Pyrethroids are an important class of insecticides, and thousands of tons of these compounds are used in the United States every year. This study characterized exposures to pyrethroids and assessed demographic, socioeconomic, and lifestyle factors that modulate pyrethroid exposure using data from the National Health and Nutrition Examination Survey (NHANES) 2007–2012, a nationally representative survey of the non-institutionalized population of the United States. Urinary levels of commonly used biomarkers of pyrethroid exposure, including 3-phenoxybenzoic acid (3-PBA), 4-fluoro-3-phenoxybenzoic acid (F-PBA), and cis-dibromovinyl-dimethylcyclopropane carboxylic acid (DBCA), were determined by liquid chromatography-tandem mass spectrometry. The detection rate of 3-PBA, a nonspecific metabolite of several pyrethroids, was 78.1% in adults (N = 5233) and 79.3% in children (N = 2295). The detection rates of all other pyrethroid metabolites were <10%. The median urinary level of 3-PBA in adults was 0.47 μg/L (interquartile range, 0.14–1.22 μg/L). For children, the median urinary level was 0.49 μg/L (interquartile range, 0.17–1.29 μg/L). Age, gender, family income-to-poverty ratio (PIR), levels of physical activity, alcohol intake, and body mass index were associated with 3-PBA levels in adults. In children, age, gender, race/ethnicity, and PIR were associated with 3-PBA levels. 3-PBA levels also differed significantly across NHANES cycles, with higher levels observed in NHANES 2011–2012. Geometric mean 3-PBA levels in U.S. adults were 0.41 μg/L in NHANES 2007–2008, 0.41 μg/L in NHANES 2009–2010, and 0.66 μg/L in NHANES 2011–2012. In U.S. children, geometric mean 3-PBA levels were 0.40 μg/L in NHANES 2007–2008, 0.46 μg/L in NHANES 2009–2010, and 0.70 μg/L in NHANES 2011–2012. These results demonstrate that pyrethroid exposures remain a current environmental health concern and lay the foundation for further preclinical and epidemiological studies assessing human health risks associated with pyrethroids.

We investigated the profiles and levels of perfluoroalkyl carboxylic acid (PFCA) contamination in Pacific cod (Gadus macrocephalus) from the North Pacific Ocean. The mean concentrations of PFCAs containing 8 to 14 carbon atoms (C8–C14) in edible Pacific cod muscle ranged from 216 to 670 pg g⁻¹ wet weight in the Northeast Pacific Ocean (Seattle, Vancouver, Alaska, and Russia), from 819 to 1710 pg g⁻¹ wet weight in Japanese coastal waters (Hokkaido, Aomori, Iwate, Miyagi, Tottori, and Shimane), and from 288 to 892 pg g⁻¹ wet weight in Korean waters (Sokcho, Busan, and Yeosu). These results indicate there are geographical differences in the distribution of PFCAs. The long-chain PFCAs (C9–C14) contributed 96% of the total PFCA concentration across Japan, whereas they contributed only 33% of the total PFCA concentration in the USA and Canada. Long-chain PFCA concentrations in cod samples collected in Japanese and Korean waters were about three to four times those in samples from the USA, Canada, and Russia. Because seafood is considered an important dietary source of PFCAs, high concentrations of long-chain PFCAs in Pacific cod from Japanese and Korean waters may affect human dietary exposure and blood concentrations of long-chain PFCAs.

Perfluoroalkyl substances (PFASs) are a family of synthetic, fluorinated organic compounds. They have been widely used in industrial applications and consumer products and widespread in the environment, wildlife and human. Experimental and epidemiologic evidence suggested that PFASs are capable of interfering with endocrine processes and have potential reproductive and developmental toxicities. Polycystic ovarian syndrome (PCOS), one of the main reasons of female infertility, is a common endocrine disorder in reproductive age women. We performed a case-control study to evaluate associations between PCOS-related infertility and PFASs concentrations in plasma. A total of 180 infertile PCOS-cases and 187 healthy controls were recruited from the Center for Reproductive Medicine of Shandong University. Blood specimens were collected at enrollment and analyzed for ten PFASs using liquid chromatography-tandem mass spectrometry. Multivariable logistic regression procedure was used to estimate odds ratios (ORs) and 95% confidence intervals (CIs) for each PFAS. Perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) were the dominant PFASs in the plasma of participants, with the median concentration of 5.07 ng/mL and 4.05 ng/mL, respectively. The median levels of individual PFAS were not significantly different between PCOS-cases and controls. While adjusted for the potential confounders (age, BMI, household income, education level, employment status, age at menarche, menstrual volume), the plasma concentration of perfluorododecanoic acid (PFDoA), a 12 carbons lengths of perfluorocarboxylic acids, was associated with a significantly increased risk of PCOS-related infertility (medium vs low tertile: OR = 2.36, 95% CI: 1.12, 4.99, P = 0.02; high vs low tertile: OR = 3.04, 95% CI: 1.19, 7.67, P = 0.02), with the P trend 0.01. No significant relationship was observed between PCOS-related infertility and other PFAS analytes in the adjusted model, despite perfluoroundecanoic acid showed a negative association (P trend 0.03). The potential reproductive health effects of PFASs and the underlying mechanisms merit further investigation in the future.

The bioaccumulation and biomagnification of 22 major perfluoroalkyl substances (PFAS) were investigated in tissues of polar bears (Ursus maritimus) and their major prey species, the ringed seal (Pusa hispida), from the Scoresby Sound region of East Greenland. In polar bear liver the mean Σ4PFSA (perfluoroalkyl sulfonic acid) concentration (C4, C6, C8 and C10) was 2611 ± 202 ng/g wet weight (ww; 99% perfluorooctane sulfonate (PFOS)) and two orders of magnitude higher than the 20 ± 3 ng/g ww (89% PFOS) concentration in fat. The mean Σ4PFSAs in seal liver was 111 ± 5 ng/g ww (98% PFOS) and three orders of magnitude higher relative to the 0.05 ± 0.01 ng/g ww concentration in blubber (100% perfluorohexane sulfonate). Perfluoro-1-octane sulfonamide (FOSA) was quantifiable in bear (mean 10 ± 1.4 ng/g ww) and seal (mean 0.6 ± 0.1 ng/g ww) liver but not in fat or blubber. The mean Σ13PFCAs (C4–C18; perfluoroalkyl carboxylic acids) in bear liver (924 ± 71 ng/g ww) was much greater than in seal liver (74 ± 6 ng/g ww). In bear fat and seal blubber, the mean Σ13PFCAs were 15 ± 1.9 and 0.9 ± 0.1 ng/g ww, respectively. Longer chain C11 to C14 PFCAs dominated in bear fat and seal blubber (60–80% of Σ13PFCA), whereas shorter-chain C9 to C11 PFCAs dominated in the liver (85–90% of Σ13PFCA). Biomagnification factors (BMFs) were orders of magnitude greater for PFHxS and C9 to C13 PFCAs when based on bear liver to seal blubber rather than bear liver to seal liver, and PFCA (C9 to C13) BMFs decreased with increasing chain length. Seal blubber to bear liver BMFs better reflects the dietary exposure relationship of PFAS between bears and seals.

Microalgae are widely used as representative primary producers in ecotoxicology, while macrophytes are much less studied. Here we compared the bioavailability and cellular toxicity pathways of 2 h-exposure to 10−6 mol L−1 Cu in the macrophyte Elodea nuttallii and the green microalga Chlamydomonas reinhardtii.Uptake rate was similar but faster in the algae than in the macrophyte, while RNA-Sequencing revealed a similar number of regulated genes. Early-regulated genes were congruent with expected adverse outcome pathways for Cu with Gene Ontology terms including gene regulation, energy metabolism, transport, cell processes, stress, antioxidant metabolism and development. However, the gene regulation level was higher in E. nuttallii than in C. reinhardtii and several categories were more represented in the macrophyte than in the microalga. Moreover, several categories including oxidative pentose phosphate pathway (OPP), nitrate metabolism and metal handling were only found for E. nuttallii, whereas categories such as cell motility, polyamine metabolism, mitochondrial electron transport and tricarboxylic acid cycle (TCA) were unique to C. reinhardtii. These differences were attributed to morphological and metabolic differences and highlighted dissimilarities between a sessile and a mobile species. Our results highlight the efficiency of transcriptomics to assess early molecular responses in biota, and the importance of studying more aquatic plants for a better understanding on the impact and fate of environmental contaminants.

Plastic debris has become an environmental problem during recent years. Among the plastic debris, microplastics (<5 mm; MPLs) imply an extra problem due to their capacity to enter into the fauna through ingestion. In this work, we study the capacity of three MPLs, that include high-density polyethylene (HDPE), polystyrene (PS) and polystyrene carboxylate (PS-COOH), to sorb 18 perfluoroalkyl substances (PFASs; including carboxylic acids, sulphonates and one sulphonamide) from the surrounding waters (freshwater and seawater).Conclusions drawn from the results are that perfluoro sulphonates and sulphonamides have more tendency to be sorbed onto MPLs. In addition, PS and PS-COOH have more affinity for PFASs than HDPE. Finally, the increment of conductivity and pH of the water decreases the exposure time that is necessary to reach equilibrium. However, the presence of salts decreases the tendency of PFASs to be sorbed onto plastic surfaces. These results highlight the problem associated with the presence of MPLs in inland and marine waters since toxic compounds can be sorbed onto surrounding plastics that could be ingested by aquatic fauna.

The impact of point and diffuse sources for 26 per- and polyfluoroalkyl substances (PFASs) in northern Europe were investigated by studying Swedish rivers (n = 40) and recipient seawater (Baltic Sea and Kattegat; n = 18). Different composition profiles were observed in the rivers, with ten rivers having a remarkably high fraction of perfluoroalkane sulfonic acids (PFSAs; 65% of the ƩPFASs) as compared to other rivers (19%) suggesting major impact of one or several source types dominated by PFSAs. Population density and low latitude (south) were strongly correlated to the widely used perfluorooctanesulfonic acid (PFOS), perfluorooctanoic acid (PFOA) as well as to perfluorohexanesulfonic acid (PFHxS). Significant relationships between several PFCAs and PFSAs (i.e. perfluorobutanoic acid (PFBA), perfluoroheptanoic acid (PFHpA), PFOA, perfluorobutanesulfonic acid (PFBS), and PFHxS) and dissolved organic carbon (DOC) were detected (p < 0.05), indicating chemical binding and co-transport with DOC in fresh water and seawater. Partial least squares regression analysis showed that perfluoroalkyl carboxylic acids (PFCAs) were related to latitude according to their perfluorocarbon chain length (C3, C7, C8, C9, C10 and C11), with longer chains associated with higher latitudes. This suggests the presence of mechanisms promoting higher prevalence of longer chained PFCAs in the north, e.g. precursor degradation, and/or aerosol associated stabilization of PFCAs and their precursors.

Per- and polyfluoroalkyl substances (PFASs) were detected in the atmosphere of a source region in Tianjin, China. Fluorotelomer alcohols (FTOHs) were the dominant neutral PFASs in the atmosphere with total concentrations of 93.6-131 pg/m3 and 8:2 FTOH contributing the most, whereas perfluorooctane sulfonamide derivatives (PFOSAs) were two magnitudes lower or undetected. In comparison, ionic PFASs (perfluoroalkyl carboxyl acids (PFCAs)) in the atmosphere were detected at similar or even higher levels. At wastewater treatment plants (WWTPs), the air over influent was found with higher levels of FTOHs than over aeration tank and effluent; whereas in the air over the aeration tank, the concentrations of PFOSAs and nonvolatile ionic PFASs substantially increased, suggesting a possible direct release of ionic PFASs to the atmosphere besides the atmospheric conversion from volatile precursors. In the air phase, a low proportion (1-5%) of PFCAs was subjected to dry deposition in the source region. Interestingly, the dry-deposition-to-bulk-air ratios of PFCA analogues were the lowest at medium chain lengths (C8 and C9) and increased with either shorter or longer chain length. The extraordinary affinity of shorter-chain PFCAs (C6-C7) to particles was presumed to be due to their smaller molecular size favoring the interactions between the carboxyl head groups and specific sorption sites on particulate matter.

The aim of this study was to gain an understanding of the transport of C4–10 perfluoroalkyl carboxylic acids (PFCAs) and C4,6,8 perfluoroalkyl sulfonic acids (PFSAs) in a water-saturated sediment column representing a riverbank filtration scenario under near-natural conditions. Short-chain PFCAs and PFSAs with up to six C-atoms showed complete tracer-like breakthrough. Longer chain ones were retarded due to sorption to the sediment or due to other processes in the aqueous phase. The study reports the first column derived sediment–water partition coefficients ranging from 0.01 cm3 g−1 to 0.41 cm3 g−1 for C4,6 PFSAs and from 0.0 cm3 g−1 to 6.5 cm3 g−1 for C4,5,6,8,9 PFCAs. The results clearly indicate that short-chain PFCAs and PFSAs may pose a problem if contaminated surface waters are used for drinking water production via riverbank filtration.

Naphthenic acids (NA) are used in a variety of commercial and industrial applications, and are primary toxic components of oil sands wastewater. We investigated developmental and metabolic responses of tadpoles exposed to sub-lethal concentrations of a commercial NA blend throughout development. We exposed Lithobates pipiens tadpoles to 1 and 2 mg/L NA for 75 days and monitored growth and development, condition factor, gonad and liver sizes, and levels of liver glucose, glycogen, lipids and cholesterol following exposure. NA decreased growth and development, significantly reduced glycogen stores and increased triglycerides, indicating disruption to processes associated with energy metabolism and hepatic glycolysis. Effects on liver function may explain reduced growth and delayed development observed in this and previous studies. Our data highlight the need for greater understanding of the mechanisms leading to hepatotoxicity in NA-exposed organisms, and indicate that strict guidelines may be needed for the release of NA into aquatic environments.