A modified QuEChERS sample processing method for the determination of per- and polyfluoroalkyl substances (PFAS) in environmental biological matrices.

QuEChERS (quick, easy, cheap, effective, rugged, and safe) sample processing methods have previously been applied to a range of compounds and matrices. This study presents a modified QuEChERS sample processing method that was validated and employed for 24 per- and polyfluoroalkyl substances (PFAS) for various biological matrices. PFAS are a group of synthetic chemicals that have attracted substantial attention as some compounds are acknowledged to be persistent, toxic, and bioaccumulative. It is crucial to determine PFAS in diverse environmental matrices. Currently, limited sample processing methods for PFAS in biological matrices are available and the majority only focus on a few compounds such as perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA). Thus, there is a demand to develop a sample processing method which is effective for many commonly tested PFAS compounds in environmental biological samples. In this study, the detailed sample processing procedures and method performance are described. The highlights of this method are: •The extraction solvent and salts were adjusted for PFAS extraction from environmental biological matrices.•The modified QuEChERS method is effective for extraction and cleanup from a variety of matrices including algae, plants, invertebrates, amphibians, and fish.

Impacts of divalent cations (Mg2+ and Ca2+) on PFAS bioaccumulation in freshwater macroinvertebrates representing different foraging modes.

Per- and polyfluoroalkyl substances (PFAS) have extensively contaminated freshwater aquatic ecosystems where they can be transported in water and partition to sediment and biota. In this paper, three freshwater benthic macroinvertebrates with different foraging modes were exposed to environmentally relevant concentrations of eight perfluoroalkyl carboxylates (PFCA), three perfluoroalkyl sulfonates (PFSA), and three fluorotelomer sulfonates (FTS) at varying divalent cation concentrations of magnesium (Mg2+) and calcium (Ca2+). Divalent cations can impact PFAS partitioning to solids, especially to sediments, at higher concentrations. Sediment dwelling worms (Lumbriculus variegatus), epibenthic grazing snails (Physella acuta), and sediment-dwelling filter-feeding bivalves (Elliptio complanata) were selected due to their unique foraging modes. Microcosms were composed of synthetic sediment, culture water, macroinvertebrates, and PFAS and consisted of a 28-day exposure period. L. variegatus had significantly higher PFAS bioaccumulation than P. acuta and E. complanata, likely due to higher levels of interactions with and ingestion of the contaminated sediment. "High Mg2+" (7.5 mM Mg2+) and "High Ca2+" (7.5 mM Ca2+) conditions generally had statistically higher bioaccumulation factors (BAF) than the "Reference Condition" (0.2 mM Ca2+ and 0.2 mM Mg2+) for PFAS with perfluorinated chain lengths greater than eight carbons. Long-chain PFAS dominated the PFAS profiles of the macroinvertebrates for all groups of compounds studied (PFCA, PFSA, and FTS). These results indicate that the study organism has the greatest impact on bioaccumulation, although divalent cation concentration had observable impacts between organisms depending on the environmental conditions. Elevated cation concentrations in the microcosms led to significantly greater bioaccumulation in the test organisms compared to the experimental reference conditions for long-chain PFAS.

Spatial and temporal variability of per- and polyfluoroalkyl substances (PFAS) in environmental media of a small pond: Toward an improved understanding of PFAS bioaccumulation in fish.

Per- and polyfluoroalkyl substances (PFAS) are highly fluorinated compounds with many industrial applications, for instance as ingredients in fire-suppressing aqueous film-forming foams (AFFF). Several PFAS have been demonstrated to be persistent, bioaccumulative and toxic. This study better characterizes the bioaccumulation of PFAS in freshwater fish through a spatial and temporal analysis of surface water and sediment from a stormwater pond in a former Naval air station (NAS) with historic AFFF use. We sampled environmental media from four locations twice per week for five weeks and sampled fish at the end of the sampling effort. The primary PFAS identified in surface water, sediment, and biota were perfluorooctane sulfonate (PFOS) and perfluorohexane sulfonate (PFHxS) followed by perfluorooctanoic acid (PFOA) in environmental media and perfluoroheptane sulfonate (PFHpS) in biota. We observed significant temporal variability in surface water concentrations at the pond headwaters following stochastic events such as heavy rainfall for many compounds, particularly PFHxS. Sediment concentrations varied most across sampling locations. In fish, liver tissue presented the highest concentrations for all compounds except PFHxS, which was highest in muscle tissue, suggesting the influence of fine-scale aqueous PFAS fluctuations on tissue distribution. Calculated log bioaccumulation factors (BAFs) ranged from 0.13 to 2.30 for perfluoroalkyl carboxylates (PFCA) and 0.29-4.05 for perfluoroalkane sulfonates (PFSA) and fluctuated greatly with aqueous concentrations. The variability of PFAS concentrations in environmental media necessitates more frequent sampling efforts in field-based studies to better characterize PFAS contamination in aquatic ecosystems as well as exercising caution when considering single time-point BAFs due to uncertainty of system dynamics.

Resonance coupling between chiral quasi-BICs and achiral molecular excitons in dielectric metasurface J-aggregate heterostructures.

The realization of flexible tuning and enhanced chiral responses is vital for many applications in nanophotonics. This study proposes to manipulate the collective optical responses with heterostructures consisting of chiral dielectric metasurfaces and achiral J-aggregates. Owing to the resonance coupling between the chiral quasi-bound states in the continuum (QBICs) and the achiral exciton mode, large mode splitting and anticrossing are observed in both the transmission and circular dichroism (CD) spectra, which indicates the formation of hybrid chiral eigenmodes and the realization of the strong coupling regime. Considering that the radiative and dissipative damping of the hybrid eigenmodes depends on the coherent energy exchange, the chiral resonances can be flexibly tuned by adjusting the geometry and optical constants for the heterostructure, and the CD of the three hybrid eigenmodes approach the maximum (∼1) simultaneously when the critical coupling conditions are satisfied, which can be promising for enhanced chiral light-matter interactions.

Bioaccumulation of per- and polyfluoroalkyl substances by freshwater benthic macroinvertebrates: Impact of species and sediment organic carbon content.

Per- and polyfluoroalkyl substances (PFAS) in aquatic environments have caused global concern due to their persistence, toxicity, and potential bioaccumulation of some compounds. As an important compartment of the aquatic ecosystem, sediment properties impact PFAS partitioning between aqueous and solid phases, but little is known about the influence of sediment organic carbon content on PFAS bioaccumulation in benthic organisms. In this study, three freshwater benthic macroinvertebrates - worms (Lumbriculus variegatus), mussels (Elliptio complanata) and snails (Physella acuta) - were exposed for 28 days to PFAS spiked synthetic sediment equilibrated with a synthetic surface water. Using microcosms, sediment organic carbon content - 2%, 5% and 8% - was manipulated to assess its impact on PFAS bioaccumulation. Worms were found to have substantially greater PFAS bioaccumulation compared to mussels and snails. The bioaccumulation factors (BAFs) and biota sediment accumulation factors (BSAFs) in worms were both one to two magnitudes higher than in mussels and snails, likely due to different habitat-specific uptake pathways and elimination capacities among species. In these experiments, increasing sediment organic carbon content decreased the bioaccumulation of PFAS to benthic macroinvertebrates. In worms, sediment organic carbon content was hypothesized to impact PFAS bioaccumulation by affecting PFAS partitioning and sediment ingestion rate. Notably, the BSAF values of 8:2 fluorotelomer sulfonic acid (FTS) were the largest among 14 PFAS for all species, suggesting that the benthic macroinvertebrates probably have different metabolic mechanisms for fluorotelomer sulfonic acids compared to fish evaluated in published literature. Understanding the impact of species and sediment organic carbon on PFAS bioaccumulation is key to developing environmental quality guidelines and evaluating potential ecological risks to higher trophic level species.

Exposure pathways and bioaccumulation of per- and polyfluoroalkyl substances in freshwater aquatic ecosystems: Key considerations.

Due to the bioaccumulative behavior, toxicity, and recalcitrance to degradation, per- and polyfluoroalkyl substances (PFAS) are a focus for many researchers investigating freshwater aquatic ecosystems. PFAS are a diverse set of chemicals that accumulate and transport quite differently in the environment depending on the length of their fluoroalkyl chains and their functional groups. This diversity in PFAS chemical characteristics combined with varying environmental factors also impact the bioaccumulation of these compounds in different organisms. In this review, we evaluate environmental factors (such as organic carbon, proteins, lipids, and dissolved cations) as well as PFAS characteristics (head group, chain-length, and concentration) that contribute to the significant variation seen in the literature of bioaccumulation metrics reported for organisms in aquatic ecosystems. Of the factors evaluated, it was found that PFAS concentration, dissolved organic matter, sediment organic matter, and biotransformation of precursor PFAS tended to significantly impact reported bioaccumulation metrics the most. Based on this review, it is highly suggested that future studies provide sufficient details of important environmental factors, specific organism traits/ behavior, and PFAS concentrations/compounds when reporting on bioaccumulation metrics to further fill data gaps and improve our understanding of PFAS in aquatic ecosystems.

Concentrations, distribution, sources, and ecological risk assessment of heavy metals in agricultural topsoil of the Three Gorges Dam region, China.

Concentrations, distribution, sources, and ecological risk of seven heavy metals including chromium (Cr), nickel (Ni), copper (Cu), zinc (Zn), lead (Pb), cadmium (Cd), and mercury (Hg) in agricultural topsoil samples of the Three Gorges Dam region, China were investigated in this study. Among seven heavy metals, Zn had the highest mean concentration (149 mg kg(-1)) in the agricultural topsoil, followed by Cr (66 mg kg(-1)), Cu (52.2 mg kg(-1)), Pb (13.0 mg kg(-1)), Ni (8.5 mg kg(-1)), Cd (0.29 mg kg(-1)), and Hg (0.08 mg kg(-1)). Enrichment factor (EF) values of Zn, Cu, Cd, and Hg were higher than 1.5, indicating that Zn, Cu, Cd, and Hg were the major pollutants in this study area. The average potential ecological risk index (RI) value was 147, suggesting that heavy metals in the agricultural topsoil in the study area had a low ecological risk. The result of factor analysis (FA) and correlation analysis showed that long-term use of chemical fertilizer and pesticides, natural rock weathering, and atmospheric deposition were the several main sources of seven heavy metals in agricultural topsoil of the Three Gorges Dam region. Factor analysis-multiple linear regression (FA-MLR) results indicated that the most important source in this area was long-term use of chemical fertilizer and pesticides, which contributed 70 % for Cu and Zn, 62 % for Cd, and 72 % for Hg. More attention must be paid to the extensive use of chemical fertilizers and pesticides containing heavy metals which have been accumulated in the agricultural soil.

Concentrations and risk assessment of polychlorinated biphenyls and polybrominated diphenyl ethers in surface sediments from the East Lake, China.

The concentrations of polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) in surface sediment samples collected from the East Lake, China in winter 2012 and summer 2013 were analyzed in this study. The total PCB and PBDE concentrations ranged from not detected to 107.1 ng g(-1) dw and from 9.7 to 151.3 ng g(-1) dw, respectively. PCB-28, 101 and 180 were dominant congeners in both winter and summer. BDE-28 (44 %) was the dominant congener in winter and summer, followed by BDE-99 (28 %) and BDE-47 (26 %). The concentrations of PCBs in the sediment samples collected in summer were higher than those in winter, while the concentrations of PBDEs did not show much seasonal variations. Source analysis showed that the PCBs probably originated from urban runoff, industrial pollution and atmospheric deposition, and the PBDEs probably originated from historical usage of penta-BDE mixtures. Potential eco-toxicological risks caused by PCBs were found in about 5 % of the sampling sites; PBDEs had moderate eco-toxicological risk in 80 % sampling sites in the East Lake, China.

Distribution, potential source and ecotoxicological risk of polychlorinated biphenyls and polybrominated diphenyl ethers in the surface water of the Three Gorges Dam region of the Yangtze River, China.

Distributions, potential sources and ecotoxicological risks of PCBs and PBDEs in surface water of the Three Gorges Dam (TGD) region (Yangtze River, China) were investigated. Samples were collected from 18 sites from upstream (UTGD) and downstream (DTGD) of the TGD. Thirty-two PCBs and ten PBDEs were analyzed. ΣPCBs from the UTGD and DTGD ranged from 10.6 to 26.1 and 1.7 to 29.8 ng L(-1), respectively. ΣPBDEs from the UTGD and DTGD ranged from 2.0 to 17.6 and 0.8 to 11.1 ng L(-1), respectively. The total concentrations of PCBs and PBDEs showed a declining trend from the UTGD to DTGD. Independent-samples t test analysis showed no statistical significance of ΣPCBs and ΣPBDEs between the UTGD and DTGD samples. Principal component analysis indicated the difference of potential sources and levels of PCBs and PBDEs in the study area. The potential eco-toxicological risk of PCBs in surface water of the TGD region is very low, whereas special attention needs to be paid to PBDEs in the study area.

Distribution and ecological risk assessment of organochlorine pesticides in surface sediments from the East Lake, China.

Organochlorine pesticides (OCPs) are ubiquitous pollutants, and their presence in urban lakes is a concern for human and ecological health. Surface sediments in the East Lake, China, were collected in winter 2012 and summer 2013 to investigate concentrations, distribution patterns, possible sources, and potential ecological risks of OCPs in this area. The total concentrations of 14 OCPs ranged from 6.3 to 400 ng g(-1) dry weight (dw) with an average concentration of 79 ng g(-1) dw. The mean values of hexachlorocyclohexanes (HCHs) (α-, ß-, γ-, and δ-HCH) and dichlorodiphenyltrichloroethanes (DDTs) (p,p'-DDE, p,p'-DDD, and p,p'-DDT) were 36 and 7.6 ng g(-1) dw, accounting for 45 and 10 % of the total OCPs, respectively. The concentrations of OCPs in sediment samples collected in winter were significantly higher than those in summer, especially the HCHs, of which in winter were two times greater than summer. Composition analyses indicated that DDTs and endosulfan were mainly from historical contribution. Historical use of technical HCH and new input of lindane were probably the source of HCHs in the East Lake. Most sampling sites of HCHs and DDTs were found to have the potential ecological risk based on levels specified in the sediment quality standards.

Occurrence, distribution and seasonal variations of polychlorinated biphenyls and polybrominated diphenyl ethers in surface waters of the East Lake, China.

Polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) in the surface water of the East Lake, China were investigated in winter (2012) and summer (2013). A hundred and eight samples were collected from 36 sampling sites and analyzed for the 31 PCB and 10 PBDE congeners. Concentrations of both PCBs and PBDEs showed obvious seasonal variations. The average PCB concentrations in the East Lake ranged from 3.17 to 6.09 ng L(-1) in winter and 0.19 to 0.99 ng L(-1) in summer. CB-44, 105, 118 and 179 were dominant in both winter and summer. The average PBDE concentrations in the East Lake ranged from 2.92 to 5.54 ng L(-1) in winter and 0.67 to 1.51 ng L(-1) in summer. BDE-47 was predominant in both winter and summer, which accounted for more than 37% of the total PBDEs concentration from all sampling sites. Independent-Samples t-test showed statistical significance of ΣPCBs and ΣPBDEs between winter and summer samples. The analysis of distribution, pattern and seasonal variations indicated the different potential sources of PCBs and PBDEs in the East Lake. The potential eco-toxicological risk was also discussed in the study.

Distribution and ecological assessment of heavy metals in surface sediments of the East Lake, China.

Concentrations and risk assessment of chromium (Cr), nickel (Ni), copper (Cu), zinc (Zn), arsenic (As), lead (Pb), cadmium (Cd) and mercury (Hg) were investigated in 106 samples of surface sediments from the East Lake, China in this study. The mean concentration of Zn was highest among the eight heavy metals (225 mg kg(-1)), followed by As (191 mg kg(-1)), Cr (145 mg kg(-1)), Cu (55 mg kg(-1)), Ni (27.1 mg kg(-1)), Pb (7.93 mg kg(-1)), Cd (0.94 mg kg(-1)) and Hg (0.21 mg kg(-1)). Niuchao Hu was less polluted by heavy metals compare to the other four lakelets of the East Lake. The correlations among these heavy metals and the results of principal component analysis indicated that the distribution of Cd, Pb and Hg was related to anthropogenic activities, whereas Cu, As and Cr were affected by the parent rocks. Zinc and Ni were influenced both by anthropogenic activities and parent rocks. Based on the Sediment Quality Guidelines, the results of toxicity assessment indicated that adverse effects caused by Cr and As would be expected frequently. Nickel, Zn, Cd and Hg may cause adverse effects occasionally and Cu and Pb may cause toxicity infrequently. Arsenic was found to have the highest acute toxicity by toxic units (TUs), followed by Cr, Ni, Zn, Hg, Cu, Cd and Pb. The potential ecological risk index analysis indicated that As, Cd and Hg had considerable or high ecological risk, whereas Cr, Ni, Cu, Zn and Pb had low ecological risk. The potential ecological risk index (RI) of the heavy metals in the surface sediments of East Lake was 483, indicating considerable ecological risk. Close attention should be paid to pollution of the heavy metals in East Lake, China.

Concentrations, distributions, sources, and risk assessment of organochlorine pesticides in surface water of the East Lake, China.

East Lake resides in the urban area of Wuhan City and is the largest urban lake in China. The concentrations of 16 organochlorine pesticides (OCPs) were analyzed in 108 surface water samples collected from the East Lake. The total concentrations of OCPs ranged from not detected to 120 ng L(-1) with predominance of δ-HCH, heptachlor, and α-HCH. The mean values of HCHs and DDTs were 7.40 and 5.70 ng L(-1), respectively, accounting for 40 and 31 % of the total OCPs. For the five lakelets in East Lake, Houhu Lake exhibited the highest concentrations of HCHs, DDTs, and total OCPs, which has been used actively for fisheries and surrounded by suburban rural areas and farmlands. Historical lindane or technical HCH input was probably the source of HCH, while technical DDTs might be the source of DDT in the East Lake. The ratio between heptachlor and its metabolic products indicated recent input of heptachlor. Although the combining ecological risks for all aquatic species in the East Lake calculated by species sensitivity distribution reached approximately 10(-5), the OCPs in the East Lake had slight effects on aquatic organisms. The carcinogenic risks and non-carcinogenic hazard indices of DDTs and HCHs indicated that water in the East Lake was not suitable as water sources for human. However, the results indicated the water quality was safe for people to swim in the urban lake.