Due to the complex sources and fate of perfluoroalkyl substance (PFAS), their source apportionment in the environment remains a challenge. A data set of 11 straight-chain PFAS in 139 samples of fish in the Great Lakes was analyzed using positive matrix factorization (PMF) to investigate their primary sources, whose spatial variations were examined against the surrounding environmental factors. PMF analysis produced five fingerprints. Factor 1 (72% of Σ₁₁PFAS, dominated by PFOS) probably represented emissions from primary sources (such as consumer products) and secondary sources (precursors), and increased in average abundance from west to east across the Great Lakes. Factor 2 (13% of Σ₁₁PFAS) and factor 3 (7% of Σ₁₁PFAS), highly loaded with long-chain PFAS and PFNA, respectively, were thought to represent PVDF manufacture or processing in metal plating. They showed higher contributions in sparsely populated Lakes Superior and Huron. Factor 4 (5% of Σ₁₁PFAS, highly loaded with PFOS and PFHxS) presented hot spots near current and former air force bases, suggesting it was related to aqueous film-forming foams (AFFFs). Factor 5 (4% of Σ₁₁PFAS) contained primarily PFOS and PFOSA, which may imply metabolism of precursors (PFOSA) to PFOS in vivo. Unexpectedly, the spatial trends of the five sources all showed abnormally low values near the more urbanized Chicago and Milwaukee in Lake Michigan, which may be due to their unique wastewater and stormwater infrastructure or may arise from atmospheric transport of precursors. Our study indicated that PMF was an effective tool to identify sources of PFAS in fish despite absorption, distribution, metabolism, and excretion (ADME) processes which might alter fingerprints in fish relative to their surrounding environment.

Volatile organic compounds (VOCs) are easily degraded by oxidants during atmospheric transport. Therefore, the contribution of VOCs to ozone (O₃) and secondary organic aerosol (SOA) formation at a receptor site is different from that in a source area. In this study, hourly concentrations of VOCs and other pollutants, such as O₃, NOx, HONO, CO, and PM₂.₅, were measured in the suburbs (Daxing district) of Beijing in August 2019. The photochemical initial concentrations (PICs), in which the photochemical losses of VOCs were accounted for, were calculated to evaluate the contribution of the VOCs to O₃ and SOA formation. The mean (±standard deviation) measured VOC concentrations and the PICs were 11.2 ± 5.7 and 14.6 ± 8.4 ppbv, respectively, which correspond to O₃ formation potentials (OFP) of 57.8 ± 26.3 and 103.9 ± 109.4 ppbv and SOA formation potentials (SOAP) of 8.4 ± 4.1 and 10.3 ± 7.4 μg m⁻³, respectively. Alkenes contributed 80.5% of the consumed VOCs, followed by aromatics (13.3%) and alkanes (6.2%). The contributions of the alkenes and aromatics to the OFPPICₛ were 56.8% and 30.3%, respectively; while their corresponding contributions to the SOAPPICₛ were 1.9% and 97.3%, respectively. The OFPPICₛ was linearly correlated with the observed O₃ concentrations (OFPPICₛ = 41.5 + 1.40 × cO₃, R² = 0.87). The O₃ formation was associated with a VOC-limited regime at the receptor site based on the measured VOCs and changed to a transition regime and a NOx sensitive regime based on the PIC. Our results suggest that more attention should be paid to biogenic VOCs when studying O₃ formation in summer in Beijing, while the control of anthropogenic aromatic compounds should be given priority in terms of SOA formation.

Understanding which factors affect the process of leaf litter decomposition is crucial if we are to predict changes in the functioning of stream ecosystems as a result of human activities. One major activity with known consequences on streams is agriculture, which is of particular concern in tropical regions, where forests are being rapidly replaced by crops. While pesticides are potential drivers of reduced decomposition rates observed in agricultural tropical streams, their specific effects on the performance of decomposers and detritivores are mostly unknown. We used a microcosm experiment to examine the individual and joint effects of an insecticide (chlorpyrifos) and a fungicide (chlorothalonil) on survival and growth of detritivores (Anchytarsus, Hyalella and Lepidostoma), aquatic hyphomycetes (AH) sporulation rate, taxon richness, assemblage structure, and leaf litter decomposition rates. Our results revealed detrimental effects on detritivore survival (which were mostly due to the insecticide and strongest for Hyalella), changes in AH assemblage structure, and reduced sporulation rate, taxon richness and microbial decomposition (mostly in response to the fungicide). Total decomposition was reduced especially when the pesticides were combined, suggesting that they operated differently and their effects were additive. Importantly, effects on decomposition were greater for single-species detritivore treatments than for the 3-species mixture, indicating that detritivore species loss may exacerbate the consequences of pesticides of stream ecosystem functioning.

Bioaccessibility is essential for evaluating dietary intake of contaminants. However, there is insufficient information on the dependence of dietary intake and risk assessment of dichlorodiphenyltrichloroethane and its metabolites (DDXs) and hexachlorocyclohexane isomers (HCHs) on bioaccessibility. Here, we investigated the bioaccessibilities of DDXs and HCHs in various foods and their influences on assessing exposure in the residents of Beijing City, China. Forty-three major foods in five types (fruit, vegetables, cereals, aquatic food, and meat) were sampled, and the bioaccessibility of DDXs and HCHs was evaluated using a static in vitro gastrointestinal digestion model. The bioaccessibility of DDXs in different food types ranked in the order of meat > vegetables > fruit > cereals > aquatic food, with mean ± standard deviation values of 62.2 ± 22.1%, 20.5 ± 10.6%, 12.4 ± 3.66%, 11.2 ± 9.69%, and 10.7 ± 4.97%, respectively. The highest average bioaccessibility of HCHs was found in meat (83.4 ± 14.2%), followed by fruit (41.0 ± 12.5%), vegetables (37.6 ± 18.1%), aquatic foods (24.2 ± 9.22%), and cereals (8.73 ± 4.07%). The estimated daily intakes (EDI) of the sum of DDXs and the sum of HCHs based on the bioaccessible concentration were only about 17% and 55% of the total EDI based on the residual concentration, respectively. Meat was found to play a more important role in EDI after bioaccessibility correction. The proportion of the population with potential non-carcinogenic and carcinogenic risks markedly decreased when considering bioaccessibility. It was concluded that bioaccessibility should be integrated into dietary exposure evaluation.

The development of an eco-friendly and reliable process for the production of nanomaterials is essential to overcome the toxicity and exorbitant cost of conventional methods. As such, a facile and green synthesis method is introduced for the preparation of lignin mediated silver nanoparticles (L-Ag NPs). This is produced by reducing Ag precursors using lignin biopolymers which are formulated by pulsed laser irradiation and an ultrasonication process. Lignin operates as both a reducing and stabilizing agent. The various analytical techniques of ultraviolet–visible spectroscopy, transmission electron microscope and X-ray diffractometer studies were employed to verify the formation of non-aggregated spherical L-Ag NPs with an average size as small as 7–8 nm. The selective sensing capability of the synthesized L-Ag NPs was examined for the detection of hydrogen peroxide and mercury ions in an aqueous environment. Furthermore, the superior catalytic performance of L-Ag NPs was demonstrated by the rapid conversion of toxic 4-nitrophenol and nitrobenzene as targeted pollutants to the corresponding amino compounds. A plausible catalytic reduction mechanism for the removal of toxic nitro-organic pollutants over L-Ag NPs is proposed. This research coincides with existing studies and affirms that L-Ag NPs are an effective sensor that be applied as a catalytic material within environmental remediation and also alternative biomedical applications.

Application of alternating current in electrocoagulation and activation of persulfate (AEC-PS) for the effective removal of humic acid (HA) from aqueous solution was evaluated. In order to optimize the removal efficiency HA by the AEC-PS process, several influencing parameters such as pH, reaction time, PS dose, current density (CD), concentration of NaCl, initial concentration of HA, and coexisting cations and anions influence were investigated. From the batch experiments, the highest HA removal efficiency obtained was 99.4 ± 0.5% at pH of 5, reaction time of 25 min, CD of 4.5 mA/cm², PS dose of 200 mg/L, and NaCl concentration of 0.75 g/L for an initial HA concentration of 30 mg/L. When CD increased from 1.25 to 4.5 mA/cm², the HA removal efficiency was improved from 88.8 ± 4.4% to 96.1 ± 1.5%. In addition, the type of coexisting cations and anions exerted a significant role, leading to a reduction in the removal efficiency of HA. To investigate the dominant free activated radical, radical scavengers such as tert-butyl alcohol and ethanol were employed. It was observed that both OH and SO₄⁻ radicals substantially contributed to the removal of HA, and the contribution of SO₄⁻ radical was higher than that of OH radical, suggesting that AEC-PS process could serve as a novel and effective treatment technique for the removal of organic matters from aqueous sources.

A long-term case of residual pollution is studied after 20 years since the largest mining accident in Spain (the Aznalcóllar spill) happened. This pollution is manifested through a surface zoning consisting of bare soils (B0), sparsely vegetated soils (B1), and densely vegetated and recovered soils (B2). A biopiles treatment with a mixture of contaminated soils (B0 and B1) with recovered soils (B2) at 50% (w/w), and vermicompost addition (50 tons ha-1) was evaluated. To assess the effectiveness of treatments, total, water-soluble, and bioavailable fractions of the most polluting elements in the zone (Cu, Zn, As, Pb, Cd, and Sb) was analyzed. To evaluate the potential risk of contamination for the ecosystem, a bioassay with earthworm Eisenia andrei was carried out. Twenty years after the accident, there are still soils where total As and Pb exceed the regulatory levels and water-soluble Zn and As exceed the toxicity guidelines. According to toxicity bioassay, weight variation and juvenile production of earthworms showed an improvement after biopiles treatment, with values that trend to be similar to those of recovered soils. The only bioaccumulated element in earthworms was Cd (BAF>1), both in polluted as in treated soils, which indicates the possible existence of exclusion mechanisms of the other pollutants by earthworms. The comparison between biopiles and polluted soils showed no significant differences for the bioaccumulation factor of trace elements, with the exception of Zn and Cu, which slightly increased after treatment. According to our results, biopiles treatment combined with vermicompost addition is a good technique for the recovery of residual contaminated areas, by the improvement of soil properties and the reduction of the potential toxicity; anyway, monitoring of soils and organisms is needed to prevent the increase of bioavailability of some potentially pollutant elements over time.

Coupling of nitrogen removal processes with nitrification (NRₙ) are vital synergistic nitrogen elimination mechanisms in aquatic environments. However, the effects of antibiotics on NRₙ are not well known. In the present work, 20-day continuous-flow experiments combined with ¹⁵N tracing techniques and quantitative PCR were performed to simulate the impact of sulfamethoxazole (SMX, a sulfonamide antibiotic) with near in situ concentration on NRₙ processes in sediments of Yangtze Estuary. Results showed that SMX with near in situ concentration significantly decreased NRₙ, NRw (uncoupling of nitrogen removal processes with nitrification) and actual nitrogen removal rates via inhibiting nitrogen transformation functional genes (AOB, narG, nirS, nosZ) and anammox 16S rRNA gene, while the coupling links between nitrification and nitrogen removal processes were not broken by the exposure. The proportion of NRₙ in total nitrogen removal processes decreased by approximately 10% with SMX addition, due to the different inhibition on AOB, denitrifying genes and anammox 16S rRNA gene. N₂O production and nitrite accumulation remarkably increased with SMX addition under simultaneous nitrification and denitrification, and they strongly correlated with each other. The more severely inhibition on nirS gene (13.6–19.8%) than Nitrospira nxrB gene (0.3–8.2%) revealed that the increased nitrite accumulation with SMX addition mainly occurred in heterotrophic denitrification, suggesting that the increased N₂O production was dominated by the heterotrophic nitrite reduction. Moreover, we estimated that the ratio of external inorganic N eliminated by actual nitrogen removal can upgrade to 6.4–7.4% under circumstances of no inhibition by SMX. This study revealed the effects of SMX with near in situ concentration on NRₙ processes and illustrated the microbial mechanism on functional genes level. Our results highlighted the inhibitory effects of SMX on NRₙ may contribute to reactive N retention and N₂O production in estuarine and coastal ecosystems.

Many estuaries have undergone severe saltwater intrusion in addition to simultaneously experiencing serious heavy metal pollution. To explore the effect of water density stratification associated with saltwater intrusion on the behaviour of heavy metals (Cr, Co, Ni, Cu, Zn, As, Pb, and Cd) in water and sediments, a field survey was conducted in a typical estuary (Modaomen). The content, distribution, and mobility of heavy metals were investigated, as well as the influence of environmental factors on their future. The results showed that Modaomen estuary was characterised by a notable variation in salinity along the estuary, presenting total freshwater upstream, high salinity stratification water in the mouth, and saltwater offshore. Dissolved metals presented a prominent gradient vertically, with 1.2–2.1 times higher in bottom water than in surface water and the highest contents in the highly–stratified bottom water. Elevated salinity and restricted mixing induced by water stratification were likely the causes of this outcome. The distribution of heavy metals in sediments was greatly governed by grain size, Fe/Mn (hydr)oxides, total organic carbon, salinity, and dissolved oxygen. Comprehensive evaluation, combined with total contents and chemical fractions of heavy metals, indicated that internal release from sediments contributed a considerable part to the higher levels of heavy metals in bottom water, particularly for Zn and Pb, which was fully consistent with their status in water body, and elevated salinity and lack of oxygen were likely the primary driving factors. During the phase-partition processes between bottom water and sediments, partitioning coefficients were markedly lower in the highly stratified zone, implying that saltwater intrusion facilitated the mobility and repartitioning processes of metals. Because of increased levels and toxicity of heavy metals in water and extended residence time during saltwater intrusion, the potential damage to the estuarine ecosystem should receive more attention.

It is widely recognized that apex predators, such as large sharks with highly migratory behavior, are particularly vulnerable to pollution, mainly due to biomagnification processes. However, in highly impacted areas, mesopredator sharks with resident behavior can be as vulnerable as apex sharks. In this context, this study evaluated cadmium (Cd), mercury (Hg), lead (Pb), and rubidium (Rb) concentrations, as well as the potentially protective effects of selenium (Se) and the behavior of two non-enzymatic biomarkers, metallothionein (MT) and reduced glutathione (GSH), employing the Atlantic nurse shark Ginglymostoma cirratum as a study model and compared the results with other resident benthic sharks, as well as highly mobile apex sharks. Muscle tissue samples from 28 nurse sharks opportunistically sampled from the Brazilian Amazon Coast were analyzed. Lower metal concentrations were observed for Pb, Rb and Se in the rainy season, while statistically significant correlations between metals were observed only between Hg and Cd and Pb and Se. Molar ratio calculations indicate potential protective Se effects against Pb, but not against Cd and Hg. No associations between MT and the determined metals were observed, indicating a lack of detoxification processes via the MT detoxification route. The same was noted for GSH, indicating no induction of this primary cellular antioxidant defense. Our results indicate that benthic/mesopredator sharks with resident behavior are, in fact, as impacted as highly mobile apex predators, with the traditional detoxification pathways seemingly inefficient for the investigated species. Moreover, considering the studied population and other literature data, pollution should be listed as a threat to the species in future risk assessments.