma Aldrich, Taufkirchen, Germany) Ammonium hydroxide (Fisher Scientific, Schwerte, Germany) VII Materials and instrumentation: Hydroxylated polystyrene divenylbenzene (ENV+), Isolute, 150 mg, 6 mL (Biotage, Uppsala, Sweden) Freestyle SPE unit (LCTech GmbH, Obertaufkirchen, Germany) Chemicals: Methanol (Biosolve, Valkenswaard, Netherlands) Disodium hydrogen phosphate, potassium dihydrogen phosphate (abcr GmbH, Karlsruhe, Germany) VIII Materials and instrumentation: Graphitized carbon black (ENVI-Carb), Supelclean, 150 mg, 6 mL (Sigma Aldrich, Steinheim, Germany) Freestyle SPE unit (LCTech GmbH, Obertaufkirchen, Germany) Chemicals: Methanol (Biosolve, Valkenswaard, Netherlands) Dichloromethane (Fisher Scientific GmbH, Schwerte, Germany) Glycine, formic acid, sodium hydroxide (Sigma Aldrich, Taufkirchen, Germany) S14 Table S4. Chemicals and instrumentation for the instrumental methods Chromatography AD. Method Material A Instrumentation: HPLC: Varian 212LC Column: Thermo Acclaim Trinity P1 2.1x50mm, 3 um Mass Spectrometer: Varian 320 MS Software: MS Workstation (Varian) Chemicals: Acetonitrile (Merck, Darmstadt, Germany) Ammonia, Acetic acid (Sigma Aldrich, St. Louis, United States of America) B Instrumentation: UHPLC: Nexera X2 (Shimadzu) Column: Waters Acquity BEH Amide 2.1x100mm, 1.7 um Mass Spectrometer: Qtrap 5500 (AB Sciex) Software: Analyst 1.6.2 (Build 8489) (AB Sciex) Chemicals: Acetonitrile (Carl Roth GmbH, Karslruhe, Germany) Ammonium formate (Sigma Aldrich, Schnelldorf, Germany) C1/C2 Instrumentation: UHPLC: Acquity i-Class (Waters) Column: Waters Acquity UPLC HSS T3, 2.1x50mm, 1.8 um (C1) Thermo ScientificTM Hypercarb, 2.1x100mm, 3.0 um (C2) Mass Spectrometer: Xevo TQ-S (Waters) Software: MassLynx (Waters) Chemicals: Acetonitrile, methanol, ammonium formate (Biosolve, Valkenswaard, Netherlands) Diethylamine (Sigma Aldrich, Taufkirchen, Germany) D1/D2 Instrumentation: SFC: Acquity UPC2 (Waters) Column: Waters Acquity UPC2 BEH 3.0x100mm, 1.7 um (D1) Waters Acquity UPC2Torus Diol 3.0x100mm, 1.7 um (D2) Mass Spectrometer: Synapt G2S (Waters) Software: MassLynx (Waters) Chemicals: Carbon dioxide (Air Products, Pennsylvania, USA) Methanol, ammonium hydroxide (Biosolve, Valkenswaard, Netherlands) Formic acid (Sigma Aldrich, Taufkirchen, Germany) S15 A B C1 C2 D1/D2 Figure S2. Gradient profiles of the mobile phases as a function of time for A) MMLC on a Acclaim Trinity P1 column; solvent A: H2O/ACN 98/2, 5 mM NH4COO, pH 5.5; solvent B: H2O/ACN 20/80, 20 mM NH4COO, pH 5.5; B) HILIC on an Acquity BEH Amide column; solvent A: H2O/ACN 95/5, 5 mM NH4COO, pH 3; solvent B: H2O/ACN 5/95, 5 mM NH4COO, pH 3; C1) RPLC on an Acquity UPLC HSS T3; solvent A: H2O, 5 mM COOH; solvent B: MeOH, 5 mM COOH; C2) RPLC on a porous graphitic carbon Hypercarb column; solvent A: H2O, 0.1 % diethylamine; solvent B: ACN, 0.1 % diethylamine; D1/D2) SFC on an A cquity UPC2 BEH and Torus Diol column, respectively; solvent A: CO2; solvent B: MeOH/H2O 95/5, 0.2 % NH4OH; make -up: 0.3 mL min -1 MeOH/H2O 90/10, 0.1 % COOH, pH 6. S16 Table S5A. Chromatography A (MMLC-MS/MS) mass spectrometric parameters (see also footnote). Index ESI mode Q1 m/z Q2 m/z Capillary [V] Collision energy [eV] ID-4 pos 171 112 52 8 ID-4 pos 171 84 52 16 ID-6 pos 185 126 44 8.5 ID-6 pos 185 69 44 21 ID-15 pos 113 84 80 14.5 ID-15 pos 113 70 80 17 ID-17 pos 202 102 64 13 ID-17 pos 202 84 64 23.5 ID-21 pos 134 72 36 9 ID-21 pos 134 57 36 22 ID-23 pos 150 91 48 15.5 ID-23 pos 150 65 48 32 ID-26 pos 127 85 64 13.5 ID-26 pos 127 68 64 21 ID-29 pos 171 126 32 9.5 ID-29 pos 171 69 32 19.5 ID-30 pos 175 143 44 6.5 ID-30 pos 175 115 44 14 ID-32 pos 152 135 52 14.5 ID-32 pos 152 93 52 24.5 ID-35 pos 118 101 60 9.5 ID-35 pos 118 71 60 16 ID-36 pos 132 114 48 10.5 ID-36 pos 132 70 48 14 ID-41 pos 70 43 60 16.5 ID-45 pos 136 91 36 13 ID-45 pos 136 65 36 31 ID-46 pos 114 79 72 11 ID-46 pos 114 96 72 9.5 ID-48 pos 242 143 30 6.5 ID-48 pos 242 113 30 26 ID-52 pos 212 119 64 15.5 ID-52 pos 212 94 64 13.5 ID-53 pos 249 156 72 10 ID-53 pos 249 92 72 19.5 ID-56 pos 122 105 56 12 ID-56 pos 122 77 56 23.5 ID-58 pos 240 133 60 16.5 ID-58 pos 240 108 60 17 ID-60 pos 199 106 76 18.5 ID-60 pos 199 77 76 40 ID-61 pos 228 186 56 15 ID-61 pos 228 96 56 21 ID-62 pos 217 199 88 16 ID-62 pos 217 152 88 35.5 ID-63 pos 327 99 44 20 ID-63 pos 327 251 44 7.5 ID-64 pos 227 184 40 13.5 ID-64 pos 227 107 40 36 ID-9 neg 237 80 -96 -27 ID-9 neg 237 206 -96 -19.5 ID-12 neg 195 80 -56 -25.5 ID-12 neg 195 95 -56 -17 ID-13 neg 162 82 -40 -12.5 ID-13 neg 162 40 -40 -15.5 ID-14 neg 111 80 -52 -20 ID-14 neg 111 96 -52 -19.5 S17 ID-16 neg 206 80 -64 -28 ID-16 neg 206 135 -64 -15 ID-18 neg 107 80 -44 -19 ID-18 neg 107 45 -44 -30 ID-19 neg 155 80 -88 -29.5 ID-19 neg 155 121 -88 -13.5 ID-20 neg 125 97 -52 -13.5 ID-20 neg 125 80 -52 -28.5 ID-22 neg 128 85 -40 -9 ID-22 neg 128 42 -40 -13 ID-24 neg 135 80 -48 -15 ID-24 neg 135 64 -48 -45 ID-25 neg 172 80 -72 -24.5 ID-25 neg 172 108 -72 -17.5 ID-33 neg 149 99 -60 -22 ID-33 neg 149 80 -60 -38.5 ID-34 neg 273 150 -76 -27.5 ID-34 neg 273 209 -76 -21.5 ID-37 neg 83 41 -56 -9 ID-37 neg 83 66 -56 -23 ID-39 neg 171 80 -90 -25.5 ID-39 neg 171 107 -90 -20 ID-40 neg 182 106 -56 -17.5 ID-40 neg 182 62 -56 -16.5 ID-43 neg 207 143 -68 -21 ID-43 neg 207 80 -68 -29 ID-44 neg 185 80 -72 -26 ID-44 neg 185 121 -72 -19 ID-47 neg 361 81 -72 -21 ID-47 neg 361 133 -72 -31.5 ID-47 neg 361 81 -72 -21 ID-47 neg 361 133 -72 -31.5 ID-51 neg 170 79 -128 -25 ID-51 neg 170 62 -128 -29 ID-54 neg 249 205 -84 -21.5 ID-54 neg 249 189 -84 -28.5 ID-57 neg 249 108 -92 -29 ID-57 neg 249 156 -92 -20.5 ESI-MS/MS parameters: ESI needle voltage 4000 V; ionization source temperature 50°C; drying gas temperature (N2) 200 °C; nebulizer gas pressure (N2) 55 psi; drying gas pressure (N2) 18 psi; CID gas pressure (Ar) 2 mTorr; resolution of Q1 and Q2 1 u; centroid mode for acquisition S18 Table S5B. Chromatography B (HILIC-MS/MS) mass spectrometric parameters (see also footnote). Index ESI mode Q1 m/z Q2 m/z DP [V] EP [V] CE [V] CXP [V] ID-2 pos 113 84 140 10 20 10 ID-2 pos 113 70 140 10 23 10 ID-2 pos 113 56 140 10 23 10 ID-3 pos 171 154 76 10 19 14 ID-3 pos 171 81 76 10 31 10 ID-3 pos 171 95 76 10 29 10 ID-4 pos 171 112 61 10 17 10 ID-4 pos 171 55 61 10 37 8 ID-4 pos 171 84 61 10 27 10 ID-5 pos 191 102 66 10 23 12 ID-5 pos 191 72 66 10 23 12 ID-5 pos 191 116 66 10 19 12 ID-6 pos 185 126 46 10 17 12 ID-6 pos 185 69 46 10 33 10 ID-6 pos 185 41 46 10 55 8 ID-7 pos 161 72 66 10 23 10 ID-7 pos 161 116 66 10 17 12 ID-7 pos 161 42 66 10 59 8 ID-9 pos 239 131 141 10 29 10 ID-9 pos 239 70 141 10 41 8 ID-9 pos 239 56 141 10 67 8 ID-11 pos 174 72 66 10 25 14 ID-11 pos 174 129 66 10 17 12 ID-11 pos 174 42 66 10 69 10 ID-15 pos 113 84 236 10 29 10 ID-15 pos 113 56 236 10 31 8 ID-15 pos 113 70 236 10 29 10 ID-17 pos 202 102 61 10 25 10 ID-17 pos 202 62 61 10 25 8 ID-17 pos 202 44 61 10 49 8 ID-21 pos 134 72 61 10 19 10 ID-21 pos 134 42 61 10 49 8 ID-21 pos 134 44 61 10 33 8 ID-23 pos 150 91 61 10 25 8 ID-23 pos 150 65 61 10 51 10 ID-23 pos 150 58 61 10 19 8 ID-26 pos 127 85 101 10 25 10 ID-26 pos 127 43 101 10 45 8 ID-26 pos 127 68 101 10 39 10 ID-28 pos 91 65 171 10 25 10 ID-28 pos 91 39 171 10 43 8 ID-28 pos 91 50 171 10 59 8 ID-29 pos 171 126 71 10 19 12 ID-29 pos 171 69 71 10 31 12 ID-29 pos 171 41 71 10 53 8 ID-32 pos 152 135 96 10 23 12 ID-32 pos 152 77 96 10 55 10 ID-32 pos 152 79 96 10 41 10 ID-35 pos 118 101 81 10 21 12 ID-35 pos 118 71 81 10 27 12 ID-35 pos 118 42 81 10 51 6 ID-36 pos 132 114 86 10 21 12 ID-36 pos 132 70 86 10 27 10 ID-36 pos 132 45 86 10 37 8 ID-37 pos 85 68 76 10 25 10 ID-37 pos 85 43 76 10 21 6 ID-37 pos 85 41 76 10 43 6 ID-41 pos 70 43 120 10 30 7 S19 ID-41 pos 70 28 120 10 45 7 ID-41 pos 70 42 120 10 55 7 ID-42 pos 126 43 106 10 49 8 ID-42 pos 126 85 106 10 21 10 ID-42 pos 126 84 106 10 23 10 ID-45 pos 136 91 131 10 23 12 ID-45 pos 136 65 131 10 45 10 ID-45 pos 136 39 131 10 71 8 ID-46 pos 114 44 121 10 43 8 ID-46 pos 114 79 121 10 21 10 ID-46 pos 114 69 121 10 23 10 ID-48 pos 242 143 66 10 19 14 ID-48 pos 242 85 66 10 41 10 ID-48 pos 242 43 66 10 59 8 ID-49 pos 69 42 120 10 25 7 ID-49 pos 69 29 120 10 45 7 ID-49 pos 69 41 120 10 40 7 ID-50 pos 278 92 106 10 35 10 ID-50 pos 278 65 106 10 65 8 ID-50 pos 278 109 106 10 33 10 ID-52 pos 212 77 96 10 53 10 ID-52 pos 212 119 96 10 29 12 ID-52 pos 212 94 96 10 27 12 ID-53 pos 249 156 151 10 19 14 ID-53 pos 249 92 151 10 33 12 ID-53 pos 249 108 151 10 29 10 ID-56 pos 122 105 56 10 23 12 ID-56 pos 122 77 56 10 37 12 ID-56 pos 122 79 56 10 29 10 ID-58 pos 240 133 81 10 29 12 ID-58 pos 240 108 81 10 29 10 ID-58 pos 240 106 81 10 39 12 ID-59 pos 142 89 100 10 40 10 ID-59 pos 142 125 100 10 30 15 ID-59 pos 142 106 100 10 37 15 ID-60 pos 199 106 131 10 33 12 ID-60 pos 199 77 131 10 67 10 ID-60 pos 199 79 131 10 57 10 ID-61 pos 228 186 71 10 25 16 ID-61 pos 228 68 71 10 53 10 ID-61 pos 228 43 71 10 61 8 ID-63 pos 327 99 100 10 35 12 ID-63 pos 327 81 100 10 85 10 ID-63 pos 327 175 100 10 17 17 ID-64 pos 227 184 81 10 29 16 ID-64 pos 227 212 81 10 27 6 ID-64 pos 227 107 81 10 55 10 ID-9 neg 237 80 -160 -10 -55 -10 ID-9 neg 237 107 -160 -10 -32 -15 ID-9 neg 239 82 -160 -10 -55 -10 ID-10 neg 167 80 -105 -10 -32 -9 ID-10 neg 167 107 -105 -10 -24 -11 ID-10 neg 167 81 -105 -10 -26 -9 ID-12 neg 195 80 -85 -10 -44 -9 ID-12 neg 195 95 -85 -10 -26 -11 ID-12 neg 195 79 -85 -10 -26 -9 ID-13 neg 162 82 -65 -10 -20 -9 ID-13 neg 162 78 -65 -10 -44 -9 ID-13 neg 162 40 -65 -10 -36 -5 ID-14 neg 111 80 -95 -10 -30 -9 ID-14 neg 111 96 -95 -10 -30 -11 ID-14 neg 111 81 -95 -10 -24 -9 ID-16 neg 206 80 -100 -10 -42 -9 S20 ID-16 neg 206 135 -100 -10 -26 -13 ID-16 neg 206 42 -100 -10 -60 -7 ID-18 neg 107 80 -35 -10 -28 -9 ID-18 neg 107 45 -35 -10 -20 -7 ID-18 neg 107 81 -35 -10 -24 -9 ID-19 neg 155 80 -80 -10 -42 -9 ID-19 neg 155 33 -80 -10 -34 -15 ID-19 neg 155 137 -80 -10 -28 -13 ID-20 neg 125 97 -70 -10 -25 -10 ID-20 neg 125 80 -70 -10 -45 -10 ID-20 neg 127 82 -70 -10 -45 -10 ID-22 neg 128 42 -75 -10 -36 -7 ID-22 neg 128 85 -75 -10 -14 -7 ID-22 neg 128 26 -75 -10 -110 -5 ID-24 neg 135 80 -60 -10 -25 -16 ID-24 neg 135 64 -60 -10 -75 -16 ID-24 neg 137 82 -60 -10 -25 -16 ID-25 neg 172 80 -155 -10 -38 -9 ID-25 neg 172 108 -155 -10 -28 -11 ID-25 neg 172 66 -155 -10 -36 -9 ID-33 neg 149 80 -80 -10 -30 -9 ID-33 neg 149 99 -80 -10 -34 -11 ID-33 neg 149 83 -80 -10 -26 -9 ID-34 neg 273 80 -170 -10 -68 -9 ID-34 neg 273 150 -170 -10 -38 -13 ID-34 neg 273 209 -170 -10 -34 -19 ID-38 neg 240 80 -130 -10 -56 -9 ID-38 neg 240 176 -130 -10 -32 -15 ID-38 neg 240 35 -130 -10 -64 -15 ID-39 neg 171 80 -125 -10 -38 -9 ID-39 neg 171 107 -125 -10 -28 -11 ID-39 neg 171 107 -125 -10 -36 -11 ID-40 neg 182 42 -105 -10 -60 -7 ID-40 neg 182 106 -105 -10 -26 -11 ID-40 neg 182 62 -105 -10 -26 -7 ID-43 neg 207 80 -80 -10 -50 -9 ID-43 neg 207 143 -80 -10 -32 -13 ID-43 neg 207 163 -80 -10 -18 -15 ID-44 neg 185 80 -145 -10 -40 -9 ID-44 neg 185 121 -145 -10 -30 -11 ID-44 neg 185 170 -145 -10 -32 -15 ID-47 neg 361 81 -120 -10 -60 -10 ID-47 neg 361 197 -120 -10 -30 -10 ID-47 neg 363 83 -120 -10 -60 -10 ID-54 neg 249 205 -100 -10 -32 -15 ID-54 neg 249 189 -100 -10 -45 -11 ID-54 neg 249 93 -100 -10 -35 -7 ID-57 neg 249 108 -65 -10 -36 -11 ID-57 neg 249 113 -65 -10 -14 -9 ID-57 neg 249 92 -65 -10 -48 -11 ESI-MS/MS parameters: Ion spray voltage: 5500 V (pos), -4500 V (neg); Curtain gas: 45 psi; Temperature: 550 °C; Ion Source gas 1 (nebulizer gas): 55 psi; Ion Source gas 2 (heater gas): 65 psi S21 Table S5C. Chromatography C1/C2 (RPLC-MS/MS) mass spectrometric parameters (see also footnote). Index ESI mode Q1 m/z Q2 m/z Cone [V] Collision energy [eV] ID-2 pos 130 84 2 18 ID-2 pos 130 113 2 12 ID-4 pos 171 84 20 20 ID-4 pos 171 112 20 14 ID-5 pos 191 58 4 24 ID-5 pos 191 102 4 14 ID-6 pos 185 69 2 24 ID-6 pos 185 126 2 12 ID-9 pos 239 88 6 24 ID-9 pos 239 131 6 18 ID-15 pos 113 56 12 20 ID-15 pos 113 84 12 18 ID-17 pos 202 62 16 16 ID-17 pos 202 102 16 16 ID-21 pos 134 72 24 14 ID-21 pos 134 85 24 10 ID-23 pos 150 58 2 14 ID-23 pos 150 91 2 20 ID-26 pos 127 43 2 20 ID-26 pos 127 85 2 16 ID-28 pos 91 47 24 8 ID-28 pos 91 74 24 8 ID-29 pos 171 69 2 22 ID-29 pos 171 126 2 12 ID-30 pos 175 115 2 16 ID-30 pos 175 143 2 8 ID-32 pos 152 93 38 24 ID-32 pos 152 135 38 16 ID-35 pos 118 71 12 16 ID-35 pos 118 101 12 14 ID-36 pos 132 69 40 14 ID-36 pos 132 114 40 14 ID-37 pos 85 41 60 14 ID-37 pos 85 68 60 12 ID-41 pos 70 43 42 14 ID-42 pos 126 43 50 18 ID-42 pos 126 85 50 14 ID-46 pos 114 69 12 16 ID-46 pos 114 79 12 14 ID-48 pos 264 165 44 16 ID-48 pos 264 202 44 12 ID-52 pos 212 77 28 32 ID-52 pos 212 119 28 20 ID-53 pos 249 65 2 40 ID-53 pos 249 156 2 14 ID-55 pos 250 41 18 22 ID-55 pos 250 81 18 22 ID-57 pos 251 93 50 22 ID-57 pos 251 157 50 18 ID-58 pos 240 108 2 20 ID-58 pos 240 133 2 20 ID-60 pos 199 106 54 26 ID-60 pos 199 167 54 4 ID-61 pos 228 96 30 28 ID-61 pos 228 186 30 18 ID-63 pos 327 99 10 26 ID-63 pos 327 175 10 12 S22 ID-1 neg 195 59 2 18 ID-1 neg 195 75 2 20 ID-8 neg 287 143 4 36 ID-8 neg 287 207 4 22 ID-10 neg 167 80 10 22 ID-10 neg 167 137 10 16 ID-12 neg 195 80 2 28 ID-12 neg 195 95 2 20 ID-13 neg 162 78 4 22 ID-13 neg 162 82 4 14 ID-14 neg 111 80 8 16 ID-14 neg 111 96 8 14 ID-16 neg 206 80 48 24 ID-16 neg 206 135 48 18 ID-18 neg 107 43 8 10 ID-18 neg 107 80 8 18 ID-20 neg 125 45 32 16 ID-20 neg 125 97 32 12 ID-22 neg 128 42 10 10 ID-22 neg 128 85 10 14 ID-24 neg 135 80 58 14 ID-24 neg 135 91 58 8 ID-25 neg 172 80 2 22 ID-25 neg 172 108 2 20 ID-27 neg 157 79 2 18 ID-31 neg 173 80 30 24 ID-31 neg 173 109 30 18 ID-33 neg 149 80 4 18 ID-33 neg 149 99 4 18 ID-34 neg 273 150 26 26 ID-34 neg 273 209 26 22 ID-38 neg 240 80 64 26 ID-38 neg 240 176 64 20 ID-39 neg 171 80 2 26 ID-39 neg 171 107 2 20 ID-40 neg 182 42 4 18 ID-40 neg 182 106 4 18 ID-43 neg 207 80 42 30 ID-43 neg 207 143 42 26 ID-44 neg 185 80 6 24 ID-44 neg 185 121 6 22 ID-47 neg 361 81 6 22 ID-47 neg 361 197 6 24 ID-50 neg 276 80 58 40 ID-50 neg 276 156 58 26 ID-51 neg 170 79 14 30 ID-51 neg 170 106 14 16 ID-51 neg 170 79 2 24 ID-51 neg 170 106 2 16 ID-54 neg 249 189 2 32 ID-54 neg 249 205 2 24 ESI-MS/MS parameters: Capillary Voltage 1000 – 1420 V (+/-); Source Temperature 150 °C; Desolvation Temperature 600 °C; Cone Gas Flow 150 L h-1; Collision Gas Flow 0.15 mL min-1; Nebuliser Gas Flow 100 psi S29 Figure S4. Retention factors k’ versus logD for all PMOCs and all chromatographic methods. Method abbreviations: A) MMLC-MS/MS; B) HILIC-MS/MS; C1/C2) RPLC-MS/MS; D1/D2) SFC-HRMS S30 Figure S5. Number of PMOCs that were amenable to the different combinations of enrichment and instrumental methods. S31 Table S9. Enrichment and instrumental methods that were successfully applied for analysis of the different PMOCs (indicated with +). Combinations of enrichment and instrumental methods that were used in the target screening of water samples are listed in the last column with their individual estimated method detection limits (MDLs). Index Applicability of enrichment methods Applicability of instrumental methods Method combinations applied in the target screening of water samples In gray: methods that led to only not-detects In blue: methods that led to at least one detect In parentheses: estimated MDL [ng L-1] I II III IV V VI VII VIII A B C1 C2 D1 D2 ID-1 n.t. n.t. n.t. n.t. - - - - - - + + - - ID-2 n.t. n.t. - + + - + - - + + + - - B-IV (37), C1-V (335) ID-3 n.t. n.t. + - - - - - - + - - + + B-III (0.4) ID-4 - + - - - - - + + + + + - + A-II (0.5), C2-VIII (60), D2-VIII (2000) ID-5 n.t. n.t. + - - - - - - + - - - + B-III (0.06) ID-6 - + - + - - - + + + + + + + A-II (5.5), B-IV (5), C2-VIII (0.5) ID-7 n.t. n.t. - + n.t. n.t. n.t. n.t. - + - - - - B-VI (1250) ID-8 n.t. n.t. n.t. n.t. + - - - - - - + - - C2-V (1.2) ID-9 - - - - - - - + + + + + - + C2-VIII (3), D2-VIII (5) ID-10 n.t. n.t. - - + - - - - + + - - - C1-V (600) ID-11 n.t. n.t. - - - - - - - + - - - + ID-12 + - + - + - - - + + - + + + A-I (189), B-III (3.9), C2-V (600) ID-13 + - - + + - - - + + + + + + A-I (16.8), B-IV (11), C2-V (0.5), D2-V (10) ID-14 + - + - - - - + + + - + + + A-I (367), B-III (375), C2-VIII (39) ID-15 - + - + - + - - + + + + + + A-II (15.4), B-IV (19), C1-VI (600), D1-VI (10), D2-VI (15) ID-16 + - + - + - - - + + + + + + A-I (182), B-III (0.6), C2-V (0.2), D2-V (4) ID-17 - + - + - + + + + + + + + + A-II (46), B-IV (3), C2-VII (42), D1-VII (30) ID-18 - - - + + - - - + + + + + + B-IV (12), C1-V (60) ID-19 - - - - - - - - + + - - - + ID-20 + - + - + - - - + + - + + + A-I (219), B-III (20), C2-V (10), D2-V (40) S32 ID-21 - + - + - + + + + + + + + + A-II (30), B-IV (0.9), C2-VI (600) ID-22 + - - + - - - + + + + - - - A-I (500), B-IV (38), C1-VIII (2.5) ID-23 - + + - - - + + + + + - + + A-II (0.3), B-III (0.75), C1-VIII (0.2), D2-VIII (2.5) ID-24 + - - + + - - - + + + + + + A-I (15.6), B-IV (140), C1-V (10), D2-V (55) ID-25 + - + - + - + - + + - + + + A-I (167), B-III (0.04), C2-V (6), D2-V (140) ID-26 - + - + - + + + + + + - + + A-II (176), B-IV (23), C1-VIII (10), D1-VIII (1.4) ID-27 n.t. n.t. n.t. n.t. - - - - - - + + - - ID-28 n.t. n.t. + - - - - - - + + - - - B-III (0.3) ID-29 - + - + - - - + + + + + + + A-II (3.1), B-IV (1.4), C2-VIII (0.7), D1-VIII (0.6) ID-30 - - n.t. n.t. - - + - + - + - - - C1-VII (100) ID-31 n.t. n.t. n.t. n.t. - - - - - - + + + + C2-V (60) ID-32 - + + - - - - + + + + - + + A-II (11.4), B-III (0.12), C1-VIII (1.2), D1-VIII (0.9) ID-33 + - + - + - - - + + + + + + A-I (55.1), B-III (0.21), C1-V (3), D2-V (0.7) ID-34 + - + - + - + - + + + + + + A-I (4.0), B-III (0.2), C1-V (0.6) ID-35 - - - - - + + - + + + + + + C1-VII (0.1) ID-36 - + - + - + + - + + + - + + A-II (50.9), B-IV (1), C1-VI (600) ID-37 + - - + - - - + + + + - + + A-I (372), B-IV (70), D1-VIII (20) ID-38 n.t. n.t. + - - - + - - + + - + + B-III (0.2), C1-VII (1), D2-VII (8) ID-39 - - + - + - + - + + + + + + B-III (0.6), C2-V (18), D2-V (2.5) ID-40 + - - + + + + - + + + + + + B-IV (50), C1-V (2), D2-V (32) ID-41 - - - + - - - - + + + - - - B-IV (7.6) ID-42 n.t. n.t. - + - + + + - + + - + + B-IV (1.2), C1-VII (0.8), D1-VII (0.6) ID-43 + - + + + - + - + + + + + + A-I (10), B-III (15), C1-VII (10), D2-VII (10) ID-44 + - + - + - + - + + - + + + A-I (26.6), B-III (2.6), C2-V (9), D2-V (3) ID-45 - + + - - - - + + + + - + + A-II (9.6), B-III (0.07) ID-46 - + - + - - + - + + - - + + A-II (14.6), B-IV (1400), C1-VII (600) ID-47 + - - - + - + - + + + + + + A-I (0.6), C1-V (1.5) ID-48 - + - - - - + - + + + - + + A-II (15.7), C1-VII (6) ID-49 n.t. n.t. - - - - - - - + - - - - S33 ID-50 n.t. n.t. + - - - + - - + + - - - B-III (4), C1-VII (0.01) ID-51 + - n.t. n.t. - - + + + - + + + + A-I (105), C2-VIII (1.6), D2-VII (100) ID-52 - + - + + - - + + + + - + + A-II (3.2), B-IV (0.5), C1-VIII (1), D1-VIII (0.6) ID-53 - + n.t. n.t. - - + - + - + - + + A-II (3.9), C1-VII (60) ID-54 + - - + + - + + + + + + + + A-I (20.6), B-IV (2.9), C1-VII (91) ID-55 n.t. n.t. n.t. n.t. - - + - - - - - + - D1-VII (2000) ID-56 - + - - - - - - + + - - - + A-II (85) ID-57 + - + - + - + + + + + - + + A-I (5.7), B-III (20), C1-V (1.7), D2-V (3.2) ID-58 - + + - + + - + + + + - + + A-II (4.3), B-III (0.28), C1-VIII (1.5), D1-VIII (1.5) ID-59 n.t. n.t. - - - - - - - + - - - - ID-60 - - + - - + - - + + + - + + B-III (0.02), C1-VI (60), D1-VI (9) ID-61 - + - + + - - + + + + + + + A-II (7.5), B-IV (0.5), C1-VIII (0.02), D2-VIII (0.7) ID-62 - + n.t. n.t. - - + - + - + - + + A-II (71.1), D1-VII (15), D2-VII () ID-63 - + + - - - + + + + + - + + A-II (72.1), B-III (0.5), C1-VIII (100), D1-VIII (120) ID-64 - - - - - - - - + + - - + + Method abbreviations – Enrichment methods: I) SPE-WAX; II) SPE-WCX; III) SPE-Multilayer; IV) Evaporation; V) SPE-WAX; VI) SPE-MSX; VII) SPE-ENV+; VIII) SPE-EnviCarb Instrumental methods: A) MMLC-MS/MS; B) HILIC-MS/MS; C1/C2) UHPLC-MS/MS; D1/D2) SFC-HRMS + enrichment or chromatographic method applicable - enrichment or chromatographic method not applicable n.t. not tested S34 Figure S6. Frequency of detection (including all methdos) and maximum estimated concentration of the detected PMOCs in the 14 water samples. S35 Table S10. Chromatography method-specific detection frequencies (number of samples) of the detected PMOCs in the 14 water samples. Index Detection frequency Chromatography A (with Enrichment I/II) Detection frequency Chromatography B (with Enrichment III/IV) Detection frequency Chromatography C1/C2 (with Enrichment V-VIII) Detection frequency Chromatography D1/D2 (with Enrichment V-VIII) ID-2 - 2 2 - ID-3 - 4 - - ID-6 2 - 1 - ID-8 - - 3 - ID-9 - - 1 - ID-12 1 1 - - ID-13 12 13 13 12 ID-14 8 2 4 - ID-15 5 4 - - ID-16 13 7 10 5 ID-17 - - 1 1 ID-18 - 3 - - ID-20 - - 1 3 ID-22 - 5 5 - ID-23 6 - 5 1 ID-24 - 1 5 2 ID-25 - 9 6 2 ID-26 3 7 8 14 ID-28 - 1 - - ID-29 1 - 3 1 ID-32 6 10 8 8 ID-33 5 8 10 13 ID-34 - - 1 - ID-37 - 6 - 8 ID-38 - 1 1 1 ID-39 - 4 10 14 ID-40 2 1 3 3 ID-41 - 2 - - ID-42 - - 6 7 ID-43 3 - 1 4 ID-44 3 10 13 13 ID-45 6 5 - - ID-46 9 - 1 - ID-47 - - 4 - ID-50 - - 2 - ID-51 - - 12 1 ID-52 14 - 8 7 ID-54 - 4 - - ID-57 3 - 2 4 ID-58 4 - 14 11 ID-60 - - - 2 ID-61 - 5 10 1 ID-63 7 10 4 5