Though many persistent organic pollutants (POPs) are closely regulated the human population is still exposed to these ubiquitous chemicals from the environment and diet. Safe management and human biomonitoring of POPs is necessary to understand the risk of exposure. Within human biomonitoring the mass of sample is often limited, therefore robust methods using smaller sample amounts are necessary. This study developed a 96-well plate solid phase extraction (SPE) method for determination of selected POPs: polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs), polybrominated diphenyl ethers (PBDEs), hexabromocyclododecane (HBCD) and non-persistent novel flame retardants (NFRs) in low volume blood serum. Non-destructive clean-up coupling Oasis HLB extraction plate with Phree phospholipid removal plate was employed. Extraction efficiency was determined at low and high concentrations in certified reference materials NIST SRM 1957 and 1958, respectively. Target compounds deviated from certified values on average by 15% and 21% for SRM 1957 and SRM 1958, respectively. Observed limit of detections (LODs) ranged from 0.36 pg/mL (PCB 180) to 66.07 pg/mL (δ-HCH). The applicability for real samples is demonstrated on 48 samples from pregnant women enrolled in the pilot phase of the CELSPAC: TNG study. In total, 30 target compounds were detected in at least one sample. The method developed here provides a fast and reliable analysis of human blood serum with possibility to introduce automation for the sample preparation procedure.

Every day we are exposed to a cocktail of anthropogenic compounds many of which are biologically active and capable of inducing negative effects. The simplest way to monitor contaminants in a population is via human biomonitoring (HBM), however conventional targeted approaches require foreknowledge of chemicals of concern, often have compound specific extractions and provide information only for those compounds. This study developed an extraction process for human biomarkers of interest (BoE) in urine that is less compound specific. Combining this with an ultra-high resolution mass spectrometer capable of operating in full scan, and a suspect and non-targeted analysis (SS/NTA) approach, this method provides a more holistic characterization of human exposure. Sample preparation development was based on enzymatically hydrolysed urine spiked with 34 native standards and extracted by solid-phase extraction (SPE). HRMS data was processed by MzMine2 and 80% of standards were identified in the final data matrix using typical NTA data processing procedures.

The diet is the main route that polycyclic aromatic hydrocarbons (PAHs) enter the body and measuring breast milk is one of the best ways to understand the maternal body burden and can be passed on to infants. In this study, it was determinate the concentrations of 23 PAHs in 60 milk samples taken from 3 cities in Colombia and to determine the potential routes of exposure and risk to human health. On average, concentration for the ∑PAHs across all locations was 186.6 ng g−1, lipid mass (LM), with city means of 260.1, 175.7, and 123.9 ng g−1 LM for Cartagena, Bogota and Medellin, respectively. Monte Carlo simulations were used to estimate the hazard quotient (HQ) and incremental lifetime cancer risk (ILCR) for infant dietary exposure to PAHs. HQs were below the safe thresholds (HQ = 1) while ILCRs were greater than the reference value equal to 10−6 (mg kg−1day−1). Dietary source assessment indicated that fish is a significant source of PAHs, with mothers that consumed fish at least once per week having ∼2.5 times greater PAH milk concentrations than other groups. While a disparity was also observed among consumers of exclusively marine (∑PAHs 198.5 ng g−1 LM) or freshwater fish (∑PAHs 85.7 ng g−1 LM). However, geographical considerations can be significant in this finding.

Human exposure to organic contaminants is widespread. Many of these contaminants show adverse health effects on human population. Human biomonitoring (HBM) follows the levels and the distribution of biomarkers of exposure (BoE), but it is usually done in a targeted manner. Suspect and non-targeted screening (SS/NTS) tend to find BoE in an agnostic way, without preselection of compounds, and include finding evidence of exposure to predicted, unpredicted known and unknown chemicals. This study describes the application of high-resolution mass spectrometry (HRMS)-based SS/NTS workflow for revealing organic contaminants in urine of a cohort of 200 children from Slovenia, aged 6–9 years. The children originated from two regions, urban and rural, and the latter were sampled in two time periods, summer and winter. We tentatively identified 74 BoE at the confidence levels of 2 and 3. These BoE belong to several classes of pharmaceuticals, personal care products, plasticizers and plastic related products, volatile organic compounds, nicotine, caffeine and pesticides. The risk of three pesticides, atrazine, amitraz and diazinon is of particular concern since their use was limited in the EU. Among BoE we tentatively identified compounds that have not yet been monitored in HBM schemes and demonstrate limited exposure data, such as bisphenol G, polyethylene glycols and their ethers. Furthermore, 7 compounds with unknown use and sources of exposure were tentatively identified, either indicating the entry of new chemicals into the market, or their metabolites and transformation products. Interestingly, several BoE showed location and time dependency. Globally, this study presents high-throughput approach to SS/NTS for HBM. The results shed a light on the exposure of Slovenian children and raise questions on potential adverse health effects of such mixtures on this vulnerable population.

Capsule: This study highlights the importance of utilizing zooplankton and integrated omics techniques for characterizing the toxic effects of algal blooms.

To address the lack of high-resolution electron ionisation mass spectral libraries (HR-[EI+]-MS) for environmental chemicals, a retention-indexed HR-[EI+]-MS library has been constructed following analysis of authentic compounds via GC-Orbitrap MS. The library is freely provided alongside a compound database of predicted physicochemical properties. Currently, the library contains over 350 compounds from 56 compound classes and includes a range of legacy and emerging contaminants. The RECETOX Exposome HR-[EI+]-MS library expands the number of freely available resources for use in full-scan chemical exposure studies and is available at: https://doi.org/10.5281/zenodo.4471217.

Arctic warming associated with global climate change poses a significant threat to populations of wildlife in the Arctic. Since lipids play a vital role in adaptation of organisms to variations in temperature, high-resolution mass-spectrometry-based lipidomics can provide insights into adaptive responses of organisms to a warmer environment in the Arctic and help to illustrate potential novel roles of lipids in the process of thermal adaption. In this study, we studied an ecologically and economically important species—Arctic char (Salvelinus alpinus)—with a detailed multi-tissue analysis of the lipidome in response to chronic shifts in temperature using a validated lipidomics workflow. In addition, dynamic alterations in the hepatic lipidome during the time course of shifts in temperature were also characterized. Our results showed that early life stages of Arctic char were more susceptible to variations in temperature. One-year-old Arctic char responded to chronic increases in temperature with coordinated regulation of lipids, including headgroup-specific remodeling of acyl chains in glycerophospholipids (GP) and extensive alterations in composition of lipids in membranes, such as less lyso-GPs, and more ether-GPs and sphingomyelin. Glycerolipids (e.g. triacylglycerol, TG) also participated in adaptive responses of the lipidome of Arctic char. Eight-week-old Arctic char exhibited rapid adaptive alterations of the hepatic lipidome to stepwise decreases in temperature while showing blunted responses to gradual increases in temperature, implying an inability to adapt rapidly to warmer environments. Three common phosphatidylethanolamines (PEs) (PE 36:6|PE 16:1_20:5, PE 38:7|PE 16:1_22:6, and PE 40:7|PE 18:1_22:6) were finally identified as candidate lipid biomarkers for temperature shifts via machine learning approach. Overall, this work provides additional information to a better understanding of underlying regulatory mechanisms of the lipidome of Arctic organisms in the face of near-future warming.

Indoor dust is an important exposure route to anthropogenic chemicals used in consumer products. Plasticizers are common product additives and can easily leach out of the product and partition to dust. Investigations of plasticizers typically focus on a subset of phthalate esters (PEs), but there are many more PEs in use, and alternative plasticizers (APs) are seeing greater use after recognition of adverse health effects of PEs. In this study we use full scan high resolution mass spectrometry for targeted and suspect screening of PEs and APs in house dust and to assess the potential risk of human exposure. House dust samples from Eastern Slovakia were investigated and concentrations of ∑12PEs and ∑5APs ranged 12–2765 μg/g and 45–13,260 μg/g, respectively. APs were at similar levels to PEs, indicating common usage of these compounds in products in homes. Evaluation of individual compound toxicity combined with human intake via dust ingestion suggested PEs are of lower priority compared to semivolatile organic compounds such as polychlorinated biphenyls due to their lower toxicity. However, cumulative risk assessment (CRA) is a more appropriate evaluation of risk, considering the presences of many PEs in dust and their similar toxic mode of action. CRA based on median toxicity reference values (TRVs) suggested acceptable risks for dust ingestion, however, the wide range of literature-derived TRVs is a large uncertainty, especially for the APs. Use of newer TRVs suggest risk from dust ingestion alone, i.e. not even considering diet, inhalation, and dermal contact. Additionally, screening of full-scan instrumental spectra identified a further 40 suspect PE compounds, suggesting the CRA based on the 12 target PEs underestimates the risk.

There is growing concern about possible effects of exploitation of the Alberta Oil Sands on the ambient environment, including possible effects on populations of fishes in the Athabasca River and farther downstream in Lake Athabasca and the Slave River. The concentrations of metals in dorsal muscle tissue of five fish species, namely, goldeye, northern pike, walleye, whitefish, and burbot, from the Slave, Peace, and Athabasca Rivers were quantified. A suite of 25 metals including As, Hg, Se, Tl, and V was analyzed. Most metals showed insignificant variations in concentration among locations. Concentrations of five metals, As, Hg, Se, Tl, and V, displayed considerable variations among locations and were of sufficient magnitude to be of interest. Concentrations of Hg did not changed greatly among locations, however, since it was detected at concentrations of concern and the use of the selected fishes was a local source of food for humans and pets, it was of interest. Concentrations of As, Se, Tl, and V in dorsal muscle of certain fishes in the farthest downstream sites on the Slave River were greater than those in the same tissues and species in the farther upstream sites on the Peace and Athabasca Rivers. This phenomenon was most prevalent with Tl and to a lesser extent with As and Se. Nevertheless, concentrations were not of concern for the health of human consumers.

Because compounds accumulate through dry periods and enter aquatic systems in just a few seasonal events such as snowmelt and summer storms, surface waters in semi-arid, cold regions, such as the Canadian Prairies, are particularly vulnerable to loading of contaminant from runoff events from surfaces. This study assessed concentrations of metals and selected trace organics entering a river via surface runoff from an urban region and how these semi-arid regions with large seasonal variations in temperature might differ from more temperate regions. Selected potentially harmful elements (PHEs) including, Mn with Cr, Cu, Zn, Ba and U all exceeded guideline discharge values set by the Canadian Council of the Ministers of the Environment (CCME) by as much as 16-fold. Variation among discharges during spring, summer and winter was observed. For example, across the whole city, an estimated 6 kg of zinc was discharged in a spring storm, 36 kg in a summer storm and 17 tonnes in snowmelt. The mass of Zn discharged is similar to the annual loading estimated for Stockholm, Sweden, but in Saskatoon, Saskatchewan, Canada, the bulk of runoff was during snowmelt. The mean sum of poly- and per-fluoroalkyl substances (PFAS) in stormwater was 9.0 ng L−1, which is consistent with concentrations observed in other Canadian cities (6.5–16 ng L−1). These concentrations of PFAS are likely due to dispersed sources and orders of magnitude less than thresholds for toxicity to fish and aquatic invertebrates.

Among the nitrated and oxygenated polycyclic aromatic hydrocarbons (NPAHs and OPAHs) are some of the most hazardous substances to public health, mainly because of their carcinogenicity and oxidative potential. Despite these concerns, the concentrations and fate of NPAHs and OPAHs in the atmospheric environment are largely unknown. Ambient air concentrations of 18 NPAHs, 5 quinones, and 5 other OPAHs were determined at two urban and one regional background sites in central Europe. At one of the urban sites, the total (gas and particulate) concentrations of ς10OPAHs were 10.0 ± 9.2 ng/m3 in winter and 3.5 ± 1.6 ng/m3 in summer. The gradient to the regional background site exceeded 1 order of magnitude. ς18NPAH concentrations were typically 1 order of magnitude lower than OPAHs. Among OPAHs, 9-fluorenone and (9,10)-anthraquinone were the most abundant species, accompanied by benzanthrone in winter. (9,10)-Anthraquinone represented two-thirds of quinones. We found that a large fraction of the target substance particulate mass was carried by submicrometer particles. The derived inhalation bioaccessibility in the PM10 size fraction is found to be ≈5% of the total ambient concentration of OPAHs and up to ≈2% for NPAHs. For 9-fluorenone and (9,10)-anthraquinone, up to 86 and 18%, respectively, were found at the rural site. Our results indicate that water solubility could function as a limiting factor for bioaccessibility of inhaled particulate NPAHs and OPAHs, without considerable effect of surfactant lipids and proteins in the lung lining fluid.

A recent data set for 22 poly- and per-fluorinated compounds (PFASs) in Ponar grab samples of surface sediments and cores from the Great Lakes of North America was examined for concentrations, loads, correlations with geographical coordinates and depth (time), and for sources. Correlations were determined by multivariate regression analyses. Source apportionment of PFASs was carried out by positive matrix factorization (PMF) for two cores from Lake Ontario. For the five lakes together, the total load of PFASs in sediments was estimated to be 245 ± 24 tonnes, which is about half the load for total PCBs. The recent annual loading was 1812 ± 320 kg/yr. Concentrations and inventories of PFASs were greatest in Lakes Erie and Ontario. Since 1947, concentrations of perfluorooctane sulfonic acid (PFOS) in ten cores have increased exponentially as a function of time with doubling times between 10 and 54 yr and have leveled off in three cores since 2000. PMF demonstrated an effective grouping of two particle-associated factors, characterized mainly by longer-chain PFASs (C ≥ 8) and two other factors of mainly shorter-chain compounds (C ≤ 6). Two factors feature only one dominant compound: factor 1, PFOS, and factor 3, perfluorobutane sulfonic acid (PFBS). of all factors, factor 3 with PFBS has the largest contribution (47.8%). Significant scores for perfluorohexane sulfonic acid (PFHxS) and PFBS, along with flat or decreasing PFOS contributions since 2003, indicate that the replacement of PFOS with these compounds is beginning to take effect in the environment.

Since their inclusion in the Stockholm Convention, there has been a need for global monitoring of perfluorooctane sulfonate (PFOS), its salts and perfluorooctanesulfonyl fluoride (PFOSF), along with other non-listed highly fluorinated compounds. Passive air samplers (PAS) are ideal for geographic coverage of atmospheric monitoring. The most common type of PAS, using polyurethane foam (PUF) as a sorbent, was primarily developed for non-polar semivolatile organic compounds (SVOCs) and are not well-validated for polar substances such as the per- and polyfluoroalkyl substances (PFASs), however, they have been used for some PFASs, particularly PFOS. To evaluate their applicability, PAS were deployed for measurement of PFASs in outdoor and indoor air. Outdoors, two types of PAS, one consisting of PUF and one of XAD-2 resin, were deployed in an 18-week calibration study in parallel with a low-volume active air sampler (LV-AAS) in a suburban area. Indoors, PUF-PAS were similarly deployed over 12 weeks to evaluate their applicability for indoor monitoring. Samples were analysed for perfluoroalkyl carboxylic acids (PFCAs), perfluoroalkyl sulfonates (PFSAs), perfluorooctane sulfonamides (FOSAs), and perfluorooctane sulfonamidoethanols (FOSEs). In outdoor air, 17 out of the 21 PFAS were detected in more than 50% of samples, with a median ∑17PFASs of 18.0 pg m−3 while 20 compounds were detected in indoor air with a median concentration ∑20PFASs of 76.6 pg m−3 using AAS samplers. PFOS was the most common PFAS in the outdoor air while PFBA was most common indoors. Variability between PAS and AAS was observed and comparing gas phase and particle phase separately or in combination did not account for the variation observed. PUF-PAS may still have a valuable use in PFAS monitoring but more work is needed to identify the applicability of passive samplers for ionic PFAS.

Current and historical concentrations of 22 poly- and perfluorinated compounds (PFASs) in sediment collected from Lake Superior and northern Lake Michigan in 2011 and Lake Huron in 2012 are reported. The sampling was performed in two ways, Ponar grabs of surface sediments for current spatial distribution across the lake and dated cores for multi-decadal temporal trends. Mean concentrations of the sum of PFASs (∑PFASs) were 1.5, 4.6 and 3.1 ng g-1 dry mas (dm) in surface sediments for Lakes Superior, Michigan and Huron, respectively. of the five Laurentian Lakes, the watersheds of Superior and Huron are the less densely populated by humans, and concentrations observed were typically less and from more diffuse sources, due to lesser urbanization and industrialization. However, some regions of greater concentrations were observed and might indicate more local, point sources. In core samples concentrations ranged from 7 that include perfluoro-n-octane sulfonate (PFOS) bind more strongly to sediment, which resulted in more accurate analyses of temporal trends. Shorter-chain PFASs, such as perfluoro-n-butanoic acid which is the primary replacement for C8 PFASs that have been phased out, are more soluble and were identified in some core layers at depths corresponding to pre-production periods. Thus, analyses of temporal trends of these more soluble compounds in cores of sediments were less accurate. Total elemental fluorine (TF) and extractable organic fluorine (EOF) indicated that identified PFASs were not a significant fraction of fluorine containing compounds in sediment (

Honeybee losses have been attributed to multiple stressors and factors including the neonicotinoid insecticides (NIs). Much of the study of hive contamination has been focused upon temperate regions such as Europe, Canada and the United States. This study looks for the first time at honey, pollen and bees collected from across the Nile Delta in Egypt in both the spring and summer planting season of 2013. There is limited information upon the frequency of use of NIs in Egypt but the ratio of positive identification and concentrations of NIs are comparable to other regions. Metabolites of NIs were also monitored but given the low detection frequency, no link between matrices was possible in the study. Using a simple hazard assessment based upon published LD50 values for individual neonicotinoids upon the foraging and brood workers it was found that there was a potential risk to brood workers if the lowest reported LD50 was compared to the sum of the maximum NI concentrations. For non-lethal exposure there was significant risk at the worst case to brood bees but actual exposure effects are dependant upon the genetics and conditions of the Egyptian honeybee subspecies that remain to be determined.

The temporal and spatial trends in sediment of 22 poly- and perfluorinated (PFAS) compounds were investigated in the southern Great Lakes Erie and Ontario as well as Lake St. Clair. Surface concentrations measured by Ponar grab samples indicated a trend for greater concentrations near to urban sites. Mean concentrations ∑22PFAS were 15.6, 18.2 and 19 ng g−1 dm for Lakes St. Clair, Erie and Ontario, respectively. Perfluoro-n-butanoic acid (PFBA) and Perfluoro-n-hexanoic acid (PFHxA) were frequently determined in surface sediment and upper core samples indicating a shift in use patterns. Where PFBA was identified it was at relatively great concentrations typically >10 ng g−1 dm. However as PFBA and PFHxA are less likely to bind to sediment they may be indicative of pore water concentrations Sedimentation rates between Lake Erie and Lake Ontario differ greatly with greater rates observed in Lake Erie. In Lake Ontario, in general concentrations of PFAS observed in core samples closely follow the increase in use along with an observable change due to regulation implementation in the 1970s for water protection. However some of the more water soluble PFAS were observed in deeper core layers than the time of production could account for, indicating potential diffusion within the sediment. Given the greater sedimentation rates in Lake Erie, it was hoped to observe in greater resolution changes since the mid-1990s. However, though some decrease was observed at some locations the results are not clear. Many cores in Lake Erie had clearly observable gas voids, indicative of gas ebullition activity due to biogenic production, there were also observable mussel beds that could indicate mixing by bioturbation of core layers. This publication looks at the spatial and temporal trends in PFAS in the sediment of Lake Erie, Ontario and St Clair. Temporal trends are assessed through multiple core samples taken across the lake while spatial variation is from a greater number of surface sediment Ponar samples to provide greater resolution. Temporal trends mostly identify an increase in PFAS in sediment with time. However, more water-soluble compounds have been measured at depths greater than use would cause and may imply that for some PFAS cores are not ideal sample tools.

Inorganic carbon (IC), total organic carbon (OC), and black carbon (BC) were analyzed in eight sediment cores obtained from deep water (>30 m) sediments in the Chippewa and south Chippewa basins, as well as Green Bay in Lake Michigan. These cores were segmented at high resolution and radio-dated to reconstruct a detailed history of deposition to the lake both spatially and temporally since ca. 1850 CE. To help interpret the depositional record, cores were also characterized for stable isotopes (13C and 15N), as well as particle size distribution, density, organic matter (OM), and other parameters. Fine (silt and clay) sediment particles contained OM of primarily lacustrine algal biomass origin. Sedimentation fluxes showed large increases in OM and OC fluxes through much of the lake during the onset of industrialization and the period of rapid industrialization to onset of Great Lakes environmental legislation. In contrast, fluxes and loading of BC increased dramatically in the southern basin until the 1930's, then decreased substantially after the 1940's. This observation was due largely to results from site M009 nearest the steel mills and industrial zones of Chicago and northern Indiana. Together, whole lake loadings of OM and BC provide evidence that changing industrial activity and legislation intended to curb air pollution in the Great Lakes region have had a fairly rapid and dramatic impact. In contrast, legislation intended to decrease eutrophication through reductions in nutrient loading to the lake have not had a similar impact on sedimentation of OM in the lake.

In two recently published reports, hazards posed by dietary exposure to organophosphate and neonicotinoid plant protection products on the European honey bee (Apis mellifera L.) in Egypt were investigated. Using concentrations reported in those studies, an assessment of hazards posed by these two classes of insecticides to humans due to consumption of Egyptian honey from the Nile Delta during both spring and summer was performed. Twenty-eight compounds including metabolites were assessed for exposure of adult Egyptians based on the best- and worst-case scenarios. Even for the worst-case scenario, exposure to these two classes of pesticides in honey was 15-fold less than hazard index value of 1.0 for adverse effects on humans. Based upon this analysis, people exposed to these insecticides through consumption of honey products would be unlikely to exhibit adverse health outcomes.

In the current study, by combining ultra-high resolution (UHR) MS1 spectra, MS2 spectra, and derivatization, three hydroxylated isomers of 2-ethylhexyl tetrabromobenzoate (OH-TBB) were identified in Firemaster® 550 and BZ-54 technical products. Also, a new LC-UHRMS method, using atmospheric pressure chemical ionization (APCI), was developed for simultaneous analysis of OH-TBB, TBB, hydroxylated bis(2-ethylhexyl)-tetrabromophthalate (OH-TBPH) and TBPH in 23 samples of dust collected from houses in Saskatoon, SK, Canada. OH-TBBs were detected in 91% of samples, with a geometric mean concentration of 0.21 ng/g, which was slightly less than those of OH-TBPH (0.35 ng/g). TBB was detected in 100% of samples of dust with a geometric mean concentration of 992 ng/g. Significant (p 

Despite the fact that most persistent toxic substances have hardly been primarily emitted for several decades, their concentrations are only slowly decreasing in the global oceans. Surface seawater samples were collected along a 38°–24° N/28°–67° W transect in the subtropical North Atlantic Ocean. While the concentration levels of hexachlorobenzene (2.1–6.1 pg L−1), dichlorodiphenyltrichloroethane (DDT, up to 2.1 pg L−1) and polychlorinated biphenyls (PCB, 10.8–24.9 pg L−1) were in the same range as observed earlier in the North Atlantic, hexachlorocyclohexane (HCH, 90–627 pg L−1) was found elevated, partly also relative to previous measurements in the same sea region. Hereby, the ratio α-HCH/γ-HCH was very low, 0.09–0.13. Chlordane and endosulfan were found in the range

Polycyclic aromatic hydrocarbons (PAHs) are released to the environment from oil sands operations and from natural sources in Alberta, Canada. Concentrations of 16 USEPA priority PAHs were measured in tissues of fishes collected from three locations on the Athabasca River in Alberta and two downstream locations on the Slave River in the Northwest Territories, Canada. A total of 425 individual fish were collected including 89 goldeye (Hiodon alosoides), 93 whitefish (Coregonus clupeaformis), 104 northern pike/jackfish (Esox lucius), 96 walleye (Sander vitreus) and 43 burbot/loche mariah/mariah (Lota lota). Fish were sampled during the summer and fall of 2011 and spring of 2012. Dorsal muscle of fishes from upstream reaches of the Athabasca River, close to oil sands extraction and upgrading activities, contained greater concentrations of individual PAHs than concentrations in muscle of fishes from further downstream in the Slave River. Concentrations of the sum of USEPA indicator PAHs (∑PAHs) in fishes collected in the vicinity of Fort McKay, closest to oil sands activities, varied among seasons with average concentrations ranging from 11 (burbot, summer) to 1.2 × 102 ng/g, wm (burbot, spring) with a mean of 48 ng/g, wm. Concentrations of ∑PAHs in fishes collected in the vicinity of Fort Resolution, the location most distant from oil sands activities, also varied among species and seasons, with average concentrations ranging from 4.3 (whitefish, summer) to 33 ng/g, wm (goldeye, summer) with a mean of 13 ng/g, wm. Significant differences in concentrations of ∑PAHs in muscle were observed within goldeye, jackfish, walleye and whitefish among sites. Health risks posed by PAHs to humans were assessed probabilistically using a B[a]P equivalents approach (B[a]Peq). The average lifetime risk of additional cancers for humans who consumed fish was deemed to be within an 'acceptable' range of risk (i.e. less than 10-6).

To examine the uptake of dioxin-like compounds (DLCs), common roaches (Rutilus rutilus) were exposed for 28 days to differently contaminated sediments from two major European rivers in a purpose-built facility. Dietary transfer of DLCs was investigated by exposing fish to sediments inoculated or non-inoculated with black worms (Lumbriculus variegatus). Dioxin-like polychlorinated biphenyls (DL-PCBs), polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), measured via high-resolution gas chromatography/high-resolution mass spectrometry (HRGC/HRMS) in sediments and whole fish, were used to calculate toxicity equivalent quotients (TEQs). TEQs were compared with biological toxicity equivalent quotients (BEQs) determined via the 7-ethoxyresorufin-O-deethylase (EROD) assay, performed with mammalian (H4IIE) and fish (RTL-W1) liver cell lines. TEQs and BEQs indicated an uptake of sediment-borne DLCs by roach, which was independent of sediment contamination levels, but rather reflected sediment-specific characteristics. For most sediment treatments, DLC uptake did not increase with time. Highest congener-specific uptake (DL-PCB 123) was 10-fold compared to control. Exposure to worm-inoculated sediment of highest overall DLC contamination caused a 2-fold (TEQ and H4IIE BEQ) greater uptake of DLCs by fish compared to the respective non-inoculated treatment. H4IIE cells showed the greatest sensitivity (0.37 ± 0.25 pM TCDD) and the strongest correlation with TEQs (r2 = 0.79), hence, they seem to be best suited for DLC screening of sediments and biota, amended by compound-specific instrumental analysis if required.

Neonicotinoid insecticides (NIs) and their transformation products were detected in honey, pollen and honey bees, (Apis mellifera) from hives located within 30 km of the City of Saskatoon, Saskatchewan, Canada. Clothianidin and thiamethoxam were the most frequently detected NIs, found in 68 and 75% of honey samples at mean concentrations of 8.2 and 17.2 ng g-1 wet mass, (wm), respectively. Clothianidin was also found in >50% of samples of bees and pollen. Concentrations of clothianidin in bees exceed the LD50 in 2 of 28 samples, while for other NIs concentrations were typically 10-100-fold less than the oral LD50. Imidaclorpid was detected in ~30% of samples of honey, but only 5% of pollen and concentrations were

Biochars have increasingly been used as adsorbents for organic and inorganic contaminants in soils. However, during the carbonization process of pyrolysis, contaminants, including polycyclic aromatic hydrocarbons (PAHs) and polychlorinated dioxins and furans (PCDD/DF) can be generated. In this study, biochars made from sawdust, were prepared at various temperatures ranging from 250 to 700 °C. The Microtox® and rat hepatoma cell line H4IIE-luc assays were used to characterize the general toxic and effects, mediated through the aryl hydrocarbon receptor (AhR), or dioxin-like potencies of organic extracts of biochars. The greatest total concentrations of PAHs (8.6 × 102 μg kg−1) and PCDD/DF (6.1 × 102 pg g−1) were found in biochar generated at 400 °C and 300 °C, respectively. Results of the H4IIE-luc assay, which gives total concentrations of 2,3,7,8-TCDD equivalents (TEQH4IIE-luc), indicated that total potencies of aryl hydrocarbon receptor (AhR) agonists were in decreasing order: 300 °C > 250 °C > 400 °C > 500 °C > 700 °C. The 2,3,7,8-tetrachlorodibenzo-p-dioxin equivalents (TEQchem) calculated as the sum of products of 16 PAHs and 17 PCDD/DF congers multiplied by their respective relative potencies (RePs) was less than that of TEQH4IIE-luc determined by use of the bioanalytical method, with the H4IIE-luc assay, which measures the total dioxin-like potency of a mixtures. The ratio of TEQchem/TEQH4IIE-luc was in the range of 0.7%–3.8%. Thus, a rather small proportion of the AhR-mediated potencies extracted from biochars were identified by instrumental analyses. Results of the Microtox test showed similar tendencies as those of the H4IIE-luc test, and a linear correlation between EC50 of Microtox test and EC20 of H4IIE-luc test was found. The results demonstrated that biochars produced at higher pyrolysis temperatures (>400 °C) were less toxic and had lower potencies of AhR-mediated effects, which may be more suitable for soil application.

Concentrations of products of biotransformation of polycyclic aromatic hydrocarbons (PBPAH) were measured in bile of five fishes of nutritional, cultural and ecological relevance from the Athabasca/Slave river system. Samples were collected in Alberta and the Northwest Territories, Canada, during three seasons. As a measure of concentrations of PBPAHs to which fishes are exposed and to gain information on the nature and extent of potential exposures of people or piscivorous wildlife, concentrations of biotransformation products of two- and three-ringed, four-ringed and five-ringed PAHs were measured using synchronous fluorescence spectroscopy. Spatial and seasonal differences were observed with greater concentrations of PBPAHs in samples of bile of fish collected from Fort McKay as well as greater concentrations of PBPAHs in bile of fish collected during summer compared to those collected in other seasons. Overall, PBPAHs were greater in fishes of lower trophic levels and fishes more closely associated with sediments. In particular, goldeye (Hiodon alosoides), consistently contained greater concentrations of all the PBPAHs studied.

Previously unreported natural and synthetic organo-bromine compounds (NSOBCs) have been found to contribute more than 99% of total organic bromine (TOB) in environmental matrices. We recently developed a novel untargeted method (data-independent precursor isolation and characteristic fragment, DIPIC-Frag) and identified ∼2000 NSOBCs in two sediments from Lake Michigan. In this study, this method was used to investigate the distributions of these NSOBCs in 23 surficial samples and 24 segments of a sediment core from Lake Michigan. NSOBCs were detected in all 23 surficial samples and exhibited 10- to 100-fold variations in peak abundance among locations. The pattern of distributions of NSOBCs was correlated with depth of the water column (r2 = 0.61, p < 0.001). Hierarchical cluster analysis showed that sediments in close proximity exhibited similar profiles of NSOBCs. Distributions of NSOBCs in 24 segments of a sediment core dated from 1766 to 2008 were investigated, and samples from similar depths exhibited similar profiles of NSOBCs. NSOBCs were grouped into four clusters (soft-cluster analysis) with different temporal trends of abundances. 515 and 768 of the NSOBCs were grouped into cluster 1 and cluster 3 with increasing temporal trends, especially since 1950, indicating that abundances of these compounds might have been affected by human activities.

The majority of halogenated organic compounds present in the environment remain unidentified. To address this data gap, we recently developed an untargeted method (data-independent precursor isolation and characteristic fragment; DIPIC-Frag) for identification of unknown organo-bromine compounds. In this study, the method was adapted to enable untargeted screening of natural and synthetic organo-iodine compounds (NSOICs) in sediments. A total of 4,238 NSOIC peaks were detected in sediments from Lake Michigan. Precursor ions and formulas were determined for 2,991 (71%) of the NSOIC peaks. These compounds exhibited variations in abundances (

The novel brominated flame retardants (NBFRs), bis(2-ethylhexyl)-2,3,4,5-tetrabromophthalate (TBPH) and 2-ethylhexyl-2,3,4,5 tetrabromobenzoate (TBB) are components of the flame retardant mixture Firemaster 550 and both TBPH and TBB have recently been listed as high production volume chemicals by the US EPA. These NBFRs have been detected in several environmental matrices but very little is known about their toxic effects or potencies. Results of in vitro assays demonstrated potentials of these NBFRs to modulate endocrine function through interactions with estrogen (ER) and androgen receptors (AR) and via alterations to synthesis of 17-β-estradiol (E2) and testosterone (T), but in vivo effects of these chemicals on organisms are not known. Therefore a 21-day short term fish fecundity assay with Japanese medaka (Oryzias latipes) was conducted to investigate if these NBFRs affect endocrine function in vivo. Medaka were fed a diet containing either 1422 TBPH:1474 TBB or 138:144μg/g food, wet weight (w/w). Cumulative production of eggs was used as a measure of fecundity and abundances of transcripts of 34 genes along the hypothalamus-pituitary-gonadal-liver (HPGL) axis were quantified to determine mechanisms of observed effects. Cumulative fecundity was impaired by 32% in medaka exposed to the greatest dose of the mixture of TBPH/TBB. A pattern of global down-regulation of gene transcription at all levels of the HPGL axis was observed, but effects were sex-specific. In female medaka the abundance of transcripts of ERβ was lesser in livers, while abundances of transcripts of VTG II and CHG H were greater. In male medaka, abundances of transcripts of ERα, ERβ, and ARα were lesser in gonads and abundances of transcripts of ERβ and ARα were lesser in brain. Abundances of transcripts of genes encoding proteins for synthesis of cholesterol (HMGR), transport of cholesterol (HDLR), and sex hormone steroidogenesis (CYP 17 and 3β-HSD) were significantly lesser in male medaka, which might have implications for concentrations of sex hormones. The results of this study demonstrate that exposure to components of the flame retardant mixture Firemaster® 550 has the potential to impair the reproductive axis of fishes.

Year-round monitoring for perfluoroalkyl acids (PFAAs) along the west coast of South Korea targeting long-term changes in water and coastal organisms has been conducted since 2008. In this study, we present the most recent 5-years of accumulated data and scrutinize the relationship between concentrations in water and biota highlighting bioaccumulation characteristics. Twelve individual PFAAs in samples of water (. n=. 43) and biota (. n=. 59) were quantified by use of HPLC-MS/MS after solid phase extraction. In recent years, concentrations of PFAAs in water have been generally decreasing, but profiles of relative concentrations of individual PFAAs vary among location and year. Bioaccumulation of PFAAs in various organisms including fishes, bivalves, crabs, gastropods, shrimps, starfish, and polychaetes varied among species. However, overall bioaccumulation of PFAAs was dependent on corresponding concentrations of PFAAs in water within an area. In organ-specific distributions of PFAAs, greater concentrations of PFAAs were found in intestine of fish (green eel goby). This result suggests that PFAAs are mainly accumulated via dietary exposure, while greater concentrations were found in gill and intestine of bivalve (oyster) which suggests both waterborne and dietary exposures to these organisms. Concentrations of PFAAs in biota did not decrease over time (2008-2010), indicating that continuing bioaccumulation followed by slow degradation or excretion of PFAAs accumulated in biota. Overall, spatio-temporal distributions of PFAAs in water and bioaccumulation characteristics seemed to be associated with recent restrictions of PFOS-based products and uses of PFBS-based substitutes.

Ultra-High Resolution LC/mass spectrometry (LC-UHRMS; Thermo Fisher Q-Exactive) was used to identify two novel isomers of hydroxylated bis(2-ethylhexyl)-tetrabromophthalate (OH-TBPH) which were unexpectedly observed in a commercial standard of TBPH. By combining ultra-high resolution (UHR) mass spectra (MS1), mass errors to theoretical [TBPH-Br+O]- were 2.1 and 1.0 ppm for the two isomers, UHR-MS2 spectra and NMR analysis; the structures of the two compounds were identified as hydroxylated TBPH with a hydroxyl group on the aromatic ring. Relatively great proportions of the two isomers of OH-TBPH were detected in two technical products, Firemaster 550 (FM-550; 0.1% and 6.2%, respectively) and Firemaster BZ 54 (BZ-54; 0.1% and 7.9%), compared to a commercial standard (0.4% and 0.9%). To simultaneously analyze OH-TBPH isomers and TBPH in samples of dust, a method based on LC-UHRMS was developed to quantify the two compounds, using negative and positive ion modes, respectively. The instrumental limit of detection for TBPH was 0.01 μg/L, which was 200-300 times better than traditional methods (2.5 μg/L) based on gas chromatography-mass spectrometry. The analytical method combined with a Florisil cleanup was successfully applied to analyze TBPH and OH-TBPH in 23 indoor dust samples from Saskatoon, Saskatchewan, Canada. Two OH-TBPH isomers, OH-TBPH1 and OH-TBPH2, were detected in 52% and 91% of dust samples, respectively. Concentrations of OH-TBPH2 (0.35 ± 1.0 ng/g) were 10-fold greater than those of OH-TBPH1 (0.04 ± 0.88 ng/g) in dust, which was similar to profiles in FM-550 and BZ-54. TBPH was also detected in 100% of dust samples with a mean concentration of 733 ± 0.87 ng/g. A significant (p < 0.001) log-linear relationship was observed between TBPH and OH-TBPH isomers, further supporting the hypothesis of a common source of emission. Relatively small proportions of OH-TBPH isomers were detected in dust (0.01% ± 0.67 OH-TBPH1 and 0.1% ± 0.60 OH-TBPH2), which were significantly less than those in technical products (p < 0.001). This result indicated different environmental behaviors of OH-TBPH and TBPH. Detection of isomers of OH-TBPH is important, since compounds with phenolic groups have often shown relatively greater toxicities than nonhydroxylated analogues. Further study is warranted to clarify the environmental behaviors and potential toxicities of OH-TBPH isomers.

Concentrations of 14 organophosphorus insecticides (OPs) were measured in Apis mellifera L. (European honeybee) and hive matrices (honey and bee bread). Samples were collected from seven randomly selected colonies in central Saskatchewan during the summer of 2013. LC-MS/MS was used to identify and quantify individual OP by use of a modified quick easy cheap effective rugged safe (QuEChERS) method. Diazinon, dimethoate, and chlorpyrifos-oxon were the only OPs detected in honey with mean concentrations of 0.3, 1.5, and 0.2 ng/g, wet mass (wm), respectively. Fenamiphos, chlorpyrifos, and chlorpyrifos methyl were the only OPs detected in bee bread, with mean concentrations of 0.4, 2.7, and 15.8 ng/g, wm, respectively, while ethoprop, malathion, and dichlorvos were the only OPs detected in bees with mean concentrations of 1.4, 3.7, and 889.2 ng/g, wm, respectively. Total hazard quotients (HQs), based on lethality of bees exposed to OPs in honey and pollen consumed by bees ranged from 0.01 to 0.06 and based on lethality of bees from direct exposure to OPs ranged from 0.3 to 0.4 which suggests little hazard of OPs to Saskatchewan beehives.

Narrow river-valley reservoirs are typically spatially heterogeneous. Little is known about how (a) water quality and algal community composition change longitudinally along a reservoir and (b) how algal composition and production change as a reservoir ages. To address these unknowns, multiple sediment cores were collected from mid-channel locations along the longitudinal axis of Lake Diefenbaker, Saskatchewan, Canada, a long, narrow river-valley reservoir on the Canadian Prairies. Profiles of concentrations of various pigments in sediment cores were measured to infer spatial and temporal trends in algal biomass and community composition. Diverse mixtures of pigments derived from filamentous and colonial cyanobacteria, diatoms, chlorophytes, and other phyla were observed. Spatial patterns of sedimentation of pigments (nmol m-2 yr-1) in surficial sediments suggest increases in algal biomass with distance down-reservoir, with maximum inferred biomass occurring in mid-reservoir. This is consistent with general knowledge of patterns of primary production in narrow, river-valley reservoirs. However, myxoxanthophyll, a biomarker of filamentous or colonial cyanobacteria, detected only at sites furthest down-reservoir, did not follow this general trend. Temporally, an increase in algal biomass occurred at down-reservoir locations after 1990, followed by a substantial increase after 2000 at the majority of sites. Profiles of concentrations of pigments exhibited no clear trends to support the prevailing paradigm that predicts an initial upsurge in trophic status upon formation of reservoirs. This pattern may result from limited penetration of light in the early years after reservoir formation. This study reinforces the need for paleolimnological analyses among hydrologic zones of large reservoirs.

Spatial distributions of perfluoroalkyl substances (PFASs) were investigated in surface waters in Shanghai, Jiangsu and Zhejiang Provinces of eastern China during 2011. A total of 39 samples of surface waters, including 29 rivers, 6 lakes and 4 reservoirs were collected. High performance liquid chromatography/negative electrospray ionization-tandem mass spectrometry (HPLC/(-)ESI-MS/MS) was used to identify and quantify PFASs. Concentrations of PFAS were greater in Shanghai than that in Zhejiang Province. Concentrations of the sum of PFASs (∑PFASs) in Shanghai and Kunshan ranged from 39 to 212ngL-1, while in Zhejiang Province, concentrations of ∑PFASs ranged from 0.68 to 146ngL-1. Perfluorooctanoic acid (PFOA) was the prevalent PFAS in Shanghai. In contrast, PFOA and perfluorohexanoic acid (PFHxA) were the prevalent PFASs in Zhejiang Province. Concentrations of perfluorooctane sulfonate (PFOS) ranged from

There is no clear single factor to date that explains colony loss in bees, but one factor proposed is the wide-spread application of agrochemicals. Concentrations of 14 organophosphorous insecticides (OPs) in honey bees (. Apis mellifera) and hive matrices (honey and pollen) were measured to assess their hazard to honey bees. Samples were collected during spring and summer of 2013, from 5 provinces in the middle delta of Egypt. LC/MS-MS was used to identify and quantify individual OPs by use of a modified Quick Easy Cheap Effective Rugged Safe (QuEChERS) method. Pesticides were detected more frequently in samples collected during summer. Pollen contained the greatest concentrations of OPs. Profenofos, chlorpyrifos, malation and diazinon were the most frequently detected OPs. In contrast, ethoprop, phorate, coumaphos and chlorpyrifos-oxon were not detected. A toxic units approach, with lethality as the endpoint was used in an additive model to assess the cumulative potential for adverse effects posed by OPs. Hazard quotients (HQs) in honey and pollen ranged from 0.01-0.05 during spring and from 0.02-0.08 during summer, respectively. HQs based on lethality due to direct exposure of adult worker bees to OPs during spring and summer ranged from 0.04 to 0.1 for best and worst case respectively. It is concluded that direct exposure and/or dietary exposure to OPs in honey and pollen pose little threat due to lethality of bees in Egypt.

While previous studies have found that unknown natural and synthetic organo-bromine compounds (NSOBCs) contributed more than 99% of the total organic bromine (Br) in the environment, there was no efficient method for untargeted screening to identify NSOBCs in environmental matrixes. A novel untargeted method for identifying NSOBCs, based on ultrahigh-resolution mass spectrometry (UHRMS) with the Q Exactive instrument was developed. This method included a data-independent precursor isolation and characteristic fragment (DIPIC-Frag) procedure to identify NSOBCs. A total of 180 successive 5-m/z-wide windows were used to isolate precursor ions. This resulted in a sufficient dynamic range and specificity to identify peaks of Br fragment ions for analysis. A total of 2520 peaks of NSOBC compounds containing Br were observed in sediments from Lake Michigan, United States. A new chemometric strategy which combined chromatographic profiles, isotopic peaks, precursor isolation window information, and intensities was used to identify precursor ions and chemical formulas for detecting NSOBCs. Precursor ions for 2163 of the 2520 NSOBCs peaks (86%) were identified, and chemical formulas for 2071 NSOBCs peaks (82%) were determined. After exclusion of isotopic peaks, 1593 unique NSOBCs were identified and chemical formulas derived for each. Most of the compounds identified had not been reported previously and had intensities which were 100- to 1000-fold greater than the congeners of polybrominated diphenyl ethers (PBDEs). In extracts of sediments, these compounds exhibited variations in intensities (

The use of snow and ice cores as recorders of environmental contamination is particularly relevant for per- and polyfluoroalky substances (PFASs) given their production history, differing source regions and varied mechanisms driving their global distribution. In a unique study perfluoroalkyl acids (PFAAs) were analyzed in dated snow-cores obtained from high mountain glaciers on the Tibetan Plateau (TP). One snow core was obtained from the Mt Muztagata glacier (accumulation period of 1980-1999), located in western Tibet and a second core from Mt. Zuoqiupo (accumulation period: 1996-2007) located in southeastern Tibet, with fresh surface snow collected near Lake Namco in 2010 (southern Tibet). The higher concentrations of ΣPFAAs were observed in the older Mt Muztagata core and dominated by perfluorooctanesulfonic acid (PFOS) (61.4-346 pg/L) and perfluorooctanoic acid (PFOA) (40.8-243 pg/L), whereas in the Mt Zuoqiupu core the concentrations were lower (e.g. PFOA: 37.8-183 pg/L) with PFOS below detection limits. These differences in PFAA concentrations and composition profile likely reflect the upwind sources affecting the respective sites (e.g. European/central Asian sources for Mt Muztagata and India sources for Mt Zuoqiupu). Perfluorobutanoic acid (PFBA) dominated the recent surface snowpack of Lake Namco which is mainly associated with India sources where the shorter chain volatile PFASs precursors predominate. The use of snow cores in different parts of Tibet provides useful recorders to examine the influence of different PFASs source regions and reflect changing PFAS production/use in the Northern Hemisphere. © 2013 American Chemical Society.

Total fluorine (TF), extractable organic fluorine (EOF) and poly- and per-fluorinated compounds (PFCs) were measured in eight dated cores of sediment taken along with 27 surface sediments from Lake Michigan in 2010. Based on rates of sedimentation, total concentrations of PFCs (∑PFCs) reached a maximum in the later 1990s and early 2000s. This result is consistent with rapid changes in production and subsequent sedimentation. Perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA) are still the predominant PFCs in the cores, but in surface sediments, concentrations of perfluorobutane sulfonate (PFBS) and perfluorobutanoic acid (PFBA) are now occurring at concentrations comparable to those of PFOS and PFOA. This observation is consistent with shifts in patterns of production and use in the US and Canada. Concentrations of TF in sediments were greater than those of EOF. This result is consistent with a larger proportion of un-extractable fluorinated material in both surface sediments and in cores. © 2014 Elsevier Ltd.

Ross Lake lies within the City of Flin Flon (Manitoba, Canada), a mining community originally formed by the Hudson Bay Mining and Smelting Company (now Hudbay Minerals Inc.) in 1927. At the time of this investigation, a continuous effluent stream from Hudbay Minerals (approximately 80years) and a discontinuous and unknown amount of raw and minimally treated municipal sewage (>20years, likely ending in 1951) was discharged into the north basin of the lake. Maximum concentrations of fecal sterols, such as coprostanol and terrestrial phytosterols, such as: β-sitosterol, campesterol, stigmastanol were measured in vertical sections of sediment cores, collected from Ross Lake, in the 15-16-cm section, which likely corresponds to the 1930s. Concentrations of coprostanol increased from 1, peaking at 3.6 are consistent with anecdotal information that municipal sewage was discharged into Ross Lake during the early years of urbanization, prior to changes in treatment of sewage and discharge practices that began in 1951. Finally, historical concentrations of terrestrial phytosterols followed trends similar to those of coprostanol and cholesterol and may possibly be the result of an increase in the flux of terrestrial organic matter into Ross Lake as the result of regional deforestation due to logging and fire. © 2013 Elsevier Ltd.

Per- and polyfluoroalkyl substances (PFAS) were measured systematically in a snowpack in northern Sweden to determine chemical behaviour during seasonal melt. Average PFAS concentrations were generally low, but displayed a wide range with median (range) concentrations of PFOA and PFOS of 66.5 pg L-1 (ND-122) and 20.5 pg L-1 (2.60-253) respectively. Average concentrations of the shorter chain, C4 and C5 perfluoroalkyl carboxylates (PFCAs) and perfluoroalkyl sulfonates (PFSAs), were ∼10-fold higher. Differences in the PFAS concentrations and profile were observed between surface snow and deeper layers, with evidence of PFAS migration to deeper snow layers as melt progressed. Chemical loads (ng m-2) for C4-9 PFCAs decreased gradually as melt progressed, but increased for C4, C6-8 PFSAs and the longer chain C10-12 PFCAs. This enrichment in the diminishing snowpack is an unusual phenomenon that will affect PFAS elution with meltwater and subsequent entry to catchment surface waters. © 2014 Elsevier B.V. All rights reserved.

Concentrations, distributions, fate, and partitioning of perfluoroalkyl acids (PFAAs) were investigated in surface water (n=34) collected from the Youngsan and Nakdong River Estuaries of South Korea. Thirteen individual PFAAs in water and suspended solids (SS) were quantified by use of HPLC-MS/MS. PFAAs were detected in all samples, which indicated that they were widely distributed in the study area. Greater concentrations of PFAAs were found at some inland sites which seemed to be affected by direct input from point sources, such as wastewater treatment plants, and/or indirect diffusive sources, such as surface runoff. Spatial distributions of PFAAs in estuaries along transects toward the open sea demonstrated that these chemicals were transported to the outer region primarily by water discharged during the rainy season. Field-based partition coefficients (Kd) for long-chain PFAAs (C≥8) were significantly correlated with salinity (r2=0.48 to 0.73, p

Environmental contextPerfluoroalkyl compounds are of rising environmental concern because of their ubiquitous distribution in remote regions like the Arctic. The present study quantifies these contaminants in the gas and particle phases of the Canadian Arctic atmosphere. The results demonstrate the important role played by gasparticle partitioning in the transport and fate of perfluoroalkyl compounds in the atmosphere. AbstractPolyfluoroalkyl compounds (PFCs) were determined in high-volume air samples during a ship cruise onboard the Canadian Coast Guard Ship Amundsen crossing the Labrador Sea, Hudson Bay and the Beaufort Sea of the Canadian Arctic. Five PFC classes (i.e. perfluoroalkyl carboxylates (PFCAs), polyfluoroalkyl sulfonates (PFSAs), fluorotelomer alcohols (FTOHs), fluorinated sulfonamides (FOSAs), and sulfonamidoethanols (FOSEs)) were analysed separately in the gas phase collected on PUF/XAD-2 sandwiches and in the particle phase on glass-fibre filters (GFFs). The method performance of sampling, extraction and instrumental analysis were compared between two research groups. The FTOHs were the dominant PFCs in the gas phase (20138pgm-3), followed by the FOSEs (0.423pgm-3) and FOSAs (0.54.7pgm-3). The PFCAs could only be quantified in the particle phase with low levels (0.040.18pgm-3). In the particle phase, the dominant PFC class was the FOSEs (0.38.6pgm-3). The particle-associated fraction followed the general trend of: FOSEs (∼25%)FOSAs (∼9%)FTOHs (∼1%). Significant positive correlation between ∑FOSA concentrations in the gas phase and ambient air temperature indicate that cold Arctic surfaces, such as the sea-ice snowpack and surface seawater could be influencing FOSAs in the atmosphere. © 2011 CSIRO.