Emerging Flame Retardants and Legacy POPs in Bream and Other...

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Figure 1: Sampling sites Emerging Flame Retardants and Legacy POPs in Bream and Other Limnic Samples of the German Environmental Specimen Bank Lohmann N 1 , Neugebauer F 1 , Dreyer A 2 , Ruedel H 3 , Teubner D 4 , Koschorreck J 5 1 Eurofins GfA Lab Service GmbH, Hamburg, Germany, [email protected]; 2 Eurofins GfA GmbH, Hamburg, Germany; 3 Fraunhofer Institut fuer Molekularbiologie und Angewandte Oekologie (Fraunhofer IME), Schmallenberg, Germany; 4 Trier University, Biogeography, Trier, Germany; 5 German Federal Environment Agency, Berlin, Germany Introduction In the past, conventional brominated flame retardants (BFRs) such as polybrominated diphenyl ethers (PBDEs) were identified as persistent organic pollutants (POPs) and subsequently regulated. Fire safety regulations became more stringent over the same period and regulated flame retardants were replaced by other compounds, often called novel, alternative or emerging flame retardants (eFRs). Many of these eFRs are highly chlorinated or brominated as well, and their fate and effects in the environment may be similar to those of their regulated counterparts. The German environmental specimen bank (ESB) is one of the largest cryoarchives for environmental samples and covers different ecosystems across Germany 1 . It allows for retrospective analysis of spatial and temporal trends in contaminant monitoring. EFRs were analysed with a recently developed multi-compound method using GC-API-MS/MS in bream muscle, soft body tissue of zebra mussels and suspended material from different sampling sites and years of the German ESB. Results are compared with those ones of legacy persistent organic pollutants like polybrominated diphenyl ethers (PBDEs), hexabromocyclododecane (HBCD) and other Stockholm POPs with regard to spatial and time trends. Materials and methods Samples. Samples of bream (Abramis brama) and zebra mussels (Dreissena polymorpha) were collected annually since the late 1980s by the ESB Project Team, Trier University, Germany, suspended material by Freie Universität Berlin, Germany (2005 to 2015). The sampled material was processed, cryomilled and archived in sub- samples at temperatures below -150°C by the Fraunhofer Institute for Molecular Biology and Applied Ecology (Fraunhofer IME), Department Environmental Specimen Bank, Schmallenberg, Germany. Sampling and processing were performed under well-defined and reproducible conditions according to standard operating procedures 2-4 . Sampling areas (fig. 1) were in the rivers Rhine, Saar, Danube and Elbe with the tributaries Mulde and Saale and Lake Stechlin as well Lake Belau as low anthropogenically influenced area 5 . Analysis of eBFRs and PBDEs. The analytical procedure for the determination of flame retar- dants as well as target analytes is described in detail by Neugebauer et al. 6 . After spiking with nineteen mass-labeled standards, samples were extracted by accelerated solvent extraction or Soxhlet extraction followed by a 3-step cleanup including BioBeads SX-3. Instrumental detection of eBFRs occurred using GC-API-MS/MS as modern and sensitive instrumental technique (eBFRs) resp. GC-MS (PBDEs). Analysis of HBCD. Only fish samples were analysed for HBCD. After addition of the mass-labeled standards, Organohalogen Compounds Vol. 80, 581-584 (2018) 581

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Figure 1: Sampling sites

Emerging Flame Retardants and Legacy POPs in Bream and Other Limnic Samples of the German Environmental Specimen Bank

Lohmann N1, Neugebauer F1, Dreyer A2, Ruedel H3, Teubner D4, Koschorreck J5

1 Eurofins GfA Lab Service GmbH, Hamburg, Germany, [email protected]; 2 Eurofins GfA GmbH, Hamburg, Germany; 3 Fraunhofer Institut fuer Molekularbiologie und Angewandte Oekologie (Fraunhofer IME), Schmallenberg, Germany; 4 Trier University, Biogeography, Trier, Germany; 5 German Federal Environment Agency, Berlin, Germany

Introduction In the past, conventional brominated flame retardants (BFRs) such as polybrominated diphenyl ethers (PBDEs) were identified as persistent organic pollutants (POPs) and subsequently regulated. Fire safety regulations became more stringent over the same period and regulated flame retardants were replaced by other compounds, often called novel, alternative or emerging flame retardants (eFRs). Many of these eFRs are highly chlorinated or brominated as well, and their fate and effects in the environment may be similar to those of their regulated counterparts. The German environmental specimen bank (ESB) is one of the largest cryoarchives for environmental samples and covers different ecosystems across Germany 1. It allows for retrospective analysis of spatial and temporal trends in contaminant monitoring. EFRs were analysed with a recently developed multi-compound method using GC-API-MS/MS in bream muscle, soft body tissue of zebra mussels and suspended material from different sampling sites and years of the German ESB. Results are compared with those ones of legacy persistent organic pollutants like polybrominated diphenyl ethers (PBDEs), hexabromocyclododecane (HBCD) and other Stockholm POPs with regard to spatial and time trends. Materials and methods Samples. Samples of bream (Abramis brama) and zebra mussels (Dreissena polymorpha) were collected annually since the late 1980s by the ESB Project Team, Trier University, Germany, suspended material by Freie Universität Berlin, Germany (2005 to 2015). The sampled material was processed, cryomilled and archived in sub-samples at temperatures below -150°C by the Fraunhofer Institute for Molecular Biology and Applied Ecology (Fraunhofer IME), Department Environmental Specimen Bank, Schmallenberg, Germany. Sampling and processing were performed under well-defined and reproducible conditions according to standard operating procedures 2-4. Sampling areas (fig. 1) were in the rivers Rhine, Saar, Danube and Elbe with the tributaries Mulde and Saale and Lake Stechlin as well Lake Belau as low anthropogenically influenced area 5. Analysis of eBFRs and PBDEs. The analytical procedure for the determination of flame retar-dants as well as target analytes is described in detail by Neugebauer et al. 6. After spiking with nineteen mass-labeled standards, samples were extracted by accelerated solvent extraction or Soxhlet extraction followed by a 3-step cleanup including BioBeads SX-3. Instrumental detection of eBFRs occurred using GC-API-MS/MS as modern and sensitive instrumental technique (eBFRs) resp. GC-MS (PBDEs). Analysis of HBCD. Only fish samples were analysed for HBCD. After addition of the mass-labeled standards,

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the extraction was performed by means of Soxhlet using a mixture of appropriate polar and non-polar solvents for ultratrace-analyses. The extract was further purified with sulphuric acid, followed by alumina clean-up. The measurements were performed using LC/ESI-MS/MS. Determination of hexachlorbenzenze (HCB) and other legacy organochlorine pesticides. The determination of legacy organochlorine pesticides was performed according to an analytical procedure including HRGC/HRMS described before 7. Determination of PCDD/Fs and PCBs. Bream samples were analysed using high resolution gas chromatography and high resolution mass spectrometry (HRGC/HRMS) analogue to a method described before 8,9. TEQ values are calculated by using WHO(2005)-TEFs according to the lowerbound procedure. Determination of perfluorinated alkyl substances. For analysis of bream samples mass-labeled internal standards were added to the samples before the extraction procedure using ultrasonic extraction, followed by a clean-up-procedure involving carbon black. The measurement was performed using liquid chromatography and tandem mass spectrometry (LC/MS-MS). Determination of lipid content. Determination of lipid content was performed as extractable lipids for fish samples (gravimetrically within an analytical procedure for determination of legacy organochlorine pesticides described above) resp. according to SMEDES-method for mussel samples. Data handling. To simplify the presentation of the data, the individual analytes were summarized following the lowerbound procedure in totals according to the following scheme: Abbreviation Sum (lowerbound procedure) of the following parameters Ʃ DP Syn-Dechlorane Plus, anti-Dechlorane Plus, anti-Cl10-Dechlorane Plus, anti-Cl11-Dechlorane Plus,

1,5-Dechlorane Plus Mono Adduct Ʃ Dechloranes (incl. DP) Dechlorane Plus (as Ʃ DP), Dechlorane 602, Dechlorane 603, Dechlorane 604 DBDPE Decabromodiphenylethane Ʃ DPTE 2,3-Dibrompropyl-2,4,6-tribromophenyl ether (DPTE), 2-Bromallyl-2,4,6-tribromophenyl ether

(BATE), 2,4,6-Tribromophenylallyl ether (ATE) Ʃ eBFRs 1,2-Bis(2,4,6-tribromphenoxy)ethane (BTBPE), Bis(2-ethylhexyl)-3,4,6-tribromo phthalate

(BEHTBP), 2-Ethylhexyl-2,3,4,5-tetrabromobenzoate (EHTBB), Hexabromobenzene (HBB), Pentabromotoluene (PBT), Pentabromoethylbenzene (PBEB), 2,4,6-Tribromoanisol (TBA)

Ʃ 6PBDEs BDE-28, BDE-47, BDE-99, BDE-100, BDE-153, BDE-154 BDE-209 BDE-209 Ʃ other BDEs BDE-17, BDE-49, BDE-66, BDE-71, BDE-77, BDE-85, BDE-119, BDE-126, DE-138, BDE-156,

BDE-183, BDE-184, BDE-191, BDE-196, BDE-197, BDE-206, BDE-207 Ʃ HBCD alpha-HBCD, beta-HBCD, gamma-HBCD HCB Hexachlorobenzene Ʃ DDx op-DDT, pp-DDT, pp-DDE, pp-DDD Ʃ HCH alpha-HCH, beta-HCH, gamma-HCH (Lindane) Ʃ HE Heptachlor, cis-Heptachlorepoxide, trans-Heptachloroepoxide Ʃ other OCPs Pentachlorbenzene, Aldrin, Dieldrin, Octachlorostyrene WHO(2005)-PCDD/F-TEQ 17 2,3,7,8-substituted PCDD/Fs WHO(2005)-PCB-TEQ 12 DL-PCBs NDL-PCBs 6 NDL-PCBs PFOS Perfluorooctane sulfonic acid Ʃ PFSA Perfluorobutane sulfonic acid (PFBS), Perfluorohexane sulfonic acid (PFHxS), Perfluorodecane

sulfonic acid (PFDS) PFOA Perfluorooctanoic acid Ʃ PFCA Perfluorohexanoic acid (PFHxA), Perfluoroheptanoic acid (PFHpA), Perfluorononanoic acid (PFNA),

Perfluorodecanoic acid (PFDeA), Perfluorododecanoic acid (PFDoA) Results and discussion: Levels for flame retardants and other POPs vary between sampling sites. Levels of emerging flame retardants were usually (far) lower than levels of PBDEs, organochlorine pesticides (HCB, DDx, HCHs), NDL-PCBs or PFOS in the same sample. Total concentrations of investigated eFRs were lower than total PBDE concentrations and ranged from 2,3 ng/g lw in bream (E5) to about 170 ng/g lw in bream at E4 (being dominated by DBDPE) in 2015. Mussel levels ranged from 5,1 (Sa) to 370 (S2, bream: 6,6) ng/g lw. Time trends are in most cases decreasing with time (see figure 2 as example for one sampling site). PBDE profiles were dominated by the 6 main PBDEs identified as priority substances within the EU Water Framework Directive 10. In contrast to

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PBDEs patterns of emerging flame retardants varied within the species of the sampling site (fig. 3) indicating different behaviors of accumulation of bream resp. zebra mussels.

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Figure 2: Time trends (solid line = significant, dashed line = not significant) for flame retardants and other

POPs in bream at R4 (from left to right, from top to bottom): Ʃ Dechloranes (incl. DP), Ʃ DPTE, Ʃ eBFRs, Ʃ 6PBDEs, HCB, Ʃ DDx, NDL-PCBs

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Figure 3: Pattern of emerging flame retardants in bream muscle tissue (BR), soft body tissue of zebra mussels (ZM) and suspended material (SPM) at different sampling sites (D3, E4, E5, LB, R4, S2, Sa) in 2015

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Despite the fact that the preconditions for calculating accumulation factors (especially: both predator and prey may not have come to equilibrium with their pollutant source) were not given in this study, indicative Biomagnification Factors (BMF = cpredator/cprey) resp. indicative Biota to Suspended Solids Accumulation Factors (BSSAF = cbiota/csuspended material) were calculated on basis of lipid resp. TOC-adjusted concentrations (fig. 4): Despite exact numerical figures should not be retrieved from this study, the data is indicating that BMF or BSSAF might be lower for eFR than for legacy POPs like PBDEs or organochlorine pesticides.

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retardants and other POPs (mean of all sampling years and sampling sites ± standard deviation) (Please do not retrieve exact numerical figures, only comparison between parameter groups might work)

Acknowledgements: We thank our laboratory staff for their dedicated work on the project, particularly Judith Söhler, Steffi Rolle and Bärbel Bender. The German Environment Agency is acknowledged for funding (AZ 93 04/25). References: 1. German Federal Environment Agency (Umweltbundesamt): German Environmental Specimen Bank – Concept, Berlin, October 2008. (http://www.umweltprobenbank.de/de/documents/11426 accessed 15 May 2018) 2. Klein et al: Guideline for Sampling and Sample Treatment – Bream (Abramis brama), Trier, 2012. (http://www.umweltprobenbank.de/de/documents/publications/11544 accessed 15 May 2018) 3. Ricking et al: Richtlinie zur Probenahme und Probenbearbeitung – Schwebstoff, Berlin, 2017. (https://www.umweltprobenbank.de/en/documents/publications/25629 accessed 15 May 2018) 4. Rüdel et al: Guidelines for Sampling and Sample Processing: Pulverisation and Homogenisation of Environmental Samples by Cryomilling, 2009. (https://www.umweltprobenbank.de/en/documents/publications/11939 accessed 15 May 2018) 5. Wenzel et al. (2004) Environmental Science & Technology. 38: 1654-1661. 6. Neugebauer F, Dreyer A, Lohmann N, et al. (2018): Analytical and Bioanalytical Chemistry. 410: 1375–1387 7. Lohmann et al (2014): Organohalogen Compounds. 76, 1545-1548 8. Schröter-Kermani et al. (2004): Organohalogen Compounds. 66, 1756-1759 9. Neugebauer et al. (2011): Organohalogen Compounds. 73, 1340-1343 10. Directive 2013/39/EU amending Directives 2000/60/EC and 2008/105/EC (OJ L 226, 24.08.2013, p. 1)

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