Polybrominated diphenyl ethers (PBDEs) containing two to 10 bromines are ubiquitous in the Arctic, in both abiotic and biotic samples. Hexabromocyclododecane (HBCD) is also ubiquitous in the Arctic, ...with the γ-HBCD isomer predominating in air, the α-HBCD isomer predominating in biota and similar concentrations of α-, β- and γ-HBCD found in marine sediments. Other brominated flame retardants (BFRs) found in some Arctic samples are polybrominated biphenyls (PBBs), tetrabromobisphenol A (TBBPA), 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE), hexabromobenzene (HxBBz), pentabromoethylbenzene (PBEB), pentabromotoluene (PBT), and 1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane (TBECH). Temporal trends of tetra- to heptaBDEs and HBCD show increasing concentrations or a tendency to levelling off depending on the matrix (air, sediment, biota) and location, but no uniform picture for the Arctic emerges. BDE-209 concentrations are increasing in air. PBDEs and HBCD spatial trends in seabirds and marine mammals are similar to those seen previously for polychlorinated biphenyls (PCBs), with highest concentrations found in organisms from East Greenland and Svalbard. These trends indicate western Europe and eastern North America as important source regions of these compounds via long range atmospheric transport and ocean currents. Latitudinal trends showed lower concentrations and fluxes of PBDEs at higher latitudes. The tetra-hexaBDEs and α-HBCD biomagnify in Arctic food webs. Results for BDE-209 are more conflicting, showing either only low or no biomagnification potential. PBDE and HBCD concentrations are lower in terrestrial organisms and higher in marine top predators such as some killer whale populations in Alaska and glaucous gulls from the Barents Sea area. Higher concentrations are seen near populated areas indicating local sources. Findings of BTBPE, HxBBz, PBEB, PBT and TBECH in seabirds and/or marine mammals indicate that these compounds reach the Arctic, most probably by long range atmospheric transport and accumulate in higher trophic level organisms and that increasing use as PBDE replacements will lead to increasing concentrations.
•The literature has been reviewed regarding potential new contaminants in the Arctic.•For several novel brominated flame retardants long-range transport has been shown.•Dechlorane plus and ...short-chain chlorinated paraffins accumulate in Arctic biota.•Ice cores document increasing levels of some current-use pesticides, e.g. endosulfan.•Long-range transport and bioaccumulation might also occur for octachlorostyrene.
Systematic monitoring of persistent organic pollutants (POPs) in the Arctic has been conducted for several years, in combination with assessments of POP levels in the Arctic, POP exposure and biological effects. Meanwhile, environmental research continues to detect new contaminants some of which could be potential new Arctic pollutants. This study summarizes the empirical evidence that is currently available of those compounds in the Arctic that are not commonly included in chemical monitoring programmes. The study has focused on novel flame retardants, e.g. alternatives to the banned polybrominated diphenyl ethers (PBDEs), current-use pesticides and various other compounds, i.e. synthetic musk compounds, siloxanes, phthalic acid esters and halogenated compounds like hexachlorobutadiene, octachlorostyrene, pentachlorobenzene and polychlorinated naphthalenes. For a number of novel brominated flame retardants, e.g. 2,3-bibromopropyl-2,4,6-tribromophenyl ether (DPTE), bis(2-ethylhexyl)tetrabromophthalate (TBPH), 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (TBB), 1,2-bis(2,4,6-tribromophenoxy)-ethane (BTBPE), decabromodiphenyl ethane (DBDPE), pentabromoethylbenzene (PBEB) and hexabromobenzene (HBBz), transport to the Arctic has been documented, but evidence of bioaccumulation is sparse and ambiguous. For short-chain chlorinated paraffins and dechlorane plus, however, increasing evidence shows both long-range transport and bioaccumulation. Ice cores have documented increasing concentrations of some current-use pesticides, e.g. chlorpyrifos, endosulfan and trifluralin, and bioaccumulation has been observed for pentachloroanisole, chorpyrifos, endosulfan and metoxychlor, however, the question of biomagnification remains unanswered.
Atmospheric concentrations of organochlorine pesticides (OCPs), polybrominated diphenyl ethers (PBDEs) and neutral per- and polyfluoroalkyl substances (PFAS) have been measured at Villum Research ...Station, Station Nord (North Greenland) in the period 2008–2013. Atmospheric concentrations of OCPs at the same site have been previously reported for the years 2008–2010. The detection frequency and the average concentrations of OCPs have not significantly changed since the previous study. PBDE congeners (∑13PBDEs) were measured for the first time in North Greenland at concentrations similar to those observed for other remote sites, confirming that these compounds are ubiquitous in the Northern Hemisphere. The ∑13PBDEs concentration ranged from not detected (n.d.) to 6.26 pg m−3. The BDE congeners found in more than 30% of the samples were BDE-17, BDE-28, BDE-47, BDE-71, BDE-99 and BDE-100. Also for neutral PFAS we present for the first time a multiyear series of measurements for North Greenland. The average sum of the seven measured neutral PFAS (∑7PFAS) ranged from 1.82 to 32.1 pg m−3. The most abundant compound was 8:2 FTOH (44% of ∑7PFAS), followed by 6:2 FTOH and 10:2 FTOH. Perfluoroalkyl sulfonamides (FOSA) and perfluoroalkyl sulfonamidoethanols (FOSE) were also detected but at much lower concentrations than FTOHs.
Temporal trends were investigated for all measured compounds but no significant trend in concentration was observed. Monthly average concentrations for the six years were calculated for each compound and the seasonal variation was investigated. Some OCPs and FTOHs showed seasonal variations, and in most cases a maximum was found during summer.
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•PBDEs and neutral PFASs are reported for the first time in the atmosphere of North Greenland.•Atmospheric concentrations of POPs do not show any trend in the period 2008–2013.•Some compounds showed seasonal variations, and in most cases a maximum was found during summer.•Temperature dependency was observed for a few of the investigated compounds.
Chlorinated pesticides, polybrominated- and polyfluorinated compounds have been measured in the atmosphere of North Greenland in the years 2008–2013.
The Joint Research Centre (JRC) of the European Commission has recently released two new Certified Reference Materials (CRMs) for the analysis of brominated flame retardants (BFRs): the freshwater ...sediment ERM-CC537a and the fish tissue ERM-CE102. The production of these CRMs responds to the need of expanding the offer of quality assurance/quality control tools for the analysis of BFRs in the fields of environmental analysis and food control, especially for compliance purposes. The sediment ERM-CC537a carries certified values for polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCDD) diastereoisomers in the μg/kg range (dry mass), while the fish tissue ERM-CE102 is certified for PBDEs in the ng/kg range (wet weight). ERM-CC537a is the first reference material ever available with certified values for α-, β- and γ-HBCDD. The assignment of the certified values was performed via an intercomparison of expert laboratories. The evaluation of the data confirms the improving trend, observed in recent years, regarding the comparability of PBDE measurement results. The relative standard deviation (RSD) among laboratories is slightly better for the fish material (8–11%) compared to the sediment (9–15%), despite lower mass fractions in the biota matrix. The RSD of HBCDD data (17%) reveals that they are more challenging analytes. The average measurement uncertainty declared by the participants is about 30%, but an in-depth analysis of their performance reveals that it should be feasible to reduce the uncertainty budget.
More than 1000 time-series of persistent organic pollutants (POPs) in Arctic biota from marine and freshwater ecosystems some extending back to the beginning of 1980s were analyzed using a robust ...statistical method. The Arctic area encompassed extended from Alaska, USA in the west to northern Scandinavian in the east, with data gaps for Arctic Russia and Arctic Finland. The aim was to investigate whether temporal trends for different animal groups and matrices were consistent across a larger geographical area. In general, legacy POPs showed decreasing concentrations over the last two to three decades, which were most pronounced for α-HCH and least pronounced for HCB and β-HCH. Few time-series of legacy POPs showed increasing trends and only at sites suspected to be influenced by local source. The brominated flame retardant congener BDE-47 showed a typical trend of increasing concentration up to approximately the mid-2000s followed by a decreasing concentration. A similar trend was found for perfluorooctane sulfonic acid (PFOS). These trends are likely related to the relatively recent introduction of national and international controls of hexa- and hepta-BDE congeners and the voluntary phase-out of PFOS production in the USA in 2000. Hexabromocyclododecane (HBCDD) was the only compound in this study showing a consistent increasing trend. Only 12% of the long-term time-series were able to detect a 5% annual change with a statistical power of 80% at α < 0.05. The remaining 88% of time-series need additional years of data collection before fulfilling these statistical requirements. In the case of the organochlorine long-term time-series, 45% of these would require >20 years monitoring before this requirement would be fulfilled.
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•Temporal trends of POPs in Arctic biota.•Downward trends constitute the majority of statistically significant trends.•“Newer” POPs show a more mixed pattern of trends.•Continuing existing time-series would generally lead to more powerful trend detection.
Polychlorinated biphenyls (PCBs) are banned from production and use in most countries as they are persistent organic pollutants (POPs) of concern for environment and health. Recent research has ...pointed at a new environment issue resulting from the inadvertent formation of PCBs in certain processes, in particular the pigment production. PCB-11 is a major by-product in these processes, but PCB-28, PCB-52, PCB-77 as well as the nonachlorinated PCBs and PCB-209 have been found in pigments and consumer products as well. In addition to environmental emissions via point sources, in particular related to industrial and municipal wastewater, atmospheric transport seems to be important for the global distribution of PCB-11. Thus, PCB-11 has also been detected in the polar regions. Worldwide air concentrations appear relatively uniform, but maxima have been found in urban and industrialised areas. Data on the uptake and accumulation of PCB-11 in the food chain are still inconclusive: Although food web studies do not show biomagnification, PCB-11 has been detected in humans. The human exposure might originate from the direct contact to consumer products as well as from the omnipresence of PCB-11 in the environment.
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•The pigment production has been recognised as a source of PCB-11.•Several other PCB congeners are formed inadvertently, amongst these PCB-77.•Atmospheric transport seems to be an important environmental pathway for PCB-11.•Data on bioaccumulation and biomagnification are sparse and inconclusive.•PCB-11 has been detected in humans.
This paper reviews the existing literature on human exposure to polybrominated diphenyl ethers (PBDEs), with particular focus on external exposure routes (e.g. dust, diet, and air) and the resulting ...internal exposure to PBDEs (e.g. breast milk and blood). Being lipophilic and persistent organic compounds, PBDEs accumulate in lipid-rich tissues. Consequently, food items like fish from high trophic levels or lipid-rich oils have been found to contain relatively high concentrations of PBDEs, thus presenting an important exposure pathway to humans. The presence of PBDEs in various products of everyday use may lead to some additional exposure in the home environment. Dust seem to be an aggregate of the indoor source, and the ingestion of dust conveys the highest intake of BDE-209 of all sources, possibly also of other PBDE congeners. The PBDE exposure through dust is significant for toddlers who ingest more dust than adults. Infants are also exposed to PBDEs via breast milk. Internal human exposure has generally been found to be one order of magnitude larger in North America than in Europe and Asia. These differences cannot solely be explained by the dietary intake as meat products are the only food group where some differences has been observed. However, indoor air and dust concentrations have been found to be approximately one order of magnitude higher in North America than in Europe, possibly a result of different fire safety standards. Within Europe, higher PBDE concentrations in dust were found in the UK than in continental Europe. Recent studies have shown that BDE-209 also accumulates in humans. A shift in congener composition from maternal to umbilical cord blood has been observed in several cases. A shift has also been observed for BDE-209, which is present in larger ratios in umbilical cord blood and in particular in placenta than in maternal blood.
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•The EU Horizon 2020 project HBM4EU targets seven substance groups and two metals.•Best suitable exposure biomarkers, matrices and analytical methods were suggested.•The selection was ...based on generally applicable criteria, e.g. method sensitivity.•Some conflicts were identified between the criteria and common exposure biomarkers.•Stringent quality assurance and control measures should be included and reported.
The major purpose of human biomonitoring is the mapping and assessment of human exposure to chemicals. The European initiative HBM4EU has prioritized seven substance groups and two metals relevant for human exposure: Phthalates and substitutes (1,2-cyclohexane dicarboxylic acid diisononyl ester, DINCH), bisphenols, per- and polyfluoroalkyl substances (PFASs), halogenated and organophosphorous flame retardants (HFRs and OPFRs), polycyclic aromatic hydrocarbons (PAHs), arylamines, cadmium and chromium. As a first step towards comparable European-wide data, the most suitable biomarkers, human matrices and analytical methods for each substance group or metal were selected from the scientific literature, based on a set of selection criteria. The biomarkers included parent compounds of PFASs and HFRs in serum, of bisphenols and arylamines in urine, metabolites of phthalates, DINCH, OPFRs and PAHs in urine as well as metals in blood and urine, with a preference to measure Cr in erythrocytes representing Cr (VI) exposure. High performance liquid chromatography-tandem mass spectrometry (LC-MS/MS) was the method of choice for bisphenols, PFASs, the HFR hexabromocyclododecane (HBCDD), phenolic HFRs as well as the metabolites of phthalates, DINCH, OPFRs and PAHs in urine. Gas chromatographic (GC) methods were selected for the remaining compounds, e.g. GC-low resolution MS with electron capture negative ionization (ECNI) for HFRs. Both GC–MS and LC-MS/MS were suitable for arylamines. New developments towards increased applications of GC–MS/MS may offer alternatives to GC–MS or LC-MS/MS approaches, e.g. for bisphenols. The metals were best determined by inductively coupled plasma (ICP)-MS, with the particular challenge of avoiding interferences in the Cd determination in urine. The evaluation process revealed research needs towards higher sensitivity and non-invasive sampling as well as a need for more stringent quality assurance/quality control applications and assessments.
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•Current-use chemicals detected in Baltic Sea biota cause environmental concern.•Current-use flame retardants exceed concentrations of banned ones in most species.•PCBs and DDT still ...predominate in mammals and birds, but not in fish and mussels.•Indications of biomagnification were found for PFAS and some flame retardants.•Risk management measures needed, particularly for MCCPs, HFRs and PFAS.
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.
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•Key parameters for wristbands as passive samplers were determined.•An approximate field sampling rate for silicone wristbands was determined.•Highly significant correlation between ...air and wristband levels were observed.•Silicone wristbands could clearly rank exposure.•Partitioning coefficients between air and silicone were determined for 9 PCBs.
Polychlorinated biphenyls (PCBs) were used in a number of industrial products from 1950 to 80s, including building materials. As a result, some buildings exhibit high levels of PCBs in the indoor environment. The aim of this study was to test silicone wristbands as a method for estimating personal exposure to PCBs in buildings both in controlled experiments and field settings. In the controlled study, the sampling kinetics of silicone wristbands were investigated in a 31-day uptake study. The field study focused on the application of wristbands as a personal exposure measure. It included 71 persons in a contaminated housing estate and 23 persons in a reference group. The linear uptake of PCBs ranged from 2 to 24 days for PCB-8, 18, 28, 31, 40, 44, 49, 52, 66, 99, and 101 under controlled conditions. A generic sampling rate (Rk) of 2.3 m3 d-1 corresponding to a mass transfer coefficient of 17 m h−1 was found in the controlled kinetic study. Partitioning coefficients were also determined for the nine congeners. In the field study, an apparent generic field sampling rate (Rf) of 2.6 m3 d-1 was found; when adjusted to reported hours exposed, it increased to 3.5 m3 d-1. The wristbands were shown to be a good tool for predicting airborne exposure, as there was a highly significant difference between the exposed and reference group as well as a clear trend when used for ranking of exposure. In correlation analyses, highly significant correlations were observed between air and wristband levels, though adjusting by self-reported exposure time only increased the correlation marginally in the field study. The obtained kinetic data can be used for estimating the magnitude of external exposure. The advantages provided by the wristbands in the form of easy use and handling are significant, though the limitations should also be acknowledged.
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