PFAS in fish from AFFF-impacted environments: Analytical method development and field application at a Canadian international civilian airport.

Methods targeting anionic per- and polyfluoroalkyl substances (PFAS) in aquatic biota are well established, but commonly overlook many PFAS classes present in aqueous film-forming foams (AFFFs). Here, we developed an analytical method for the expanded analysis of negative and positive ion mode PFAS in fish tissues. Eight variations of extraction solvents and clean-up protocols were first tested to recover 70 AFFF-derived PFAS from the fish matrix. Anionic, zwitterionic, and cationic PFAS displayed the best responses with methanol-based ultrasonication methods. The response of long-chain PFAS was improved for extracts submitted to graphite filtration alone compared with those involving solid-phase extraction. The validation included an assessment of linearity, absolute recovery, matrix effects, accuracy, intraday/interday precision, and trueness. The method was applied to a set of freshwater fish samples collected in 2020 in the immediate vicinity (creek, n = 15) and downstream (river, n = 15) of an active fire-training area at an international civilian airport in Ontario, Canada. While zwitterionic fluorotelomer betaines were major components of the subsurface AFFF source zone, they were rarely detected in fish, suggesting limited bioaccumulation potential. PFOS largely dominated the PFAS profile, with record-high concentrations in brook sticklebacks (Culaea inconstans) from the creek (16000-110,000 ng/g wet weight whole-body). These levels exceeded the Canadian Federal Environmental Quality Guidelines (FEQG) for PFOS pertaining to the Federal Fish Tissue Guideline (FFTG) for fish protection and Federal Wildlife Diet Guidelines (FWiDG) for the protection of mammalian and avian consumers of aquatic biota. Perfluorohexane sulfonamide and 6:2 fluorotelomer sulfonate were among the precursors detected at the highest levels (maximum of ∼340 ng/g and ∼1100 ng/g, respectively), likely reflecting extensive degradation and/or biotransformation of C6 precursors originally present in AFFF formulations.

Suspect screening of pharmaceuticals, illicit drugs, pesticides, and other emerging contaminants in Argentinean Piaractus mesopotamicus, a fish species used for local consumption and export.

The widespread distribution of contaminants of emerging concern (CECs) is a major concern due to their potential effects on human health and the environment. The insufficient sewage treatment plant infrastructures is a global problem most accentuated in less developed countries and results in the discharge of CECs to water bodies. Pacu (Piaractus mesopotamicus) is a ray-finned freshwater fish species native to the Paraná basin. It is also the most produced aquaculture fish species in Argentina since 2012. Though uninvestigated to date, the occurrence of CECs in pacu may be of high relevance due to production volumes and relevance to human exposure through fish consumption. In this study, we applied a high-resolution mass spectrometry screening method to qualitatively analyze over 100 CECs in pacu. Four extraction/cleanup methods were tested on pooled pacu fillet, including solid-phase extraction and QuEChERS. The method that produced the highest number of detections was selected for further analysis of pacu purchased in supermarkets and fish markets in Argentina between 2017 and 2020. Residues of pesticides, antibiotics, pharmaceuticals, personal care products, plasticizers, sweeteners, drug metabolites, stimulants, and illegal drugs were detected in the samples. A total of 38 CECs were detected, ranging between 24 and 35 CECs per individual sample. 100% of the samples had positive detections of caffeine, 1,7-dimethylxanthine, xanthine, benzoylecgonine, methylparaben, ethylparaben, bis(2-ethylhexyl) phthalate (DEHP), metolachlor, carbendazim, salicylic acid, 2,4-D, saccharin, cyclamate, and dodecanedioic acid. Mappings generated with correspondence analysis were used to explore similarities/dissimilarities among the detected compounds. To our knowledge this is the first report of saccharin, cyclamate, 2,4 - D, carbendazim, metolachlor, ethylparaben, propylparben, bisphenol A, DEHP, and benzotriazole in fish from Argentina, and the first report on the presence of lisinopril, metropolol acid and dodecanedioic acid in fish worldwide.

Occurrence of BMAA Isomers in Bloom-Impacted Lakes and Reservoirs of Brazil, Canada, France, Mexico, and the United Kingdom.

The neurotoxic alkaloid ß-N-methyl-amino-l-alanine (BMAA) and related isomers, including N-(2-aminoethyl glycine) (AEG), ß-amino-N-methyl alanine (BAMA), and 2,4-diaminobutyric acid (DAB), have been reported previously in cyanobacterial samples. However, there are conflicting reports regarding their occurrence in surface waters. In this study, we evaluated the impact of amending lake water samples with trichloroacetic acid (0.1 M TCA) on the detection of BMAA isomers, compared with pre-existing protocols. A sensitive instrumental method was enlisted for the survey, with limits of detection in the range of 5−10 ng L−1. Higher detection rates and significantly greater levels (paired Wilcoxon's signed-rank tests, p < 0.001) of BMAA isomers were observed in TCA-amended samples (method B) compared to samples without TCA (method A). The overall range of B/A ratios was 0.67−8.25 for AEG (up to +725%) and 0.69−15.5 for DAB (up to +1450%), with absolute concentration increases in TCA-amended samples of up to +15,000 ng L−1 for AEG and +650 ng L−1 for DAB. We also documented the trends in the occurrence of BMAA isomers for a large breadth of field-collected lakes from Brazil, Canada, France, Mexico, and the United Kingdom. Data gathered during this overarching campaign (overall, n = 390 within 45 lake sampling sites) indicated frequent detections of AEG and DAB isomers, with detection rates of 30% and 43% and maximum levels of 19,000 ng L−1 and 1100 ng L−1, respectively. In contrast, BAMA was found in less than 8% of the water samples, and BMAA was not found in any sample. These results support the analyses of free-living cyanobacteria, wherein BMAA was often reported at concentrations of 2−4 orders of magnitude lower than AEG and DAB. Seasonal measurements conducted at two bloom-impacted lakes indicated limited correlations of BMAA isomers with total microcystins or chlorophyll-a, which deserves further investigation.

Which soil Cu pool governs phytotoxicity in field-collected soils contaminated by copper smelting activities in central Chile?

Several studies have attempted to predict the so-called "phytoavailable" fraction by correlating plant responses with different soil metal pools. Most of the data derived from these studies tend to be inconsistent, making interpretations difficult. Thus, the main objective of this study was to determine which soil Cu pool (free Cu2+, salt-exchangeable Cu or total Cu) controls Cu phytotoxicity in soils near a Cu smelter in central Chile. We studied the following traits of the local plant community grown spontaneously on the study site: species richness, shoot biomass, and plant cover. The site was dominated by four early plant colonizers: Eschscholzia californica Cham., Hirschfeldia incana (L.) Lagr.-Fossat, Lolium perenne L., and Vulpia bromoides (L.) Gray. We determined exchangeable soil Cu and activity of free Cu2+ in 0.1 M KNO3 extracts using soil/solution ratio of 1/2.5. The effect of total soil Cu on plant responses was not significant (p > 0.05). In our field-collected soil series, exchangeable Cu was a better indicator of soil phytotoxicity than either total soil Cu or free Cu2+ in the soil solution. We determined upper critical threshold values for Cu exposure using the three plant traits cited above. The mean values of EC10, EC25, and EC50 (effective concentration at 10%, 25%, and 50%, respectively) of exchangeable soil Cu (in µg L-1) were 255, 391, and 533, respectively. The mean EC10, EC25 and EC50 values of pCu2+ were 7.5, 6.8, and 5.9, respectively. We highlight the importance of further studies on Cu phytotoxicity using actual field-contaminated soils.

Soil and indoor dust as environmental media of human exposure to As, Cd, Cu, and Pb near a copper smelter in central Chile.

In the present study, we assessed the non-carcinogenic and carcinogenic human health risk due to exposure to trace elements in soil and indoor dust in Puchuncaví valley. We also determined the associations between trace element concentration in hair/toenails and the estimated chronic daily intake of trace elements in soil and indoor dust. We found statistically significant association between the trace element concentration in hair/toenails and the estimated chronic daily intake of soil and indoor dust. Indoor dust was more important than soil in terms of human exposure to trace elements in Puchuncaví, due to the high concentration of trace elements on this environmental media and long periods of time that the population spends at their households. With regards to non-carcinogenic risk, we found that there was no health risk associated to soil and indoor dust exposure in the Puchuncaví valley, because none of the hazard quotient values surpassed 1.0. However, carcinogenic risk due to arsenic exposure was above the threshold value of 1.0E-04 in the population of young children (from 1 to 5 years old) in all studied areas, including the control, and in the population of children (from 6 to <18 years old) in the exposed area. Such risk values are classified as unacceptable (US EPA, 2001), requiring some target intervention from the Chilean government.

Comparison of exposure to trace elements through vegetable consumption between a mining area and an agricultural area in central Chile.

Human exposure to trace elements has been a large concern due to the potential health issues. Accordingly, this study aimed to compare the concentrations of arsenic, copper, and zinc in the edible parts of vegetables grown in a mining-agricultural area and in an exclusively agricultural area and to compare the potential human health risks of consuming vegetables from both areas. The consumption habits of the studied population were extracted from the 2010 National Alimentary Survey of Chile. In most cases, the concentrations of trace elements in the edible tissues of vegetables (lettuce, spinach, garlic, onion, carrot, potato, sweet corn, and tomato) were higher in the mining-agricultural area than those in the control area. This difference was most pronounced for leafy vegetables, with arsenic being the trace element of concern. Specifically, the arsenic concentrations in the edible tissues of lettuce and spinach were 8.2- and 5.4-fold higher, respectively, in the mining-agricultural area than in the control area. Lettuce was the vegetable of concern due to its relatively high consumption and relatively high concentration of trace elements. Nevertheless, there was no health risk associated with vegetable consumption in either the mining area or the control area because none of the HQ values surpassed 1.0.

Advances on the determination of thresholds of Cu phytotoxicity in field-contaminated soils in central Chile.

To better determine phytotoxicity thresholds for metals in the soil, studies should use actual field-contaminated soil samples rather than metal-spiked soil preparations. However, there are surprisingly few such data available for Cu phytotoxicity in field-contaminated soils. Moreover, these studies differ from each other with regards to soil characteristics and experimental setups. This study aimed at more accurately estimating Cu phytotoxicity thresholds using field-collected agricultural soils (Entisols) from areas exposed to contamination from Cu mining. For this purpose, the exposure to Cu was assessed by measuring total soil Cu, soluble Cu, free Cu2+ activity, and Cu in the plant aerial tissues. On the other hand, two bioassay durations (short-term and long-term), three plant species (Avena sativa L., Brassica rapa CrGC syn. Rbr, and Lolium perenne L.), and five biometric endpoints (shoot length and weight, root length and weight, and number of seed pods) were considered. Overall plant growth was best predicted by total Cu content of the soil. Despite some confounding factors, it was possible to determine EC10, EC25 and EC50 of total Cu in the soil. Brassica rapa was more sensitive than Avena sativa for all endpoints, while Lolium perenne was of intermediate sensitivity. For the short-term bioassay (21 days for all three species), the averaged EC10, EC25 and EC50 values of total soil Cu (in mg kg-1) were 356, 621, and 904, respectively. For the long-term bioassay (62 days for oat and 42 days for turnip), the averaged EC10, EC25 and EC50 values of total soil Cu (in mg kg-1) were 355, 513, and 688, respectively. The obtained results indicate that chronic test is a suitable method for assessing Cu phytotoxicity in field-contaminated soils.

Thresholds of arsenic toxicity to Eisenia fetida in field-collected agricultural soils exposed to copper mining activities in Chile.

Several previous studies highlighted the importance of using field-collected soils-and not artificially-contaminated soils-for ecotoxicity tests. However, the use of field-collected soils presents several difficulties for interpretation of results, due to the presence of various contaminants and unavoidable differences in the physicochemical properties of the tested soils. The objective of this study was to estimate thresholds of metal toxicity in topsoils of 24 agricultural areas historically contaminated by mining activities in Chile. We performed standardized earthworm reproduction tests (OECD 222 and ISO 11268-2) with Eisenia fetida. Total soil concentrations of Cu, As, Zn, and Pb were in the ranges of 82-1295 mg kg(-1), 7-41 mg kg(-1), 86-345 mg kg(-1), and 25-97 mg kg(-1), respectively. In order to differentiate between the effects of different metals, we used regression analysis between soil metal concentrations and earthworm responses, as well as between metal concentrations in earthworm tissues and earthworm responses. Based on regression analysis, we concluded that As was a metal of prime concern for Eisenia fetida in soils affected by Cu mining activities, while Cu exhibited a secondary effect. In contrast, the effects of Zn and Pb were not significant. Soil electrical conductivity was another significant contributor to reproduction toxicity in the studied soils, forcing its integration in the interpretation of the results. By using soils with electrical conductivity ≤ 0.29 dS m(-1) (which corresponds to EC50 of salt toxicity to Eisenia fetida), it was possible to isolate the effect of soil salinity on earthworm reproduction. Despite the confounding effects of Cu, it was possible to determine EC10, EC25 and EC50 values for total soil As at 8 mg kg(-1), 14 mg kg(-1) and 22 mg kg(-1), respectively, for the response of the cocoon production. However, it was not possible to determine these threshold values for juvenile production. Likewise, we were able to determine EC10, EC25 and EC50 of earthworm tissue As of 38 mg kg(-1), 47 mg kg(-1), and 57 mg kg(-1), respectively, for the response of the cocoon production. Finally, we determined the no-observed effect concentration of tissue As in E. fetida of 24 mg kg(-1). Thus, earthworm reproduction test is applicable for assessment of metal toxicity in field-collected soils with low electrical conductivity, while it might have a limited applicability in soils with high electrical conductivity because the salinity-induced toxicity will hinder the interpretation of the results.

Thresholds of copper phytotoxicity in field-collected agricultural soils exposed to copper mining activities in Chile.

It has been argued that the identification of the phytotoxic metal thresholds in soil should be based on field-collected soil rather than on artificially-contaminated soils. However, the use of field-collected soils presents several difficulties for interpretation because of mixed contamination and unavoidable covariance of metal contamination with other soil properties that affect plant growth. The objective of this study was to estimate thresholds of copper phytotoxicity in topsoils of 27 agricultural areas historically contaminated by mining activities in Chile. We performed emergence and early growth (21 days) tests (OECD 208 and ISO 11269-2) with perennial ryegrass (Lolium perenne L.). The total Cu content in soils was the best predictor of plant growth and shoot Cu concentrations, while soluble Cu and pCu(2+) did not well correlate with these biological responses. The effects of Pb, Zn, and As on plant responses were not significant, suggesting that Cu is a metal of prime concern for plant growth in soils exposed to copper mining activities in Chile. The effects of soil nutrient availability and shoot nutrient concentrations on ryegrass response were not significant. It was possible to determine EC10, EC25 and EC50 of total Cu in the soil of 327 mg kg(-1), 735 mg kg(-1) and 1144 mg kg(-1), respectively, using the shoot length as a response variable. However, the derived 95% confidence intervals for EC10, EC25 and EC50 values of total soil Cu were wide, and thus not allowing a robust assessment of metal toxicity for agricultural crops, based on total soil Cu concentrations. Thus, plant tests might need to be performed for metal toxicity assessment. This study suggests shoot length of ryegrass as a robust response variable for metal toxicity assessment in contaminated soils with different nutrient availability.

Effects of lime and compost on earthworm (Eisenia fetida) reproduction in copper and arsenic contaminated soils from the Puchuncaví Valley, Chile.

The Puchuncaví Valley in central Chile has been exposed to atmospheric depositions from a copper smelter. Nowadays, soils in the surrounding area are acidic and contaminated with Cu and As. The objective of this study was to determine the effectiveness of lime and compost for in situ immobilization of trace elements in the soils of the Puchuncaví Valley by using earthworms as bioindicators of toxicity. The lime and compost treatments significantly increased soil pH and decreased the soluble and exchangeable Zn, exchangeable Cu, and free Cu(2+) activity. However, the compost treatment increased soluble Cu, and soluble and exchangeable As. Lime application had no effect on earthworm reproduction in comparison with the unamended control, whereas the application of compost increased cocoon and juvenile production. There was a spatial variability of soil properties within treatments in the field plots. This allowed the identification of which soil properties were actually having an impact on earthworm reproduction. For both cocoon and juvenile production, soil organic matter (SOM) was a positive factor, i.e., more SOM increased cocoon or juvenile production. The toxicity (negative) factor was total soil As. However, total Cu and total As were well correlated (R(2)=0.80, p<0.001), hence some of the trends could have been masked. In summary, compost treatment was effective in improving the quality of soils of Puchuncaví Valley, increasing earthworm reproduction. Future Chilean legislation on maximum permissible concentrations of trace elements in soils should consider SOM content due to its effect on trace element solubility and bioavailability.