While (N-ethyl perfluorooctanesulfonamido ethanol)-based phosphates (SAmPAPs) have been proposed as a group of perfluorooctanesulfonate (PFOS) precursors, investigation of their occurrence and fate has been limited to SAmPAP diester. In this study, SAmPAP diester and triester were simultaneously determined in freshwater sediment from Taihu Lake using a newly developed UPLC-MS/MS method, and their biotransformation to PFOS in lake sediment was investigated. SAmPAP diester and triester were detected in sediments with a detection frequency of 56% and 88%, and their mean concentrations were 0.24 ± 0.11 ng/g dry weight (dw) and 0.12 ± 0.03 ng/g dw, respectively. The SAmPAP diester/triester ratio in sediment was 1.1 ± 4.2, much lower than that (6.7) observed in the technical product, and the positive correlation was found between the concentrations of SAmPAP diester and PFOS in sediments (r² = 0.45, p = 0.01), suggesting that SAmPAP diester would be biotransformed to PFOS in the lake sediment. The microbial degradation test in the lake sediments further clarified that SAmPAP diester was biodegraded to PFOS, but SAmPAP triester was highly recalcitrant to microbial degradation. This study suggests that the occurrence of SAmPAP diester in freshwater lake sediments may be an important precursor of PFOS.

We investigated how different carbonized materials, or chars (olive mill pomace biochar (BC) and urban greens pruning residues hydrochar (HC)) affect an important member of soil fauna, the terrestrial isopod Porcellio scaber. The selection behavior of isopods towards chars after a 48 h exposure was studied in (i) soil-char amended tests with single and multiple choices, and (ii) tests with chars offered as pure material. Finally, we exposed the isopods to char-amended soils for a period of 14 days to follow the effect on food consumption, body mass and activities of enzymes that are commonly altered upon stressor exposure (acetylcholinesterase, AChE, and glutathione S-transferase, GST). We showed that isopods are able to select between char amended and un-amended soil and different forms of char amendments: a clear preference for BC, and avoidance of HC were evidenced. The preferences remained the same when the chars were sterilized leading to the conclusion that initial microorganism composition was not the reason for selection, but selection was governed by other chars’ physico-chemical properties. It remains to be elucidated which of these properties were the dominant reason for the selection. We also showed that isopods intentionally use BC as food at a similar rate to alder leaves. Medium-term exposure to HC resulted in adverse effects on isopods because it led to reduced feeding and growth, in addition to increasing GST activity, although no alterations in AChE activity were found. We suggest that behavioral tests with P. scaber could be used as a fast, reliable and economically feasible screening method for determining the safety of chars for the soil environment. Results represent significant contribution in the field of char toxicity testing, highlighting the importance of tests with isopods as important members of soil meso fauna, with the aim of influencing environmental policies and quality standards.

Six different approaches are applied in the present study to apportion the sources of precipitation nitrogen making use of precipitation data of dissolved inorganic nitrogen (DIN, including NO3− and NH4+), dissolved organic nitrogen (DON) and δ15N signatures of DIN collected at six sampling sites in the mountain region of Southwest China. These approaches include one quantitative approach running a Bayesian isotope mixing model (SIAR model) and five qualitative approaches based on in-situ survey (ISS), ratio of NH4+/NO3− (RN), principal component analysis (PCA), canonical-correlation analysis (CCA) and stable isotope approach (SIA). Biomass burning, coal combustion and mobile exhausts in the mountain region are identified as major sources for precipitation DIN while biomass burning and volatilization sources such as animal husbandries are major ones for DON. SIAR model results suggest that mobile exhausts, biomass burning and coal combustion contributed 25.1 ± 14.0%, 26.0 ± 14.1% and 27.0 ± 12.6%, respectively, to NO3− on the regional scale. Higher contributions of both biomass burning and coal combustion appeared at rural and urban sites with a significant difference between Houba (rural) and the wetland site (p < 0.05). The RN method fails to properly identify sources of DIN, the ISS and SIA approach only respectively identifies DON and DIN sources, the PCA only tracks source types for precipitation N, while the CCA identify sources of both DIN and DON in precipitation. SIAR quantified the contributions of major sources to precipitation NO3− but failed for precipitation NH4+ and DON. It is recommended to use ISS and SIAR in combination with one or more approaches from PCA, CCA and SIA to apportion precipitation NO3− sources. As for apportioning precipitation NH4+ sources, more knowledge is needed for local 15N databases of NH3 and DON and 15N fractional mechanisms among gaseous, liquid and particulate surfaces in this mountain region and similar environments.

Chlorinated polyfluoroalkyl ether sulfonic acids (Cl-PFESAs) caused great concerns recently as novel fluorinated alternatives. However, information on their bioconcentration, bioaccumulation and biomagnification in marine ecosystems is limited. In this study, 152 biological samples including invertebrates, fishes, seabirds and mammals collected from Bohai Sea of China were analyzed to investigate the residual level, spatial distribution, bioaccumulation and biomagnification of Cl-PFESAs. 6:2 Cl-PFESA was found in concentrations ranging from <MDL (method detection limit) to 3.84 ng/g ww and it is the dominant congener when compared with concentrations of 8:2 Cl-PFESA. Compared with other bays and regions, levels of 6:2 Cl-PFESA are relatively high in bivalves and fishes from Liaodong Bay. These levels were also found to tend to increase as compared with those in 2010–2014. Logarithm bioaccumulation factors (BAFs) for 6:2 Cl-PFESA ranged from 2.23 to 4.21, implying the bioaccumulation of this compound. The trophic magnification factor (BMF) for 6:2 Cl-PFESA was determined to be 3.37 in the marine food web, indicating biomagnification potential along the marine food chain.

The knowledge of gene-chemical interaction can be used to derive toxicological mechanism of chemical pollutants, therefore, it might be useful to discriminate chemicals with different mechanisms. In this study, three narcotic chemicals (4-chlorophenol (4-CP), 3, 4-dichloroaniline (DCA) and 2, 2, 2-trichloroethanol (TCE)) and three specific acting chemicals (triclosan (TCS), clarithromycin (CLARY), sulfamethoxazole (SMX)) were assessed by Escherichia coli (E. coli) genome-wide knockout screening. 66, 97, 88, 144, 198 and 180 initial robust hits were identified by exposure to 4-CP, DCA, TCE, TCS, CLARY and SMX with two replicates at the concentration of IC50, respectively. The average fold change values of responsive mutants to the three narcotic chemicals were smaller than the three specific acting chemicals. The common gene ontology (GO) term of biological process enriched by the three narcotic chemicals was “response to external stimulus” (GO: 0009605). Other GO terms like “lipopolysaccharide biosynthetic process” (induced by 4-CP) and “purine nucleotide biosynthetic process” (induced by DCA) were also influenced by the narcotic chemicals. The toxic target of three known specific acting chemicals could be validated by GSEA of responsive genes. Four genes (flhC, fliN, fliH and flhD) might serve as potential biomarkers to distinguish narcotic chemicals and specific acting chemicals. The E. coli functional genomic approach presented here has shown great potential not only for the molecular mechanistic screening of chemicals, rather it can discriminate chemicals based on their mode-of-action.

Globally, millions of people who rely on groundwater for potable purposes and agriculture have been inadvertently exposed to toxic arsenic (As) because of its natural occurrence in groundwater in several countries of Asia, Europe and America. While the presence of As in groundwater and its impacts on human health have been documented in many countries, there is little information on As contamination in Pakistan. This review highlights, for the first time, the extent and severity of As-induced problems in Pakistan based on relevant published papers; discusses possible sources of As contamination of aquifers; and estimates As-induced potential health hazards in the country in relation to global data. Data from 43 studies (>9882 groundwater samples) were used to describe As variability in groundwater of Pakistan and for comparison with global data. The mean groundwater As content reported in these studies was 120 μg/L (range: 0.1–2090 μg/L; SD: ±307). About 73% of the values for mean As contents in the 43 studies were higher than the World Health Organization (WHO) permissible limit (10 μg/L) for drinking water, while 41% were higher than the permissible limit of As in Pakistan (50 μg/L). It was observed that groundwater samples in some areas of Punjab and Sindh provinces contained high As concentrations which were almost equal to concentrations reported in the most contaminated areas of the world. We predicted that the mean values of ADD, HQ and CR were 4.4 μg kg⁻¹day⁻¹ (range: 0–77 μg kg⁻¹day⁻¹), 14.7 (range: 0–256) and 0.0029 (range: 0–0.0512), respectively, based on mean As concentrations reported in Pakistan. In addition, this article proposes some integrated sustainable solutions and future perspectives keeping in view the regional and global context, as well as the on-ground reality of the population drinking As-contaminated water, planning issues, awareness among civil society and role of the government bodies. Based on available data, it is predicted that almost 47 million people in Pakistan are residing in areas where more than 50% of groundwater wells contain As concentrations above the WHO recommended limit of As in drinking water.

Systemic neonicotinoid insecticides such as imidacloprid are increasingly applied against insect pest infestations on forest trees. However, leaves falling from treated trees may reach nearby surface waters and potentially represent a neonicotinoid exposure source for aquatic invertebrates. Given imidacloprid's susceptibility towards photolysis and high water solubility, it was hypothesized that the leaves' toxicity might be modulated by UV-irradiation during decay on the forest floor, or by leaching and re-mobilization of the insecticide from leaves within the aquatic ecosystem. To test these hypotheses, the amphipod shredder Gammarus fossarum was fed (over 7 d; n = 30) with imidacloprid-contaminated black alder (Alnus glutinosa) leaves that had either been pre-treated (i.e., leached) in water for up to 7 d or UV-irradiated for 1 d (at intensities relevant during autumn in Central Europe) followed by a leaching duration of 1 d. Gammarids' feeding rate, serving as sublethal response variable, was reduced by up to 80% when consuming non-pretreated imidacloprid-contaminated leaves compared to imidacloprid-free leaves. Moreover, both leaching of imidacloprid from leaves (for 7 d) as well as UV-irradiation reduced the leaves' imidacloprid load (by 46 and 90%) thereby mitigating the effects on gammarids' feeding rate to levels comparable to the respective imidacloprid-free controls. Therefore, natural processes, such as UV-irradiation and re-mobilization of foliar insecticide residues in water, might be considered when evaluating the risks systemic insecticide applications in forests might pose for aquatic organisms in nearby streams.

The United States Environmental Protection Agency (USEPA) completed nationwide screening of six perfluoroalkyl substances in U.S. drinking water from 2013 to 2015 under the Third Unregulated Contaminant Monitoring Rule (UCMR3). UCMR3 efforts yielded a dataset of 36,139 samples containing analytical results from >5000 public water systems (PWSs). This study used UCMR3 data to investigate three aspects of per- and polyfluoroalkyl substances (PFASs) in drinking water: the occurrence of PFAS and co-contaminant mixtures, trends in PFAS detections relative to PWS characteristics and potential release types, and temporal trends in PFAS occurrence. This was achieved through bivariate and multivariate analyses including categorical analysis, concentration ratios, and hierarchical cluster analysis. Approximately 50% of samples with PFAS detections contained ≥2 PFASs, and 72% of detections occurred in groundwater. Large PWSs (>10,000 customers) were 5.6 times more likely than small PWSs (≤10,000 customers) to exhibit PFAS detections; however, when detected, median total PFAS concentrations were higher in small PWSs (0.12 μg/L) than in large (0.053 μg/L). Bivariate and multivariate analyses of PFAS composition suggested PWSs reflect impacts due to firefighting foam use and WWTP effluent as compared to other source types for which data were available. Mann-Kendall analysis of quarterly total PFAS detection rates indicated an increasing trend over time (p = 0.03). UCMR3 data provide a foundation for tiered design of targeted sampling and analysis plans to address remaining knowledge gaps in the sources, composition, and concentrations of PFASs in U.S. drinking water.

This study presents the particle size distribution and respiratory deposition estimates of airborne perfluoroalkyl acids (PFAAs) during the haze period. Size-segregated haze aerosols were collected from an urban location in Shanghai using an eight-stage air sampler. The samples were analyzed for eight PFAAs using ultra-high-performance liquid chromatography tandem triple quadrupole mass spectrometry. The quantification results showed that the concentrations of particle-bound Σ 8PFAAs ranged from 0.26 to 1.90 ng m⁻³ (mean: 1.44 ng m⁻³). All of the measured PFAAs particle size distributions had a bimodal mode that peaked respectively in accumulation size range (0.4 < Dp < 2.1 μm) and coarse size ranges (Dp > 2.1 μm), but the width of each distribution somewhat varied by compound. The emission source, molecular weight, and volatility of the PFAAs were important factors influencing the size distribution of particle-bound PFAAs. Of these compounds, PFUnDA presented a strong accumulation in the fine size range (average 75% associated with particles <2.1 μm), followed by PFOA (69%) and PFDA (64%). The human risk assessment of PFOS via inhalation was addressed and followed the same pattern as the size distribution, with a 2-fold higher risk for the fine particle fraction compared to the coarse particle fraction at urban sites. Approximately 30.3–82.0% of PFAA deposition (∑PFAA: 72.5%) in the alveolar region was associated with particles <2.1 μm, although the contribution of fine particles to the total PFAAs concentration in urban air was only 28–57% (∑8PFAAs: 48%). These results suggested that fine particles are significant contributors to the deposition of PFAAs in the alveolar region of the lung.