Characterizing the Areal Extent of PFAS Contamination in Fish Species Downgradient of AFFF Source Zones.

Most monitoring programs next to large per- and polyfluoroalkyl substances (PFAS) sources focus on drinking water contamination near source zones. However, less is understood about how these sources affect downgradient hydrological systems and food webs. Here, we report paired PFAS measurements in water, sediment, and aquatic biota along a hydrological gradient away from source zones contaminated by the use of legacy aqueous film-forming foam (AFFF) manufactured using electrochemical fluorination. Clustering analysis indicates that the PFAS composition characteristic of AFFF is detectable in water and fishes >8 km from the source. Concentrations of 38 targeted PFAS and extractable organofluorine (EOF) decreased in fishes downgradient of the AFFF-contaminated source zones. However, PFAS concentrations remained above consumption limits at all locations within the affected watershed. Perfluoroalkyl sulfonamide precursors accounted for approximately half of targeted PFAS in fish tissues, which explain >90% of EOF across all sampling locations. Suspect screening analyses revealed the presence of a polyfluoroketone pharmaceutical in fish species, and a fluorinated agrochemical in water that likely does not accumulate in biological tissues, suggesting the presence of diffuse sources such as septic system and agrochemical inputs throughout the watershed in addition to AFFF contamination. Based on these results, monitoring programs that consider all hydrologically connected regions within watersheds affected by large PFAS sources would help ensure public health protection.

Conversion of Rice Field Ecosystems from Conventional to Ecological Farming: Effects on Pesticide Fate, Ecotoxicity and Soil Properties.

Rice is an important staple food around the world, the cultivation as sustainable agriculture and food supply are key to achieving the Sustainable Development Goals (SDGs) of 2030. In order to analyze the sustainability of the rice paddy ecosystem, a comparative study was carried out during the rice growing season between paddies with conventional agriculture (CA) and ecological agriculture (EA), integrating analysis of physico-chemical characteristics of soil and soil pore water, pesticide residues, acute toxic effects and potential ecological risk, as well as aquatic invertebrate community structure dynamics. Our study found that total carbon and nitrogen present in soil were significantly higher in CA than in EA, while opposite results were found in soil pore water, implying the improvement on soil properties in EA. Neonicotinoid pesticides (thiamethoxam and thiacloprid) were still detected in EA, although no pesticides were applied after conversing CA to EA. Additionally, toxic effects to zebrafish embryos with a peak toxicity in summer (July, LC50 = 55.26 mg soil equivalent/L) were also found in EA, which was lower than in CA. The dynamics of the aquatic invertebrate community structure were correlated with the toxicity results, with higher diversity recorded in EA. Therefore, for the purpose of ecosystem sustainability, the long-term implementation of EA is highly recommended.

Assessment of pesticide residues: a comprehensive analysis of seasonal trends and health implications.

This study assessed the presence of eight pesticide residues in the Indus River, Mianwali, Pakistan, focusing on three sampling sites (S1, S2, and S3) in water, sediment, and the fish species Cyprinus carpio during both dry and wet seasons. Analysis was conducted using gas chromatography with an electron capture detector. Results indicated elevated pesticide concentrations in both seasons, with levels of 0.84 and 0.62 µg/L in water, 12.47 and 9.21 µg/g/dw in sediment, and 17.33 and 12.17 µg/g/ww in fish, with higher concentrations observed during the dry season. Cypermethrin and carbofuran were the primary pesticides detected in water, while endosulfan and cypermethrin were dominant in sediment and fish tissue, often exceeding standard safety thresholds. Principal Component Analysis (PCA) and cluster analysis revealed stronger correlations between sediment and fish muscle, with varying associations among pesticides across seasons. The Hazard Index (HI) surpassed 1 in both seasons, signaling potential health risks to humans. These findings underscore the substantial risk agricultural pesticides pose to the aquatic ecosystem and food chain, highlighting the urgent need for sustainable agricultural practices and stricter regulations to minimize pesticide use and encourage eco-friendly pest management strategies.

Occurrence and bioaccumulation of parabens and their metabolites in the biota from a subtropical freshwater river ecosystem: Implications for human exposure.

Widespread occurrence of parabens in the environment has been documented, whereas little information is available about the occurrence and bioaccumulation of parabens in the aquatic biota. In this study, plants (n = 14), plankton (n = 20), and fish muscle (n = 89) samples were collected from Dongjiang River Basin and analyzed for nine parabens and two of their metabolites using ultra-high performance liquid chromatogram-tandem mass spectrometry. All the samples contained notable concentrations of parabens and the metabolites, and the total concentrations of parabens (Σp-PBs; sum of nine parent compounds) ranged from 0.40 to 776 ng/g dry wt. MeP, EtP, and PrP were the predominant parent compounds in both plankton and fish, while in plants, MeP, BzP and EtP were the top three abundant chemicals. As the predominant metabolite, 4-HB was detected in 99% aquatic biota samples analyzed with the highest concentration (24800 ng/g, dry wt) detected in an alga. Significantly positively correlations among the concentrations of MeP, BzP, EtP and 4-HB in the fish muscle were found. Based on dry weight, bioaccumulation potentials of these chemical substances were estimated with bioaccumulation factor (BAF) values greater than 2000 L/kg, suggestive of bioaccumulative in aquatic biota. Based on the concentrations measured, the daily intake (EDI) of parabens through fish consumption was estimated with the mean EDIs as 4.20, 2.41, and 1.93 ng/kg bw/day for toddlers, children, and adults in urban, respectively. This study provides baseline information about the occurrence and fate of parabens in the aquatic environment.

Characterising contaminants distribution in marine-coastal sediments through multivariate and nonparametric statistical analyses: a complementary strategy supporting environmental monitoring and control.

This work investigates a statistical approach analysing data from monitoring activities on marine-coastal areas for environmental quality determination and surveillance. Analyses were performed on a database of the Environmental Protection and Prevention Agency of the Puglia Region. As, Cr, Ni, and Pb concentration values in marine sediments and biota from 2013 to 2015 and 2017 were processed to investigate different contaminant characteristics. Hierarchical cluster analysis identified three contaminant distribution classes with (1) highest Cr, Ni, and Pb concentrations, (2) highest As concentration, and (3) lowest contaminants concentration. The Kruskal-Wallis and Friedman tests showed that contaminant distributions were statistically different when considering the monitoring years and classes. However, statistical similarities resulted during the 2013-2017 and 2014-2015 periods. Spearman's coefficients displayed positive correlations among the pollutants in each matrix and mainly negative correlations for matrices comparison. This methodology aims to provide a practical support for monitoring to identify potential environmental deterioration over time and correlations with specific contamination sources.

The ecotoxicological effects of microplastics on aquatic food web, from primary producer to human: A review.

The prevalence of microplastics in global waters raises the concern about their potential effects on aquatic biota. In aquatic environment, microplastics are almost ubiquitously present in all compartments from surface water to benthic sediment, making them accessible to a wide range of aquatic biota occupying different habitats. Exposure to microplastics may induce detrimental implications to the health of aquatic organisms. This review describes the wide occurrence of microplastics ingestion by aquatic fauna and evaluates the ecotoxicological effects of microplastics as well as the associated chemicals on aquatic biota including phytoplankton and fauna from both freshwater and marine environments. Trophic transfer of microplastics and associated contaminants along the aquatic food chain and potential impacts on human health are also discussed. Finally, this review emphasizes the current knowledge gaps and gives recommendations for the future work.

Acute and chronic ecotoxicological effects of four pharmaceuticals drugs on cladoceran Daphnia magna.

The occurrence of pharmaceuticals in the aquatic environment has received increasing attention in recent years, as concerns have risen about their environmental persistence, biological activity and different effects toward nontarget organisms. Considering the magnitude of concentrations (ng L(-1) to mg L(-1)) and their often-specific modes of action, the assessment of physiological responses of exposed aquatic biota may provide significant information regarding the potential ecological consequences of exposure to these contaminants. The present study intended to assess the acute and chronic effects of four pharmaceuticals: acetaminophen, chlorpromazine, diclofenac sodium and propranolol in the cladoceran species Daphnia magna. Parameters such as immobility, total of offspring and rate of population increase were analyzed. Results of acute exposures showed a considerable variability of toxicity among pharmaceuticals, with the following ranking of toxicity: diclofenac (EC50 = 123.3 mg L(-1)) < propranolol (EC50 = 5.531 mg L(-1)) < acetaminophen (EC50 = 2.831 mg L(-1)) < chlorpromazine (EC50 = 1.805 mg L(-1)). The chronic toxicity data showed the exertion of reproductive adverse effects. The compounds chlorpromazine and propranolol caused a significant decrease in fecundity, and the rate of population increase parameter suffered a significant decrease from 0.33 mg L(-1) to 0.128 mg L(-1) onwards, respectively. The levels of exposure to which our test organism was acutely and chronically exposed were above those already reported in the wild. Nevertheless, the extensive production, prescription and release of pharmaceuticals drugs will continue to grow in the future, and consequently their loadings to the environment can result in potential long-term ecological risks to aquatic biota.

Usefulness of oxidative stress biomarkers in native species for the biomonitoring of pesticide pollution in a shallow lake of the Austral Pampas, Argentina.

Pesticide contamination and its adverse effects on native freshwater species continue to be a worldwide major concern, mainly in developing countries. Passive biomonitoring of pesticide pollution in shallow lakes may be achieved by the simultaneous use of fish and wetland plants. Thus, the present study aimed to evaluate the occurrence of current-use pesticides in the surface water of a shallow lake of the Austral Pampas region (Buenos Aires Province, Argentina) surrounded by intensive agricultural activities and its relationship with a battery of biomarkers, including oxidative stress and genotoxicity, in two native species, the fish Oligosarcus jenynsii and the macrophyte Bidens laevis. A total of 26 pesticide residues were analyzed, and the main ones detected were glyphosate and its metabolite aminomethylphosphonic acid (AMPA), chlorpyrifos, and imidacloprid. In O. jenynsii, hydrogen peroxide (H2O2) content in the liver increased with chlorpyrifos occurrence, while malondialdehyde (MDA) levels in the brain and liver increased with the presence of both chlorpyrifos and glyphosate. In B. laevis, H2O2 and MDA levels in leaves and roots increased with AMPA occurrence. Also, leaf H2O2 contents and root MDA levels increased with chlorpyrifos concentration. In contrast, catalase and peroxidase activities in roots decreased with AMPA and chlorpyrifos occurrence. In both species, mainly H2O2 and MDA levels demonstrated their sensitivity to be used as biomarkers in the biomonitoring of current-use pesticide pollution in shallow lakes. Their use may provide information to plan strategies for environmental conservation by government institutions or decision-makers, and to assess the biota health status.

Probabilistic risk assessment of microplastics on aquatic biota in coastal sediments.

As an emerging form of pollution, microplastic contamination of the coastal ecosystems is one of the world's most pressing environmental concerns. Coastal sediments have been polluted to varying degrees by microplastics, and their ubiquitous presence in sediments poses a threat to marine organisms. However, there is currently no ecological risk assessment of microplastics on aquatic biota in sediments. This study, for the first time, established a new procedure to evaluate the toxicity of microplastics on aquatic biota in sediments, based on the probabilistic risk assessment (PRA) concept. The choice of Zhelin Bay as the case study site was based on its severe pollution status. The average content of microplastics in the sediments of Zhelin Bay was 2054.17 items kg-1 dry weight, and these microplastics consisted of 46 different species. Microplastics in sediments exist in five different forms, with the film form being the main composition, and the majority of microplastics have particle sizes ranging from 100 to 500 µm. Correlation analysis (CA) reveals significant negative correlations between microplastic abundance, and Al2O3 and SiO2. The toxicity of microplastics, based on the PRA concept, suggests that Zhelin Bay surface sediments had a low probability (3.43%) of toxic effects on aquatic biota.

Unintentionally-produced persistent organic pollutants in the aquatic environment contaminated from historical chlor-alkali production.

Historical chlor-alkali production has led to substantial concentrations of persistent organic pollutant residues in the environment. This study systematically investigated the distribution of polycyclic aromatic hydrocarbons (PAHs), chlorinated/brominated-PAHs (Cl/Br-PAHs), polychlorinated naphthalenes (PCNs), and hexachlorobutadiene (HCBD) in sediment, lotus (Nelumbo nucifera), and fish samples from Ya-Er Lake, which is a site in China with historical chlor-alkali contamination. The average concentrations [(4.97-1.47) × 103 ng/g dry weight (dw)] of these pollutants in backfill sediments, which were dredged from the lake after chlor-alkali production stopped, were 2.68-70.87 times those in fresh lake sediments (0.622-218 ng/g dw) and reported concentrations in other areas. Correlation analyses indicated that Cl-PAHs, Br-PAHs, and PCNs likely originated from halogenation of parent PAHs in the study area, and the chlorination ratios were larger than those of bromination. The Cl(1/2/3)-PAHs/PAHs and Br(1)-PAHs/PAHs ratios were higher than those for PAHs with more halogen atoms. This contamination extended into the biota, with notable pollutant burdens found in lotus (Nelumbo nucifera, 0.305-77.3 ng/g dw) and even higher concentrations in fish (2.20-345 ng/g lipid weight). Estimated biological soil accumulation factors revealed significant enrichment in lotus organs (mean: 7.19) and fish muscle (mean: 10.65), especially the latter, which highlighted bioaccumulation and potential food chain transfer risks. The estimated daily intakes of PAHs, Cl/Br-PAHs, and HCBD through fish consumption currently pose negligible risks, while dietary intake of PCNs may present health concerns. Continuous monitoring and impact assessments are crucial for developing appropriate risk management strategies to safeguard public health.

Advances of microplastics ingestion on the morphological and behavioral conditions of model zebrafish: A review.

Concerns have been conveyed regarding the availability and hazards of microplastics (MPs) in aquatic biota due to their widespread presence in aquatic habitats. Zebrafish (Danio rerio) are widely used as a model organism to study the adverse impacts of MPs due to their several compelling advantages, such as their small size, ease of breeding, inexpensive maintenance, short life cycle, year-round spawning, high fecundity, fewer legal restrictions, and genetic resemblances to humans. Exposure of organisms to MPs produces physical and chemical toxic effects, including abnormal behavior, oxidative stress, neurotoxicity, genotoxicity, immune toxicity, reproductive imbalance, and histopathological effects. But the severity of the effects is size and concentration-dependent. It has been demonstrated that smaller particles could reach the gut and liver, while larger particles are only confined to the gill, the digestive tract of adult zebrafish. This thorough review encapsulates the current body of literature concerning research on MPs in zebrafish and demonstrates an overview of MPs size and concentration effects on the physiological, morphological, and behavioral characteristics of zebrafish. Finding gaps in the literature paves the way for further investigation.

Decoding the molecular concerto: Toxicotranscriptomic evaluation of microplastic and nanoplastic impacts on aquatic organisms.

The pervasive and steadily increasing presence of microplastics/nanoplastics (MPs/NPs) in aquatic environments has raised significant concerns regarding their potential adverse effects on aquatic organisms and their integration into trophic dynamics. This emerging issue has garnered the attention of (eco)toxicologists, promoting the utilization of toxicotranscriptomics to unravel the responses of aquatic organisms not only to MPs/NPs but also to a wide spectrum of environmental pollutants. This review aims to systematically explore the broad repertoire of predicted molecular responses by aquatic organisms, providing valuable intuitions into complex interactions between plastic pollutants and aquatic biota. By synthesizing the latest literature, present analysis sheds light on transcriptomic signatures like gene expression, interconnected pathways and overall molecular mechanisms influenced by various plasticizers. Harmful effects of these contaminants on key genes/protein transcripts associated with crucial pathways lead to abnormal immune response, metabolic response, neural response, apoptosis and DNA damage, growth, development, reproductive abnormalities, detoxification, and oxidative stress in aquatic organisms. However, unique challenge lies in enhancing the fingerprint of MPs/NPs, presenting complicated enigma that requires decoding their specific impact at molecular levels. The exploration endeavors, not only to consolidate existing knowledge, but also to identify critical gaps in understanding, push forward the frontiers of knowledge about transcriptomic signatures of plastic contaminants. Moreover, this appraisal emphasizes the imperative to monitor and mitigate the contamination of commercially important aquatic species by MPs/NPs, highlighting the pivotal role that regulatory frameworks must play in protecting all aquatic ecosystems. This commitment aligns with the broader goal of ensuring the sustainability of aquatic resources and the resilience of ecosystems facing the growing threat of plastic pollutants.

Assessment, distribution, and ecological risk of contaminants of emerging concern in a surface water-sediment-fish system impacted by wastewater.

The presence of contaminants of emerging concern in aquatic ecosystems represents an ever-increasing environmental problem. Aquatic biota is exposed to these contaminants, which can be absorbed and distributed to their organs. This study focused on the assessment, distribution, and ecological risk of 32 CECs in a Spanish river impacted by effluents from a wastewater treatment plant, analyzing the organs and plasma of common carp. Environmental concentrations in water and sediment were examined at sites upstream and downstream of the wastewater treatment plant. The two downstream sites showed 15 times higher total concentrations (12.4 µg L-1 and 30.1 µg L-1) than the two upstream sites (2.08 µg L-1 and 1.66 µg L-1). Half of the CECs were detected in fish organs, with amantadine having the highest concentrations in the kidney (158 ng g-1 w.w.) and liver (93 ng g-1 w.w.), followed by terbutryn, diazepam, and bisphenol F in the brain (50.2, 3.82 and 1.18 ng g-1 w.w.). The experimental bioaccumulation factors per organ were compared with the bioconcentration factors predicted by a physiologically based pharmacokinetic model, obtaining differences of one to two logarithmic units for most compounds. Risk quotients indicated a low risk for 38 % of the contaminants. However, caffeine and terbutryn showed an elevated risk for fish. The mixed risk quotient revealed a medium risk for most of the samples in the three environmental compartments: surface water, sediment, and fish.

Ecotoxicity of eluates obtained from Basamid® contaminated soils is pH dependent: A study with Hydra viridissima, Xenopus laevis and Danio rerio.

Agrochemicals are mostly used to deplete pests and treat diseases in terrestrial agro-ecosystems. However, their transport through the soil, by leaching and/or runoff, may cause them to reach aquatic systems. Environmental parameters, such as soil pH, can affect this transport, by influencing the magnitude of agrochemicals degradation and chemical reaction. This work aimed at investigating the influence of soil pH on the toxicity of eluates obtained from Basamid® contaminated soils to Hydra viridissima, Xenopus laevis and Danio rerio. For this, a natural soil with pH amended to 5.5, 6.5 and 7.5, was spiked with the recommended dose (RD) of Basamid® (145 mg dazomet/kg soil) and eluates (Ba-E) were prepared with the respective species culture medium. Dilutions of the eluates (0.14-100%), obtained from the three soils (Ba-E 5.5, Ba-E 6.5 and Ba-E 7.5, corresponding to soil spiked with Basamid® RD at soil pH of 5.5, 6.5 and 7.5, respectively), were used to expose the organisms. Results showed that for H. viridissima increased soil alkalinity provoked less mortality comparatively to lower soil pH [LD50,96h of Ba-E 5.5: 10.6% and LD50,96h of Ba-E 7.5: 21.2%]. As for X. laevis and D. rerio Ba-E lethal ecotoxicity was similar across soil pH (LD50,96h varied from 5.7 to 6.9% and from 2.1 to 4.3%, respectively). For malformations, 20% effect dilution (ED) in H. viridissima was significantly higher at Ba-E 7.5 (ED20,96h: 17.4%), comparatively to Ba-E 5.5 and Ba-E 6.5 (ED20,96h: 7.9% and 7.7%, respectively). From the three tested organisms and based on both lethal and sublethal effects, H. viridissima presented the highest tolerance to Basamid® eluates and soil pH was a major factor determining the fumigant toxicity, with higher soil pH levels inducing, lower toxicity. The eluates obtained from soils contaminated with RD of Basamid® induced severe effects to the three aquatic species.

Ecotoxicological Properties of Titanium Dioxide Nanomorphologies in Daphnia magna.

In this work, the structural, vibrational, morphological, and colloidal properties of commercial 15.1 nm TiO2 nanoparticles (NPs) and nanowires (NWs, 5.6 thickness, 74.6 nm length) were studied with the purpose of determining their ecotoxicological properties. This was achieved by evaluating acute ecotoxicity experiments carried out in the environmental bioindicator Daphnia magna, where their 24-h lethal concentration (LC50) and morphological changes were evaluated using a TiO2 suspension (pH = 7) with point of zero charge at 6.5 for TiO2 NPs (hydrodynamic diameter of 130 nm) and 5.3 for TiO2 NWs (hydrodynamic diameter of 118 nm). Their LC50 values were 157 and 166 mg L-1 for TiO2 NWs and TiO2 NPs, respectively. The reproduction rate of D. magna after fifteen days of exposure to TiO2 nanomorphologies was delayed (0 pups for TiO2 NWs and 45 neonates for TiO2 NPs) in comparison with the negative control (104 pups). From the morphological experiments, we may conclude that the harmful effects of TiO2 NWs are more severe than those of 100% anatase TiO2 NPs, likely associated with brookite (36.5 wt. %) and protonic trititanate (63.5 wt. %) presented in TiO2 NWs according to Rietveld quantitative phase analysis. Specifically, significant change in the heart morphological parameter was observed. In addition, the structural and morphological properties of TiO2 nanomorphologies were investigated using X-ray diffraction and electron microscopy techniques to confirm the physicochemical properties after the ecotoxicological experiments. The results reveal that no alteration in the chemical structure, size (16.5 nm for TiO2 NPs and 6.6 thickness and 79.2 nm length for NWs), and composition occurred. Hence, both TiO2 samples can be stored and reused for future environmental purposes, e.g., water nanoremediation.

Assessment of wastewater-borne pharmaceuticals in tissues and body fluids from riverine fish.

Riverine fish in densely populated areas is constantly exposed to wastewater-borne contaminants from effluent discharges. These can enter the organism through the skin, gills or by ingestion. Whereas most studies assessing the contaminant burden in exposed fish have focused either on muscle or a limited set of tissues. Here we set out to generate a more comprehensive overview of the distribution of pollutants across tissues by analyzing a panel of matrices including liver, kidney, skin, brain, muscle, heart, plasma and bile. To achieve a broad analyte coverage with a minimal bias towards a specific contaminant class, sample extracts from four fish species were analyzed by High-Performance Liquid Chromatography (HPLC) - high-resolution mass spectrometry (HRMS) for the presence of 600 wastewater-borne pharmaceutically active compounds (PhACs) with known environmental relevance in river water through a suspect-screening analysis. A total of 30 compounds were detected by suspect screening in at least one of the analyzed tissues with a clear prevalence of antidepressants. Of these, 15 were detected at confidence level 2.a (Schymanski scale), and 15 were detected at confidence level 1 following confirmation with authentic standards, which furthermore enabled their quantification. The detected PhACs confirmed with level 1 of confidence included acridone, acetaminophen, caffeine, clarithromycin, codeine, diazepam, diltiazem, fluoxetine, ketoprofen, loratadine, metoprolol, sertraline, sotalol, trimethoprim, and venlafaxine. Among these substances, sertraline stood out as it displayed the highest detection frequency. The values of tissue partition coefficients for sertraline in the liver, kidney, brain and muscle were correlated with its physicochemical properties. Based on inter-matrix comparison of detection frequencies, liver, kidney, skin and heart should be included in the biomonitoring studies of PhACs in riverine fish.

Comparison of methods for the radiological impact assessment of aquatic releases to the waters in the low countries.

Accurate assessment of the radiological impact of liquid discharges on the marine environment is challenging despite all developments in recent years. The lack of consensus on this type of assessment manifests itself even stronger when transborder issues are expected, such as in the Low Countries. Belgium and the Netherlands operate nuclear power plants with discharges in the shared estuary of the Western Scheldt, therefore if there are safety concerns, information on both sides of the border must be coherent. This work provides a comparison of two computational methods used for assessment of aquatic releases in the Western Scheldt estuary and the adjacent North Sea.The work demonstrates a fair degree of consistency in modelling the uptake and fate of key anthropogenic radionuclides. Nevertheless, there are also considerable differences found in sediment and sea species with concentrations ranging by over two orders of magnitude in some cases. These explainable differences are methodological in nature, occurring in codes that underwent extensive validation during development. Therefore, the outcomes of this work clearly demonstrate the need to produce explicit guidance that is specifically tailored to the (inter)national water system of concern. This should not be limited to releases from nuclear power plants, but also include other nuclear applications. For all these reasons, more intensive collaboration and model harmonisation across borders is essential, signalling the direction for future investigations.

Nonmetric multidimensional scaling and probabilistic ecological risk assessment of trace metals in surface sediments of Daya Bay (China) using diffusive gradients in thin films.

This research is one main objective to assess combined toxicity of trace metal mixtures in aquatic biota in coastal sediments. Coastal sediments around the world are a major reservoir of trace metals from industrial wastewater discharge. Our case study site, Daya Bay in southern China, was selected because it has been under severe man-made impacts. Diffusive gradients in thin films (DGT) technique has proven to be a good method for measuring the bioavailability of trace metals. The bioavailability and distribution of trace metals in surface sediments were investigated along with their possible biological risks. The average bioavailable (DGT-labile) concentrations (µg/L) were 0.44 (V), 0.51 (Cr), 52.49 (Mn), 0.10 (Co), 1.36 (Ni), 0.74 (Cu), 14.53 (Zn), 0.97 (As), 0.14 (Se), 6.73 (Mo), 0.17 (Cd), 0.27 (Sb), 0.10 (W), and 1.32 (Pb). Nonmetric multidimensional scaling (NMS) is a robust multivariate ordination method that makes no assumptions about the distribution of the underlying data. NMS was used to explore that DGT-labile concentrations of trace metals were influenced by sediment properties. NMS results indicated that most DGT- labile trace metals influenced by sediment properties. Risk assessment of single trace metal toxicity revealed that risk quotient (RQ) values for Mn, Cu, Zn and Pb significantly exceeded 1, demonstrating that the toxic effects of these trace metals should be not ignored. The probabilistic ecological risk assessment for integral toxicity of one mixture of 14 trace metals revealed that Daya Bay surface sediments had a low probability (9.04 %) of adverse effects on aquatic biota.

Occurrence and tissue distribution of 33 legacy and novel per- and polyfluoroalkyl substances (PFASs) in Baikal seals (Phoca sibirica).

Per- and polyfluoroalkyl substances (PFASs) are bioaccumulative and associated with adverse effects in both wildlife and humans. The occurrence of 33 PFASs was assessed in the plasma, liver, blubber, and brain of 18 Baikal seals (Phoca sibirica) (16 pups and 2 adult females) from Lake Baikal, Russia (in 2011). Of the 33 congeners analysed for: perfluorooctanosulfonic acid (PFOS), 7 long chain perfluoroalkyl carboxylic acids (C8-C14 PFCAs) and 1 branched PFCA (perfluoro-3,7-dimethyloctanoic acid; P37DMOA) were most frequently detected. The PFASs in plasma and liver with the highest median concentrations were legacy congeners: perfluoroundecanoic acid (PFUnA; plasma: 11.2 ng/g w.w.; liver: 7.36 ng/g w.w.), PFOS (plasma: 8.67 ng/g w.w.; liver: 9.86 ng/g w.w.), perfluorodecanoic acid (PFDA; plasma: 5.13 ng/g w.w.; liver: 6.69 ng/g w.w.), perfluorononanoic acid (PFNA; plasma: 4.65 ng/g w.w.; liver: 5.83 ng/g w.w.) and perfluorotridecanoic acid (PFTriDA; plasma: 4.29 ng/g w.w.; liver: 2.55 ng/g w.w.). PFASs were detected in the brain of Baikal seals, indicating that PFASs cross through the blood-brain barrier. In blubber, the majority of PFASs were detected in low abundance and concentrations. In contrast to legacy PFASs, novel congeners (e.g., Gen X) were either detected infrequently or not found in Baikal seals. The worldwide occurrence of PFASs in pinnipeds was compared and lower median concentrations of PFOS were observed in Baikal seals relative to other pinnipeds. Conversely, similar concentrations of long chain PFCAs were found in Baikal seals compared to other pinnipeds. Furthermore, human exposure was assessed by estimating weekly intakes (EWI) of PFASs through Baikal seal consumption. Although PFASs concentrations were comparatively low relative to other pinnipeds, consumption of Baikal seal could exceed current regulatory guidelines.

Probabilistic ecotoxicological risk assessment of heavy metal and rare earth element mixtures in aquatic biota using the DGT technique in coastal sediments.

Heavy metals (HMs) are routine contaminants due to their extensive use worldwide. Rare earth elements (REEs) are emerging contaminants because of their global exploitation for use in the high-tech sector. Diffusive gradients in thin films (DGT) are an effective method for measuring the bioavailable component of pollutants. This study represents the first assessment of the mixture toxicity of HMs and REEs in aquatic biota using the DGT technique in sediments. Xincun Lagoon was chosen as the case study site because it has been contaminated by pollutants. Nonmetric multidimensional scaling (NMS) analysis reveals that a wide variety of pollutants (Cd, Pb, Ni, Cu, InHg, Co, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, and Yb) are primarily impacted by sediment characteristics. Appraisal of single HM-REE toxicity reveals that the risk quotient (RQ) values for Y, Yb and Ce notably exceeded 1, demonstrating that the adverse effects of these single HMs and REEs should not be ignored. The combined toxicity of HM-REE mixtures in terms of probabilistic ecological risk assessment shows that the Xincun surface sediments had a medium probability (31.29%) of toxic effects on aquatic biota.