Toxic metals and metalloid are being rapidly added from multiple pathways to aquatic ecosystem and causing severe threats to inhabiting fauna including fish. Being common in all the type of aquatic ecosystems such as freshwater, marine and brackish water fish are the first to get prone to toxic metals and metalloids. In addition to a number of physiological/biochemical alterations, toxic metals and metalloids cause enhanced generation of varied reactive oxygen species (ROS) ultimately leading to a situation called oxidative stress. However, as an important component of antioxidant defence system in fish, the tripeptide glutathione (GSH) directly or indirectly regulates the scavenging of ROS and their reaction products. Additionally, several other GSH-associated enzymes such as GSH reductase (GR, EC 1.6.4.2), GSH peroxidase (EC 1.11.1.9), and GSH sulfotransferase (glutathione-S-transferase (GST), EC 2.5.1.18) cumulatively protect fish against ROS and their reaction products accrued anomalies under toxic metals and metalloids stress conditions. The current review highlights recent research findings on the modulation of GSH, its redox couple (reduced glutathione/oxidised glutathione), and other GSH-related enzymes (GR, glutathione peroxidase, GST) involved in the detoxification of harmful ROS and their reaction products in toxic metals and metalloids-exposed fish.

The bioaccessibility of soil heavy metals is the solubility of soil heavy metals in synthetic human digestive juice, which is usually determined using in vitro digestion test. To reveal the effects of digestive enzymes on soil heavy metals bioaccessibility, three representative in vitro digestion tests, Simple Bioaccessibility Extraction Test (SBET), Physiologically Based Extraction Test (PBET), and Simple Gastrointestinal Extraction Test (SGET), were chosen. The bioaccessibility of soil Cu, Zn, and Pb in each method were respectively evaluated with and without digestive enzymes, and the differences were compared. The results showed that the effects of digestive enzymes varied with different methods and elements. Because of digestive enzymes addition, the environmental change from acid gastric phase to neutral intestinal phase of PBET did not result in apparently decrease of the bioaccessibility of soil Cu. However, the solubility of soil Zn and Pb were pH-dependent. For SGET, when digestive enzymes were added, its results reflected more variations resulting from soil and element types. The impacts of digestive enzymes on heavy metal dissolution are mostly seen in the intestinal phase. Therefore, digestive enzyme addition is indispensable to the gastrointestinal digestion methods (PBET and SGET), while the pepsin addition is not important for the methods only comprised of gastric digestion (SBET).

The concentrations and distributions of mercury (Hg) in topsoil from four provinces and one municipality in China were investigated. A total of 1,254 samples were collected and analyzed. The average concentrations of Hg were 0.064 mg kg⁻¹ for Liaoning Province, 0.100 mg kg⁻¹ for Jiangsu Province, 0.110 mg kg⁻¹ for Zhejiang Province, 0.154 mg kg⁻¹ for Sichuan Province, and 0.098 mg kg⁻¹ for Chongqing Municipality. Although differences were found among the ranges of Hg concentrations, the average values for each region were similar with other published data. The concentrations of Hg in topsoil varied largely upon the sampling locations. More than 80 % of the soil samples from Liaoning Province, Jiangsu Province, Zhejiang Province, and Chongqing Municipality, were ranked Grade I by the China Environmental Quality Standard for Soils, which can be considered as not contaminated by Hg. The concentrations of Hg in 0.3–0.4 % of soils collected from Jiangsu Province, Zhejiang Province and Chongqing Municipality exceeded the limitation for Grade III, indicating the contamination of Hg in these sites. The sources and potential risks of Hg in these sites should be brought to attention and further investigated.

The Fenton-like degradation of nalidixic acid was studied in this work. The effects of Fe³⁺ concentration and initial H₂O₂ concentration were investigated. Increasing the initial H₂O₂ concentration enhances the degradation and mineralization efficiency for nalidixic acid, while Fe³⁺ shows an optimal concentration of 0.25 mM. A complete removal of nalidixic acid and a TOC removal of 28 % were achieved in 60 min under a reaction condition of [Fe³⁺] = 0.25 mM, [H₂O₂] = 10 mM, T = 35 °C, and pH = 3. LC–MS analysis technique was used to analyze the possible degradation intermediates. The degradation pathways of nalidixic acid were proposed according to the identified intermediates and the electron density distribution of nalidixic acid. The Fenton-like degradation reaction of nalidixic acid mainly begins with the electrophilic attack of hydroxyl radical towards the C₃ position which results in the ring-opening reaction; meanwhile, hydroxyl radical attacking to the branched alkyl groups of nalidixic acid leads to the oxidation at the branched alkyl groups.

Diet and drinking water are suggested to be major exposure pathways for perfluoroalkyl substances (PFASs). In this study, food items and water from Faroe Islands sampled in 2011/2012 were analyzed for 11 perfluoroalkyl carboxylic acids (PFCAs) and 4 perfluoroalkane sulfonic acids (PFSAs). The food samples included milk, yoghurt, crème fraiche, potatoes, fish, and fish feed, and the water samples included surface water and purified drinking water. In total, nine PFCAs and four PFSAs were detected. Generally, the levels of PFAS were in the lower picogram per gram range. Perfluorobutanoic acid was a major contributor to the total PFASs concentration in water samples and had a mean concentration of 750 pg/L. Perfluoroundecanoic acid (PFUnDA) was predominating in milk and wild fish with mean concentrations of 170 pg/g. Perfluorooctane sulfonic acid (PFOS) was most frequently detected in food items followed by PFUnDA, perfluorononanoic acid, and perfluorooctanoic acid (PFOA). Levels of PFUnDA and PFOA exceeded those of PFOS in milk and fish samples. Prevalence of long-chain PFCAs in Faroese food items and water is confirming earlier observations of their increase in Arctic biota. Predominance of short-chain and long-chain homologues indicates exposure from PFOS and PFOA replacement compounds.

Pikeperch (Sander lucioperca), European catfish (Silurus glanis), common carp (Cyprinus carpio), and gobies (Neogobius gymnotrachelus, Neogobius melanostomus) were collected from the Danube River (Belgrade section), and samples of liver, muscle, or whole-body composites (in the case of gobies) were analyzed for As, Cu, Fe, Hg, Mn, and Zn with inductively coupled plasma optical spectrometry to find out if there was a correlation between accumulation of these elements in predatory and prey species, as well as in pairs of species with overlapping diets. Concentrations of all analyzed elements were either higher (Cu, Fe, Mn, Zn) in liver than in muscle, or equal (As, Hg), except for Hg in carp, which was higher in muscle. Mercury concentration in liver and muscle of predators (catfish, pikeperch) was significantly (<10⁻⁴) higher than in prey fishes (carp and gobies). The results indicate that Hg concentration was biomagnified through the food chain. Concentrations of As, Fe, and Hg in carp liver and gobies whole-body composite were similar, but carp had significantly (<10⁻⁴) higher values of Zn and Cu in liver. The regression analysis and trendline equations indicate that the concentrations of all tested elements, except for As in liver, and Mn and Fe in muscle, were similar in predatory fish (pikeperch and catfish), on one hand, and in prey fish (carp and gobies), on the other hand. Distinctly high Zn concentration in carp is very common in this species due to its physiology. Concentrations of Hg and Zn were higher than the maximum acceptable concentration due to the high pollution level in this section of the Danube River, accordingly posing a risk for the human consumption of these fish species.

The aim of this study was to evaluate applicability of ion exchange process for organics removal from Douro River surface water at the intake of Lever water treatment plant using magnetized ion exchange resin MIEX®. Qualitative analysis of the natural organic matter present in the surface water and prediction of its amenability to removal in conventional coagulation process were assessed. Results obtained in MIEX®DOC process kinetic batch experiments allowed determination of ion exchange efficiency in dissolved organic carbon (DOC), UV absorbing organics, and true color removal. The data were compared with the efficiencies of the conventional unit processes for organics removal at Lever WTP. MIEX®DOC process revealed to be more efficient in DOC removal than conventional treatment achieving the efficiencies in the range of 61–91 %, lowering disinfection by-products formation potential of the water. DOC removal efficiency at Lever WTP depends largely on the raw water quality and ranges from 28 % for water of moderated quality to 89 % of significantly deteriorated quality. In this work, MIEX®DOC process was also used as a reference method for the determination of contribution of anionic fraction to dissolved organic matter and selectivity of the unit processes at Lever WTP for its removal.

Clotrimazole is an azole fungicide used as a human pharmaceutical that is known to inhibit cytochrome P450 (CYP) enzymatic activities, including several steroidogenic CYP. In a previous report, we showed that a 7-day exposure to clotrimazole induced the expression of genes related to steroidogenesis in the testes as a compensatory response, involving the activation of the Fsh/Fshr pathway. In this context, the aim of the present study was to assess the effect of an in vivo 21-day chronic exposure to clotrimazole (30–197 μg/L) on zebrafish testis function, i.e., spermatogenesis and androgen release. The experimental design combined (1) gene transcript levels measurements along the brain–pituitary–gonad axis, (2) 11-ketotestosterone (11-KT) quantification in the blood, and (3) histology of the testes, including morphometric analysis. The chronic exposure led to an induction of steroidogenesis-related genes and fshr in the testes as well as fshβ in the pituitary. Moreover, increases of the gonadosomatic index and of the volume proportion of interstitial Leydig cells were observed in clotrimazole-exposed fish. In accordance with these histological observations, the circulating concentration of 11-KT had increased. Morphometric analysis of the testes did not show an effect of clotrimazole on meiotic (spermatocytes) or postmeiotic (spermatids and spermatozoa) stages, but we observed an increase in the number of type A spermatogonia, in agreement with an increase in mRNA levels of piwil1, a specific molecular marker of type A spermatogonia. Our study demonstrated that clotrimazole is able to affect testicular physiology and raised further concern about the impact of clotrimazole on reproduction.

The concentrations, compositional profiles, and possible sources of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/PCDF) in water column and surface sediment samples from the lower reaches of the Yangtze River were investigated, and the potential risks posed by these chemicals were evaluated. Concentrations of the 17 2,3,7,8-substituted PCDD/PCDF in the water and sediment samples ranged from 0.45 to 10.0 pg TEQ/L (mean 2.34 pg TEQ/L) and from 0.31 to 51 pg TEQ/g dw (mean 5.25 pg TEQ/g dw), respectively. Water and sediments from the Nanjing-Nantong sections of the Yangtze River were found to have elevated PCDD/PCDF levels, and the PCDD/PCDF TEQ concentrations in 13 sediment samples exceeded the probable effect levels (PEL), above which adverse biological effects are likely. Multivariate statistical analysis indicated that the principal PCDD/PCDF contamination source for the water and sediment was the production and use of pentachlorophenol (PCP) or sodium pentachlorophenate (PCP-Na). PCDD/PCDF concentrations were stable over time near the Yangtze River Estuary but had increased sharply in recent decades in the Nanjing-Nantong section, which will have been related to the growth in industrial activities and other anthropogenic PCDD/PCDF sources. Total organic carbon (TOC) and PCDD/PCDF concentrations correlated significantly (R = 0.474, P < 0.01), suggesting that TOC plays an important role in the transport and re-distribution of PCDD/PCDF in the Yangtze River basin.

The construction and electrodes characteristics of poly(vinylchloride) (PVC)-based polymeric membrane electrode (PME) and coated graphite electrode (CGE), incorporating 1,3-alternate thiacalix[4]crown as ionophore for estimation of Hg(II) ions, are reported here. The best potential response was observed for PME-1 having membrane composition of: ionophore (6.2 mg), PVC (100.0 mg), 2-nitrophenyl octyl ether (2-NPOE; 200.0 mg), and sodium tetraphenyl borate (NaTPB; 2.0 mg); for CGE-1 with the membrane composition: ionophore (3.5 mg), PVC (40.0 mg), 2-NPOE (80.0 mg), and NaTPB (2.0 mg). The electrodes exhibits Nernstian slope of 29.16 mV/decade with PME-1 and 30.39 mV/decade with CGE-1 for Hg(II) ions over wide concentration range, i.e., 1.0 × 10⁻¹ to 5.0 × 10⁻⁶ M with PME-1 and 1.0 × 10⁻¹ to 5.0 × 10⁻⁷ M with CGE-1. Lower detection limits were found to be 9.77 × 10⁻⁶ M for PME-1 and 7.76 × 10⁻⁷ M for CGE-1 with response time varying from 10 to 20 s. Also, these electrodes work within pH range of 2.0–6.0 for PME-1 and 1.5–6.5 for CGE-1. Overall, CGE-1 has been found to be better than PME-1. CGE-1 has been used as indicator electrode for the potentiometric titration of Hg(II) ions with EDTA as well as successfully applied for determination of Hg(II) content in wastewater, insecticide, dental amalgam, and ayurvedic medicines samples with very good performance (0.9974 correlation coefficient in the comparison against volumetric method).