Dioxin-like POPs in national samples from global monitoring plan projects (2017-2019).

The global monitoring plan (GMP) established under the Stockholm Convention on Persistent Organic Pollutants (POPs) had defined ambient air, human milk or blood, and water as core matrices to be analyzed and assessed for spatial and temporal distribution. Within projects coordinated by the United Nations Environment Programme (UNEP), developing countries were offered to have other matrices analyzed for dioxin-like POPs (dl-POPs) in experienced laboratories. Subsequently, 185 samples from 27 countries located in Africa, Asia, and Latin America were collected during 2018-2019 and analyzed for polychlorinated dibenzodioxins (PCDD), dibenzofurans (PCDF), and biphenyls (PCB). Using the WHO2005 toxic equivalency approach (TEQ), the amounts of dl-POPs found were low (<1 pg TEQ/g); however, singular samples had higher values; e.g., egg from Morocco, fish from Argentina or Tunisia; soil and sediment samples. Results showed that the matrix, abiotic or biota, had more impact on the TEQ pattern than the geographic location. Independent of the location and across all samples, dl-PCB in (shell)fish and beef samples had a contribution of 75% to the total TEQ; milk (63%), chicken (52%), and butter (50.2%) more than 50%. Sediment (57% and 32%) and soil (40% and 36%)) samples were dominated by PCDD and PCDF, respectively; therein, dl-PCB had shares of 11% and 24%. Egg samples (N = 27) did not follow the general biota pattern and had 21% of the TEQ from the PCDD, 45% from PCDF, and 34% from dl-PCB; thus, indicating that abiotic matrices such as soil or other material may have an impact.

Tissue concentrations of per- and polyfluoroalkyl substances (PFAS) in German freshwater fish: Derivation of fillet-to-whole fish conversion factors and assessment of potential risks.

The European Water Framework Directive requires monitoring of bioaccumulative contaminants in fish to assess risks to human health by fish consumption and wildlife by secondary poisoning of predators. The list of priority substances for which environmental quality standards (EQSs) have been derived covers also perfluorooctane sulfonic acid (PFOS). No EQSs have yet been set for other per- and polyfluoroalkyl substances (PFAS) that are frequently detected in fish and of which some have a non-negligible risk potential compared to PFOS. As a case study, burdens for a set of PFAS were investigated for different fish species from five German freshwater sites and a Baltic Sea lagoon. PFAS concentrations were determined for composite samples of both, fillet and whole fish. On average, sum concentrations of C9-C14 perfluoroalkyl carboxylic acids, which will be banned in the European Union in 2023, reached 87% and 82% of the PFOS burdens in fillet and whole fish, respectively. The potential risk of several PFAS other than PFOS was assessed using a previously suggested relative potency factor approach, which is also applied for a proposed EQS revision. Only five of 36 fillet samples (mostly perch) exceeded the current EQS for PFOS alone. By contrast, all fillet samples exceeded the newly proposed draft EQS, which considers potential effects of further PFAS but also a lower tolerable intake value. Additionally, the dataset was used to derive fillet-to-whole fish conversion factors, which can be applied to assess human health risks by consumption of fillet if only whole fish concentrations are available.

Long-term trends of airborne halogenated flame retardants (HFRs) by means of tree leaf and shoot analyses.

The historical air pollution with halogenated flame retardants (HFRs) in Germany was assessed by investigating tree leaf and shoot samples which have been archived in the German environmental specimen bank. Samples covered the period from 1985 to 2016. 43 HFRs comprising polybrominated diphenyl ethers as well as emerging brominated and chlorinated compounds such as Dechlorane Plus, DBDPE, or DPTE, were analysed in 115 samples from ten sub sites originating from six areas characterised by different land uses, including urban as well as a background site. HFRs were observed in each sample showing the widespread distribution of HFRs in Germany in tree leaves and shoots as bioindicators of past and present atmospheric pollution. Analytes observed at elevated concentrations were BDE 209, DBDPE and DPTE. Observed HFR-levels differed between analytes as well as sampling locations, particularly prior to the year 2000. They were typically highest at conurbation areas. Concentrations at the background site often belonged to the lowest ones observed, however, lowest values were not exclusively found there. The quantification frequencies appeared to decrease from the past to most recent samples. With few exceptions, atmospheric pollution of both, legacy and emerging HFRs, decreased significantly.

Organohalogen compounds of emerging concern in Baltic Sea biota: Levels, biomagnification potential and comparisons with legacy contaminants.

While new chemicals have replaced major toxic legacy contaminants such as polychlorinated biphenyls (PCBs) and dichlorodiphenyltrichloroethane (DDT), knowledge of their current levels and biomagnification potential in Baltic Sea biota is lacking. Therefore, a suite of chemicals of emerging concern, including organophosphate esters (OPEs), short-chain, medium-chain and long-chain chlorinated paraffins (SCCPs, MCCPs, LCCPs), halogenated flame retardants (HFRs), and per- and polyfluoroalkyl substances (PFAS), were analysed in blue mussel (Mytilus edulis), viviparous eelpout (Zoarces viviparus), Atlantic herring (Clupea harengus), grey seal (Halichoerus grypus), harbor seal (Phoca vitulina), harbor porpoise (Phocoena phocoena), common eider (Somateria mollissima), common guillemot (Uria aalge) and white-tailed eagle (Haliaeetus albicilla) from the Baltic Proper, sampled between 2006 and 2016. Results were benchmarked with existing data for legacy contaminants. The mean concentrations for ΣOPEs ranged from 57 to 550 ng g-1 lipid weight (lw), for ΣCPs from 110 to 640 ng g-1 lw for ΣHFRs from 0.42 to 80 ng g-1 lw, and for ΣPFAS from 1.1 to 450 ng g-1 wet weight. Perfluoro-4-ethylcyclohexanesulfonate (PFECHS) was detected in most species. Levels of OPEs, CPs and HFRs were generally similar or higher than those of polybrominated diphenyl ethers (PBDEs) and/or hexabromocyclododecane (HBCDD). OPE, CP and HFR concentrations were also similar to PCBs and DDTs in blue mussel, viviparous eelpout and Atlantic herring. In marine mammals and birds, PCB and DDT concentrations remained orders of magnitude higher than those of OPEs, CPs, HFRs and PFAS. Predator-prey ratios for individual OPEs (0.28-3.9) and CPs (0.40-5.0) were similar or somewhat lower than those seen for BDE-47 (5.0-29) and HBCDD (2.4-13). Ratios for individual HFRs (0.010-37) and PFAS (0.15-47) were, however, of the same order of magnitude as seen for p,p'-DDE (4.7-66) and CB-153 (31-190), indicating biomagnification potential for many of the emerging contaminants. Lack of toxicity data, including for complex mixtures, makes it difficult to assess the risks emerging contaminants pose. Their occurence and biomagnification potential should trigger risk management measures, particularly for MCCPs, HFRs and PFAS.

Recent findings of halogenated flame retardants (HFR) in the German and Polar environment.

To get an overview about distribution, levels and temporal trends of polybrominated diphenyl ethers (PBDE) and halogenated flame retardants (HFR) of emerging concern, different types of environmental samples archived in the German Environment Specimen Bank as well as fish filet samples from the Arctic (n = 13) and Antarctica (n = 5) were analysed for 43 substances (24 PBDE, 19 HFR) using a multi-column clean-up and GC-API-MS/MS or GC-MS. Sample types were herring gull egg (n = 3), blue mussel (n = 3) and eelpout filet (n = 3) from the German North- and Baltic Sea, bream filet (n = 7), zebra mussel (n = 6) and suspended particulate matter (SPM, n = 7) from German freshwater ecosystems as well as tree leaves (n = 9)/shoots (n = 10), soil (n = 4), earthworm (n = 4) and deer liver (n = 7) as representatives of German terrestrial ecosystems. PBDE and emerging HFR were present in each investigated matrices from Germany and Polar regions showing their widespread distribution. The presence in Arctic and Antarctic fish samples confirms their long-range transport potential. Average concentrations of total emerging HFR were highest in SPM (26 ng g-1 dry weight (dw)), zebra mussel (10 ng g-1 dw) and herring gull egg (2.6 ng g-1 dw). Lowest levels were measured in fish filet samples from Antarctica (0.02 ng g-1 dw). Average total PBDE concentrations were highest in bream filet (154 ng g-1), herring gull egg (61 ng g-1 dw), SPM (21 ng g-1 dw), and zebra mussel 18 (ng g-1) and lowest in deer liver (0.04 ng g-1 dw). The patterns of non-fauna terrestrial samples (leaves, shoots, soil) as well as SPM were dominated by DBDPE and BDE209. Elevated proportions of DPTE and in most cases the absence of DBDPE characterized all fauna samples with the exception of Polar samples. Overall, emerging HFR appeared to be less bioaccumulative than PBDE. Temporal trends were generally decreasing with few exceptions such as DBDPE.

Temporal change of the accumulation of persistent organic pollutants (POPs) and polycyclic aromatic hydrocarbons (PAHs) in lichens in Switzerland between 1995 and 2014.

The aim of this study was to assess the temporal change of atmospheric deposition patterns of persistent organic pollutants (POPs) and polycyclic aromatic hydrocarbons (PAHs) in Switzerland between 1995 and 2014 by a passive biomonitoring with lichens. Lichen tissues sampled at 16 representative sites in the same season of 1995 and 2014 were analyzed for a total of 94 individual and 27 sum parameters of POPs and PAHs by means of gas chromatography-mass spectrometry (GC/MS). The comparative analyses showed a decrease of 40 to 80% (medians) for most of the POPs and PAHs concentration in lichens at all site categories. Reduction in tissue concentration of the polychlorinated dibenzo-p-dioxins/furans (PCDD/PCDFs), such as the highly toxic 2,3,7,8-TetraCDD and the TEQ according to WHO (2005) were 66% and 73%, respectively. For the dioxin- and non-dioxin-like PCBs, a decrease of 67% and 58% was found. The average decrease of 30 organochlorine pesticides and insecticides (OCPs) was 65%, with a 94% decrease for lindane. For the 27 PAHs and for benzo(a)pyrene, an average decrease of 58% and 59% was found. Polybrominated diphenyl ethers (PBDE) showed reduced concentrations in lichens at rural and agglomeration sites, but an increase of contamination was observed at industrial and road traffic sites. The direct comparison of changes of POPs and PAHs concentrations in lichens and of emissions between 1995 and 2014 revealed consistent results. The results of this study highlight for the first time in biota the positive effect of emission regulation of POPs in Switzerland.

Assessment of seafood contamination under the marine strategy framework directive: contributions of the German environmental specimen bank.

Descriptor 9 (D9) of the European Union Marine Strategy Framework Directive refers to the compliance of contaminant levels in fish and other seafood of a defined marine region or subregion with human health threshold values. This requires georeferenced samples that are often difficult to obtain when relying on commercial fisheries or programs designed for monitoring human exposure. The present study examines whether georeferenced samples of blue mussel (Mytilus edulis) and eelpout (Zoarces viviparus) fillet of the German environmental specimen bank (ESB) can be used in this context. The suitability of the ESB samples, procedures, and analytical methods is evaluated with respect to D9 requirements. Based on ESB data for the D9 relevant contaminants Pb, Cd, Hg, ∑4 PAHs, PCDD/Fs, dioxin-like (dl)-PCBs, and indicator non-dl-PCBs and the potentially relevant substances TBT, PFOS, PBDE, and HBCDD, the Good Environmental Status for D9 is assessed at the ESB sites in the North and Baltic Seas. The overall evaluation indicates that ESB samples are suitable for D9 assessment with the limitation that only coastal areas of the North and Baltic Seas are covered. Over a period of up to 30 years, concentrations of the D9 relevant contaminants were well below the maximum levels allowed for human consumption.

Halogenated flame retardants in tree samples applied as bioindicators for atmospheric pollution.

Coniferous shoots and deciduous tree leaf samples from 10 sites in Germany were taken in 2015 or 2016 within the German Environmental Specimen Bank sampling program and analysed for 24 polybrominated biphenyl ethers (PBDEs) and 19 additional halogenated flame retardants (HFRs). At one site, additional historic samples dating back till 2003 were also investigated. Samples were Soxhlet-extracted, cleaned-up by a non-destructive multi-step procedure involving gel permeation chromatography, and detected by GC-API-MS/MS as well as GC-MS. Besides PBDEs as classical HFRs, emerging HFRs such as Dechlorane Plus, DPTE, DBDPE, or ATE were region-wide observed demonstrating their widespread occurrence in the atmosphere. Highest concentrations in recent samples were found for DBDPE (<230-2760 pg g-1 dry weight (dw)) followed by DPTE (91-1540 pg g-1 dw), BDE209 (<156-461 pg g-1 dw), and BDE47 (<27-505 pg g-1 dw) or DP (31-122 pg g-1 dw). The overall uniform and widespread distribution as well as similar HFR levels and composition profiles observed in recent conifer shoots and corresponding deciduous tree leaves from the same area indicate a prolonged medium to long-range transport as sources. Furthermore, it is demonstrated that both tree types are generally suitable bioindicators for atmospheric pollution with HFRs, although accumulation may vary depending on HFR properties and accumulation period. The historic samples showed decreasing PBDE levels whereas no clear trend could be observed for other investigated HFRs at this site.

Biota monitoring under the Water Framework Directive: On tissue choice and fish species selection.

The study addresses the topic of suitable matrices for chemical analysis in fish monitoring and discusses the effects of data normalization in the context of the European Water Framework Directive (WFD). Differences between species are considered by comparing three frequently monitored species of different trophic levels, i.e., chub (Squalius cephalus, n = 28), (bream, Abramis brama, n = 11), and perch (Perca fluviatilis, n = 19) sampled in the German Danube. The WFD priority substances dioxins, furans and dioxin-like polychlorinated biphenyls (PCDD/F + dl-PCB), polybrominated diphenyl ethers (PBDE), α-hexabromocyclododecane (α-HBCDD), hexachlorobenzene (HCB), mercury (Hg), and perfluorooctane sulfonic acid (PFOS) as well as non-dioxin-like (ndl)-PCB were analyzed separately in fillet and carcass and whole body concentrations were calculated. Hg was analyzed in individual fish fillets and carcasses, all other substances were determined in pool samples, which were compiled on the basis of fish size (3 chub pools, 1 bream pool, 2 perch pools). The data were normalized to 5% lipid weight (or 26% dry mass in the case of Hg and PFOS) for comparison between matrices and species. Hg concentrations were generally higher in fillet than in whole fish (mean whole fish-to-fillet ratio: 0.7) whereas all other substances were mostly higher in whole fish. In the case of lipophilic substances these differences leveled after lipid normalization. Significant correlations (p ≤ .05) were detected between Hg and fish weight and age. Hg concentrations varied least among younger fish. PCDD/F, dl-PCB, ndl-PCB, PBDE, α-HBCDD and HCB correlated significantly (p ≤ .05) with lipid concentrations. Fillet-to-whole fish conversion equations and/or conversion factors were derived for all substances except α-HCBDD. Although more data also for individual fish would be desirable the results are nevertheless a step on the way to translate fillet concentrations of priority substances to whole fish concentrations.

Determination of halogenated flame retardants by GC-API-MS/MS and GC-EI-MS: a multi-compound multi-matrix method.

The extensive application of halogenated flame retardants has led to their widespread distribution in the environment. Recently, concerns emerged regarding their potential persistence, (bio)accumulation, and/or toxicity. Particularly halogenated flame retardants based on norbornene structures, like Dechlorane Plus as well as other brominated PBDE replacements, generically called emerging, novel, or alternative flame retardants, are in the focus of interest. A comprehensive analytical method for the determination of 21 halogenated flame retardants (HFRs) of different substance classes (dechloranes, brominated aromates, brominated ethers, cyclic BFR) in a broad variety of matrices (tree leaves, fish fillet, birds eggs, suspended particles) was developed in order to assess their environmental levels as well as temporal trends, especially for the use within environmental specimen banks (ESBs). In addition to the alternative HFRs, a set of 24 PBDEs were measured in the same samples, however using GC-EI-MS for detection. Samples were extracted using accelerated solvent extraction (ASE) with dichloromethane:hexane (exception: soxhlet extraction for suspended particles) followed by a multi column clean-up. Quantification was performed by API-GC-MS/MS as a modern, gentle, and sensitive technique for simultaneous detection of compounds throughout a wide range of masses and fragmentation characteristics (exception: PBDE detection using GC-EI-MS). With the exception of BDE 209, instrumental precisions of target compounds ranged from 1% to 16 % (at levels of 2 pg injection-1 for HFR, 20 pg injection-1 for DBDPE, 7-36 pg injection-1 for PBDEs). Interday precisions of the entire analytical method including extraction and clean-up were mostly below 25% for all validation matrices at spiked levels of 100 pg sample-1 for HFR (DBDPE: 1000 pg sample-1) and 1200-6000 pg sample-1 for PBDEs. The majority of analytes were investigated with expanded measurement uncertainties of less than 50%. Graphical abstract A new approach to HFR analysis in multiple environmental matrices.

Current levels and trends of selected EU Water Framework Directive priority substances in freshwater fish from the German environmental specimen bank.

Under the German environmental specimen bank programme bream (Abramis brama) were sampled in six German rivers and analysed for the priority hazardous substances dicofol, hexabromocyclododecane (HBCDD), hexachlorobenzene (HCB), hexachlorobutadiene (HCBD), heptachlor + heptachlor epoxide (HC + HCE), polybrominated diphenylethers (PBDEs), polychlorinated dibenzo-p-dioxins and -furans and dioxin-like polychlorinated biphenyls (PCDD/Fs + dl-PCBs), and perfluorooctane sulfonic acid (PFOS). The aim was to assess compliance with the EU Water Framework Directive environmental quality standards for biota (EQSBiota) for the year 2013, and to analyse temporal trends for those substances that are of special concern. General compliance was observed for dicofol, HBCDD and HCBD whereas PBDEs exceeded the EQSBiota at all sites. For all other substances compliance in 2013 varied between locations. No assessment was possible for HC + HCE at some sites where the analytical sensitivity was not sufficient to cover the EQSBiota. Trend analysis showed decreasing linear trends for HCB and PFOS at most sampling sites between 1995 and 2014 indicating that the emission reduction measures are effective. Mostly decreasing trends or constant levels were also observed for PCDD/Fs and dl-PCBs. In contrast, increasing trends were detected for PBDEs and HBCDD which were especially pronounced at one Saar site located downstream of the industries and conurbation of Saarbrücken and Völklingen. This finding points to new sources of emissions which should be followed in the coming years.

Role of dietary patterns for dioxin and PCB exposure.

Dietary patterns were related to intake and blood concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/PCDFs), dioxin-like polychlorinated biphenyls (dl-PCBs) and selected non-dioxin-like-PCBs (ndl-PCBs). Intake calculations were based on an extensive food frequency questionnaire and a congener-specific database on concentrations in Norwegian foods. The study (2003) applied a two-step inclusion strategy recruiting representative (n=73) and high consumers (n=111) of seafood and game. Estimated median intakes of sum PCDD/PCDFs and dl-PCBs of the representative and high consumers were 0.78 and 1.25 pg toxic equivalents (TEQ)/kg bw/day, respectively. Estimated median intakes of ndl-PCBs (sum chlorinated biphenyl (CB)-28, 52, 101, 138, 153, 180) were 4.26 and 6.40 ng/kg bw/day. The median blood concentrations of PCDD/PCDFs/dl-PCBs were 28.7 and 35.1 pg TEQ/g lipid, and ndl-PCBs (sum of CB-101, 138, 153 and 180) 252 and 299 ng/g lipid. The Spearman correlations between dietary intake and serum concentration were r=0.34 (p=0.017) for dl-compounds and r=0.37 (p<0.001) for ndl-PCBs. Oily fish was the major source of dl-compounds and ndl-PCBs in high and representative consumers. Four dietary patterns were identified by principal component analysis. Two were related to high intakes, one dominated by oily fish ((Omega-3)), the other by fish liver and seagull eggs ("northern coastal"). Only the latter was closely associated with high blood concentrations of dioxins and PCBs.

Bioaccumulation of polybrominated diphenyl ethers and hexabromocyclododecane in the northwest Atlantic marine food web.

Seven species of teleost fishes comprising major prey of northwest Atlantic harbor seals were analyzed for polybrominated diphenyl ethers (PBDEs). PBDE concentrations in whole fish samples (n=87) were compared with those measured previously in harbor seal blubber to evaluate the transfer of PBDEs from prey to predator. Hexabromocyclododecane (HBCD) concentrations were measured in three fish species to provide an initial estimation of HBCD contamination in this ecosystem. HBCD was detected in 87% of the fish samples at concentrations ranging from 2.4 to 38.1 ng/g, lw (overall mean 17.2+/-10.2 ng/g, lw). SigmaPBDE concentrations in fish ranged from 17.9 to 94 ng/g, lw (overall mean 62+/-34 ng/g, lw). SigmaPBDE concentrations in the harbor seals were two orders of magnitude higher than levels in the fish. Biomagnification factors (BMFs) from fish to seals averaged from 17 to 76, indicating that tetra- to hexa-BDEs are highly biomagnified in this marine food web. BDE-47 was the dominant congener in all samples, suggesting exposure to the penta-BDE mixture. The presence of higher brominated congeners including BDE-209 at measurable levels in fish and seal tissue, along with the very high biomagnification of BDE-153, as well as -155, and -154, suggests recent exposure to the octa- and deca-BDE formulations in this US coastal marine food web, as well as the additional contribution of BDE-209 debromination in fish to the loading of persistent PBDEs in the seals. This is the first study to report the occurrence of BDE-209 and other higher BDEs in commercially important marine fishes from the northwest Atlantic.