Characterizing the Organohalogen Iceberg: Extractable, Multihalogen Mass Balance Determination in Municipal Wastewater Treatment Plant Sludge.

The large number and diversity of organohalogen compounds (OHCs) occurring in the environment poses a grand challenge to analytical chemists. Since no single targeted method can identify and quantify all OHCs, the size of the OHC "iceberg" may be underestimated. We sought to address this problem in municipal wastewater treatment plant (WWTP) sludge by quantifying the unidentified fraction of the OHC iceberg using targeted analyses of major OHCs together with measurements of total and extractable (organo)halogen (TX and EOX, respectively; where X = F, Cl, or Br). In addition to extensive method validation via spike/recovery and combustion efficiency experiments, TX and/or EOX were determined in reference materials (BCR-461 and NIST SRMs 2585 and 2781) for the first time. Application of the method to WWTP sludge revealed that chlorinated paraffins (CPs) accounted for most (∼92%) of the EOCl, while brominated flame retardants and per- and polyfluoroalkyl substances (PFAS) accounted for only 54% of the EOBr and 2% of the EOF, respectively. Moreover, unidentified EOF in nonpolar CP extracts points to the existence of organofluorine(s) with physical-chemical properties unlike those of target PFAS. This study represents the first multihalogen mass balance in WWTP sludge and offers a novel approach to prioritization of sample extracts for follow-up investigation.

Organohalogenated flame retardants and organophosphate esters from home and preschool dust in Sweden: Pollution characteristics, indoor sources and intake assessment.

This study analysed settled dust samples in Sweden to assess children's combined exposure to 39 organohalogenated flame retardants (HFRs) and 11 organophosphate esters (OPEs) from homes and preschools. >94 % of the targeted compounds were present in dust, indicating widespread use of HFRs and OPEs in Swedish homes and preschools. Dust ingestion was the primary exposure pathway for most analytes, except BDE-209 and DBDPE, where dermal contact was predominant. Children's estimated intakes of ∑emerging HFRs and ∑legacy HFRs from homes were 1-4 times higher than from preschools, highlighting higher exposure risk for HFRs in homes compared to preschools. In a worst-case scenario, intakes of tris(2-butoxyethyl) phosphate (TBOEP) were 6 and 94 times lower than the reference dose for children in Sweden, indicating a potential concern if exposure from other routes like inhalation and diet is as high. The study also found significant positive correlations between dust concentrations of some PBDEs and emerging HFRs and the total number of foam mattresses and beds/m2, the number of foam-containing sofas/m2, and the number of TVs/m2 in the microenvironment, indicating these products as the main source of those compounds. Additionally, younger preschool building ages were found to be linked to higher ΣOPE concentrations in preschool dust, suggesting higher ΣOPE exposure. The comparison with earlier Swedish studies indicates decreasing dust concentrations for some banned and restricted legacy HFRs and OPEs but increasing trends for several emerging HFRs and several unrestricted OPEs. Therefore, the study concludes that emerging HFRs and OPEs are replacing legacy HFRs in products and building materials in homes and preschools, possibly leading to increased exposure of children.

Berlin statement on legacy and emerging contaminants in polar regions.

Polar regions should be given greater consideration with respect to the monitoring, risk assessment, and management of potentially harmful chemicals, consistent with requirements of the precautionary principle. Protecting the vulnerable polar environments requires (i) raising political and public awareness and (ii) restricting and preventing global emissions of harmful chemicals at their sources. The Berlin Statement is the outcome of an international workshop with representatives of the European Commission, the Arctic Council, the Antarctic Treaty Consultative Meeting, the Stockholm Convention on Persistent Organic Pollutants (POPs), environmental specimen banks, and data centers, as well as scientists from various international research institutions. The statement addresses urgent chemical pollution issues in the polar regions and provides recommendations for improving screening, monitoring, risk assessment, research cooperation, and open data sharing to provide environmental policy makers and chemicals management decision-makers with relevant and reliable contaminant data to better protect the polar environments. The consensus reached at the workshop can be summarized in just two words: "Act now!" Specifically, "Act now!" to reduce the presence and impact of anthropogenic chemical pollution in polar regions by. •Establishing participatory co-development frameworks in a permanent multi-disciplinary platform for Arctic-Antarctic collaborations and establishing exchanges between the Arctic Monitoring and Assessment Program (AMAP) of the Arctic Council and the Antarctic Monitoring and Assessment Program (AnMAP) of the Scientific Committee on Antarctic Research (SCAR) to increase the visibility and exchange of contaminant data and to support the development of harmonized monitoring programs. •Integrating environmental specimen banking, innovative screening approaches and archiving systems, to provide opportunities for improved assessment of contaminants to protect polar regions.

Dietary Intake Contributed the Most to Chlorinated Paraffin Body Burden in a Norwegian Cohort.

Determining the major human exposure pathways is a prerequisite for the development of effective management strategies for environmental pollutants such as chlorinated paraffins (CPs). As a first step, the internal and external exposure to CPs were quantified for a well-defined human cohort. CPs in participants' plasma and diet samples were analyzed in the present study, and previous results on paired air, dust, and hand wipe samples were used for the total exposure assessment. Both one compartment pharmacokinetic modeling and forensic fingerprinting indicate that dietary intake contributed the most to body burden of CPs in this cohort, contributing a median of 60-88% of the total daily intakes. The contribution from dust ingestion and dermal exposure was greater for the intake of long-chain CPs (LCCPs) than short-chain CPs (SCCPs), while the contribution from inhalation was greater for the intake of SCCPs than medium-chain CPs (MCCPs) and LCCPs. Significantly higher concentrations of SCCPs and MCCPs were observed in diets containing butter and eggs, respectively (p < 0.05). Additionally, other exposure sources were correlated to plasma levels of CPs, including residence construction parameters such as the construction year (p < 0.05). This human exposure to CPs is not a local case. From a global perspective, there are major knowledge gaps in biomonitoring and exposure data for CPs from regions other than China and European countries.

Influences of climate change on long-term time series of persistent organic pollutants (POPs) in Arctic and Antarctic biota.

Time series of contaminants in the Arctic are an important instrument to detect emerging issues and to monitor the effectiveness of chemicals regulation, based on the assumption of a direct reflection of changes in primary emissions. Climate change has the potential to influence these time trends, through direct physical and chemical processes and/or changes in ecosystems. This study was part of an assessment of the Arctic Monitoring and Assessment Programme (AMAP), analysing potential links between changes in climate-related physical and biological variables and time trends of persistent organic pollutants (POPs) in Arctic biota, with some additional information from the Antarctic. Several correlative relationships were identified between POP temporal trends in freshwater and marine biota and physical climate parameters such as oscillation indices, sea-ice coverage, temperature and precipitation, although the mechanisms behind these observations remain poorly understood. Biological data indicate changes in the diet and trophic level of some species, especially seabirds and polar bears, with consequences for their POP exposure. Studies from the Antarctic highlight increased POP availability after iceberg calving. Including physical and/or biological parameters in the POP time trend analysis has led to small deviations in some declining trends, but did generally not change the overall direction of the trend. In addition, regional and temporary perturbations occurred. Effects on POP time trends appear to have been more pronounced in recent years and to show time lags, suggesting that climate-related effects on the long time series might be gaining importance.

Influence of climate change on persistent organic pollutants and chemicals of emerging concern in the Arctic: state of knowledge and recommendations for future research.

Persistent organic pollutants (POPs) have accumulated in polar environments as a result of long-range transport from urban/industrial and agricultural source regions in the mid-latitudes. Climate change has been recognized as a factor capable of influencing POP levels and trends in the Arctic, but little empirical data have been available previously. A growing number of recent studies have now addressed the consequences of climate change for the fate of Arctic contaminants, as reviewed and assessed by the Arctic Monitoring and Assessment Programme (AMAP). For example, correlations between POP temporal trends in air or biota and climate indices, such as the North Atlantic Oscillation Index, have been found. Besides the climate indices, temperature, precipitation and sea-ice were identified as important climate parameters influencing POP levels in the Arctic environment. However, the physical changes are interlinked with complex ecological changes, including new species habitats and predator/prey relationships, resulting in a vast diversity of processes directly or indirectly affecting levels and trends of POPs. The reviews in this themed issue illustrate that the complexity of physical, chemical, and biological processes, and the rapid developments with regard to both climate change and chemical contamination, require greater interdisciplinary scientific exchange and collaboration. While some climate and biological parameters have been linked to POP levels in the Arctic, mechanisms underlying these correlations are usually not understood and need more work. Going forward there is a need for a stronger collaborative approach to understanding these processes due to high uncertainties and the incremental process of increasing knowledge of these chemicals. There is also a need to support and encourage community-based studies and the co-production of knowledge, including the utilization of Indigenous Knowledge, for interpreting trends of POPs in light of climate change.

Outside the Safe Operating Space of the Planetary Boundary for Novel Entities.

We submit that the safe operating space of the planetary boundary of novel entities is exceeded since annual production and releases are increasing at a pace that outstrips the global capacity for assessment and monitoring. The novel entities boundary in the planetary boundaries framework refers to entities that are novel in a geological sense and that could have large-scale impacts that threaten the integrity of Earth system processes. We review the scientific literature relevant to quantifying the boundary for novel entities and highlight plastic pollution as a particular aspect of high concern. An impact pathway from production of novel entities to impacts on Earth system processes is presented. We define and apply three criteria for assessment of the suitability of control variables for the boundary: feasibility, relevance, and comprehensiveness. We propose several complementary control variables to capture the complexity of this boundary, while acknowledging major data limitations. We conclude that humanity is currently operating outside the planetary boundary based on the weight-of-evidence for several of these control variables. The increasing rate of production and releases of larger volumes and higher numbers of novel entities with diverse risk potentials exceed societies' ability to conduct safety related assessments and monitoring. We recommend taking urgent action to reduce the harm associated with exceeding the boundary by reducing the production and releases of novel entities, noting that even so, the persistence of many novel entities and/or their associated effects will continue to pose a threat.

Identifying emerging environmental concerns from long-chain chlorinated paraffins towards German ecosystems.

Germany is one of several major European producers of chlorinated paraffins (CPs). This study showed that not only the legacy short-chain products (SCCPs, C10-13), but also the current-use medium- and long-chain products (MCCPs, C14-17; LCCPs, C>17) as well as the very-short-chain impurities (vSCCPs, C<10) are ubiquitous in the 72 samples collected from the coastal, terrestrial, and freshwater ecosystems across the country. The concentrations of LCCPs surpassed those of the other CPs in 40% of the biota samples. Archived bream samples collected downstream of a CP-manufacturing factory showed decreasing temporal trends of (v)SCCPs and relatively constant levels of MCCPs from 1995 to 2019; however, the overall levels of LCCPs have increased by 290%, reflecting the impact of chemical regulation policies on changes in CP production. A visualization algorithm was developed for integrating CP results from various matrices to illustrate spatial tendencies of CP pollution. Higher levels of (v)SCCPs were indicated in the former West Germany region, while MCCP and LCCP concentrations did not seem to differ between former East and West Germany, suggesting relatively equal production and use of these chemicals after the German Reunification. The results provide an early warning signal of environmental concerns from LCCPs on the eve of their booming global production and use.

Relationships between gene transcription and contaminant concentrations in Baltic ringed seals: A comparison between tissue matrices.

Ringed seals (Pusa hispida) are slowly recovering in the eastern and northern parts of the Baltic Sea after years of hunting pressure and contaminant exposure. Still, consequences of anthropogenic activities such as contaminant exposure and increasing temperatures are stressors that continue to have deleterious effects on their habitat and health. Transcription profiles of seven health-related genes involved in xenobiotic metabolism, endocrine disruption and stress were evaluated in blood, blubber, and liver of Baltic ringed seals in a multi-tissue approach. Selected persistent organic pollutants and total mercury concentrations were measured in blubber and liver, and muscle and liver of these animals, respectively. Concentrations of contaminants varied across tissues on a lipid weight basis but not with sex. mRNA transcript levels for all seven target genes did not vary between sexes or age classes. Transcript levels of thyroid hormone receptor alpha (TRα), retinoic acid receptor alpha (RARα) and heat shock protein 70 (HSP70) correlated with levels of persistent organic pollutants. TRα transcript levels also correlated positively with mercury concentrations in the liver. Of the three tissues assessed in this multi-tissue approach, blubber showed highest transcription levels of aryl hydrocarbon receptor nuclear translocator (ARNT), thyroid stimulating hormone receptor beta (TSHß), oestrogen receptor alpha (ESR1) and peroxisome proliferator activated receptor alpha (PPARα). The wide range of genes expressed highlights the value of minimally invasive sampling (e.g. biopsies) for assessing health endpoints in free-ranging marine wildlife and the importance of identifying optimal matrices for targeted gene expression studies. This gene transcript profile study has provided baseline information on transcript levels of biomarkers for early on-set health effects in ringed seals and will be a useful guide to assess the impacts of environmental change in Baltic pinnipeds for conservation and management.

Can determination of extractable organofluorine (EOF) be standardized? First interlaboratory comparisons of EOF and fluorine mass balance in sludge and water matrices.

The high proportion of unidentified extractable organofluorine (EOF) observed globally in humans and the environment indicates widespread occurrence of unknown per- and polyfluoroalkyl substances (PFAS). However, efforts to standardize or assess the reproducibility of EOF methods are currently lacking. Here we present the first EOF interlaboratory comparison in water and sludge. Three participants (four organizations) analyzed unfortified and PFAS-fortified ultrapure water, two unfortified groundwater samples, unfortified wastewater treatment plant effluent and sludge, and an unfortified groundwater extract. Participants adopted common sample handling strategies and target lists for EOF mass balance but used in-house combustion ion-chromatography (CIC) and liquid chromatography-tandem mass spectrometry (LC-MS/MS) methods. EOF accuracy ranged from 85-101% and 76-109% for the 60 and 334 ng L-1 fluorine (F) - fortified water samples, respectively, with between-laboratory variation of 9-19%, and within-laboratory variation of 3-27%. In unfortified sludge and aqueous samples, between-laboratory variation ranged from 21-37%. The contribution from sum concentrations of 16 individual PFAS (∑PFAS-16) to EOF ranged from 2.2-60% but extended analysis showed that other targets were prevalent, in particular ultra-short-chain perfluoroalkyl acids (e.g. trifluoroacetic acid) in aqueous samples and perfluoroalkyl acid-precursors (e.g. polyfluoroalkyl phosphate diesters) in sludge. The EOF-CIC method demonstrated promising accuracy, robustness and reporting limits but poor extraction efficiency was observed for some targets (e.g. trifluoroacetic acid).

Soil-air partitioning of semivolatile organic compounds in the Lesser Himalaya region: Influence of soil organic matter, atmospheric transport processes and secondary emissions.

After decades of imposed regulations about reducing the primary emissions of persistent organic pollutants (POPs), these pollutants are still present in the environment. Soils are important repositories of such persistent semivolatile organic contaminants (SVOCs), and it is assumed that SVOCs sequestered in these reservoirs are being re-mobilized due to anthropogenic influence. In this study, concentrations of organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), and polybrominated diphenyl ethers (PBDEs) in soil and air, their fugacities, fluxes and the soil-air partition coefficient (KSA) were determined for three different land cover types (glacial, remote/mountainous and urban) of the Lesser Himalayan Region (LHR). The concentrations of OCPs, PCBs and PBDEs in soils and air ranged between 0.01 and 2.8, 0.81-4.8, 0.089-0.75 ng g-1; 0.2-106, 0.027-182, and 0.011-7.26 pg m-3, respectively. The levels of SVOCs in the soil were correlated with soil organic matter (SOM) indicating that SOM is a substrate for the organic pollutants in soils. The Clausius-Clapeyron plots between ln P and inverse of temperature (1000/T) suggested that long range atmospheric transport was the major input source of PBDEs and higher chlorinated PCBs over the LHR. The uneven and wide distribution of local sources in LHR and up-slope enrichment of SVOCs explained the spatial variability and altitudinal patterns. The soils near mountain and urban lakes act as local sinks of SVOCs such as ß-HCH, pp΄-DDT, CB-28, -118, -153, BDE-47, -99, and -154, with soil-air exchange fluxes tending more toward deposition. However, the soils near glacial lakes acted as local sources of more volatile congeners of α-HCH, γ-HCH, op'-DDT, pp'-DDE and lower to medium chlorinated PCBs such as CB-18, -28, -53, -42 and BDE-47, -99, with soil-air exchange tending more toward volatilization flux.

Semi-Volatile Organic Compounds in Car Dust: A Pilot Study in Jeddah, Saudi Arabia.

People may spend a significant amount of their daily time in cars and thus be exposed to chemicals present in car dust. Various chemicals are emitted from during car use, contaminating the car dust. In this study, we compiled published and unpublished data on the occurrence of phthalates, flame retardants (FRs), polycyclic aromatic hydrocarbons (PAHs), and polychlorinated biphenyls (PCBs) in Saudi car dust. Phthalates, a class of chemical commonly used as plasticizers in different car parts, were the major pollutants found in car dust, with a median value of ∑phthalates 1,279,000 ng/g. Among other chemicals, organophosphate flame retardants (OPFRs) were found to be between 1500-90,500 ng/g, which indicates their use as alternative FRs in the car industry. The daily exposure to Saudi drivers (regular and taxi drivers) was below the respective reference dose (RfD) values of the individual chemicals. However, the estimated incremental lifetime cancer risk (ILCR) values due to chronic exposure to these chemicals was >1 × 10-5 for taxi drivers for phthalates and PAHs, indicating that the long-term exposure to these chemicals is a cause of concern for drivers who spend considerable time in cars. The study has some limitations, due to the small number of samples, lack of updated RfD values, and missing cancer slope factors for many studied chemicals. Despite these limitations, this study indicates the possible range of exposure to drivers from chemicals in car dust and warrants further extensive studies to confirm these patterns.

The effect of reduction measures on concentrations of hazardous semivolatile organic compounds in indoor air and dust of Swedish preschools.

Young children spend a substantial part of their waking time in preschools. It is therefore important to reduce the load of hazardous semivolatile organic compounds (SVOCs) in the preschools' indoor environment. The presence and levels of five SVOC groups were evaluated (1) in a newly built preschool, (2) before and after renovation of a preschool, and (3) in a preschool where SVOC-containing articles were removed. The new building and the renovation were performed using construction materials that were approved with respect to content of restricted chemicals. SVOC substance groups were measured in indoor air and settled dust and included phthalates and alternative plasticizers, organophosphate esters (OPEs), brominated flame retardants, and bisphenols. The most abundant substance groups in both indoor air and dust were phthalates and alternative plasticizers and OPEs. SVOC concentrations were lower or of the same order of magnitude as those reported in comparable studies. The relative Cumulative Hazard Quotient (HQcum ) was used to assess the effects of the different reduction measures on children's SVOC exposure from indoor air and dust in the preschools. HQcum values were low (1.0-6.1%) in all three preschools and decreased further after renovation and article substitution. The SVOCs concentrations decreased significantly more in the preschool renovated with the approved building materials than in the preschool where the SVOC-containing articles were removed.

Human Exposure to Chlorinated Paraffins via Inhalation and Dust Ingestion in a Norwegian Cohort.

Very-short- (vSCCPs, C6-9), short- (SCCPs, C10-13), medium- (MCCPs, C14-17), and long-chain chlorinated paraffins (LCCPs, C>17) were analyzed in indoor air and dust collected from the living rooms and personal 24 h air of 61 adults from a Norwegian cohort. Relatively volatile CPs, i.e., vSCCPs and SCCPs, showed a greater tendency to partition from settled indoor dust to paired stationary indoor air from the same living rooms than MCCPs and LCCPs, with median logarithmic dust-air partition ratios of 1.3, 2.9, 4.1, and 5.4, respectively. Using the stationary indoor air and settled indoor dust concentrations, the combined median daily exposures to vSCCPs, SCCPs, MCCPs, and LCCPs were estimated to be 0.074, 2.7, 0.93, and 0.095 ng/kg bw/d, respectively. Inhalation was the predominant exposure pathway for vSCCPs (median 99%) and SCCPs (59%), while dust ingestion was the predominant exposure pathway for MCCPs (75%) and LCCPs (95%). The estimated inhalation exposure to total CPs was ∼ 5 times higher when the personal 24 h air results were used rather than the corresponding stationary indoor air results in 13 paired samples, indicating that exposure situations other than living rooms contributed significantly to the overall personal exposure. The 95th percentile exposure for CPs did not exceed the reference dose.

Persistent organic pollutants (POPs) in fish species from different lakes of the lesser Himalayan region (LHR), Pakistan: The influence of proximal sources in distribution of POPs.

Fish dwelling in remote mountain water systems are sensitive to long term exposure of POPs and can be used as an important bioindicator of POPs pollution in fragile mountain ecosystems. Current study aimed to investigate the concentrations and patterns of organic pollutants in fish tissues from different lakes of the Lesser Himalayan Region (LHR). OCPs, PCBs, PBDEs were analyzed in four common edible fish species of the LHR: Oncorhynchus mykiss, Labeo rohita, Hypophthalmichthys molitrix and Orechromis aureus. The fish were collected from lakes with different types of catchment areas (glacial, non-glacial mountain region and urban region) and extent of anthropogenic influence. The levels OCPs, PCBs and PBDEs analyzed in the selected fish species were in range of 0.21-587, 6.4-138 and 1.2-14 ng g-1 lw, respectively. The ∑DDTs, higher chlorinated PCBs, tetra- and penta-BDEs were more prevalent in urban and remote lakes whereas pp'-DDE, lower chlorinated PCBs and BDE-47 and -99 were predominant in fish species from glacial lakes. ∑DDTs, ∑PCBs and ∑PBDEs showed statistically significant differences (p < 0.05) among species, trophic guilds (carnivore, herbivore and omnivore) and feeding regimes (surface, bottom and column feeder) and ∑HCH showed a significant difference only among trophic guilds. The stable isotope values of δ 15N and δ13C differed significantly among species for ∑HCH, ∑PCBs, ∑PBDEs (p < 0.05) and ∑DDT (p < 0.01). The range of δ13C values (-34 to -19‰) indicated the importance of littoral and pelagic sources of dietary carbon. Trophic position and dietary proxies were identified as important variables for explaining the variability of the studied compounds. Kohonen self-organizing maps (SOM) showed that in addition to trophic position and other physiological characteristics of fish, that the type of lakes and proximal sources of POPs were the most important predictors for distribution of organic contaminants in fish samples from LHR.

Complex Mixtures of Chlorinated Paraffins Found in Hand Wipes of a Norwegian Cohort.

Up to 18000 ng of total chlorinated paraffins (CPs) was found in hand wipes of individual adult participants in a Norwegian cohort study (n = 60), with a geometric mean (SD) value of 870 (2700) ng. The CPs covered a wide range of alkane chain lengths from C7 to C48 with variable chlorine substitution. Complex mixtures of very-short-chain (vSCCPs, C<10), short-chain (SCCPs, C10-13), medium-chain (MCCPs, C14-17), and long-chain (LCCPs, C>17) CPs were found, contributing on average 0.3%, 20%, 58%, and 22%, respectively, of the total CPs. Significant positive correlations were found between CP levels and factors related to the indoor environment and product use, including living in a house/apartment built before the ban of SCCPs, having a sofa, the number of TVs in the home, and owning a car, which mirrors CP usage as flame retardants and/or plasticizers in consumer products. Compared to previous studies of other organic contaminants in hand wipe samples from the same cohort, CPs were the most abundant flame retardants. This is the first report of CPs in hand wipes, and dermal exposure based on these data suggested that hand contact could be an important human exposure pathway for LCCPs.

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.

Chlorinated Paraffins in Two Snake Species from the Yangtze River Delta: Tissue Distribution and Biomagnification.

Very-short, short-, medium-, and long-chain chlorinated paraffins (vSCCPs, SCCPs, MCCPs, and LCCPs, respectively) were analyzed in different tissues of the terrestrial short-tailed mamushi (Gloydius brevicaudus) and the semi-aquatic red-backed rat snake (Elaphe rufodorsata) from the Yangtze River Delta, China. The total CP concentrations in liver, muscle, and adipose tissues in the two snake species were in the range of 2500-24 000, 4900-48 000, and 12-630 ng/g lw, respectively. Tissue burdens indicated that vSCCPs (C6-9) and SCCPs (C10-13) preferentially distributed to snake liver, while adipose was an important storage site and sink of MCCPs (C14-17) and LCCPs (C>18). On a lipid weight basis, vSCCPs and SCCPs were found in highest concentrations in red-backed rat snake liver and MCCPs and LCCPs in muscle, whereas for short-tailed mamushi, all CP groups were predominant in muscle, probably reflecting ecosystem/food web differences. Moreover, vSCCPs, SCCPs, MCCPs, and LCCPs were found to be biomagnified from black-spotted frogs to red-backed rat snakes with mean (maximum) biomagnification factors of 2.2 (3.4), 1.9 (3.7), 1.8 (2.8), and 1.7 (4.5), respectively. This is the first field study of biomagnification potential involving vSCCPs and LCCPs and highlights the need to include all CPs in studies.