Microplastic (MP) has been detected ubiquitously in freshwater systems. Until now MP sampling, however, is predominantly based on short-term net or pumping and filtration systems which can only provide snapshots of MP abundance; especially in flowing water bodies. To improve representativeness in the determination of MP occurrences in these aquatic compartments, an integrative approach that covers larger water volumes for a longer period of time is required. In this regard, surface water supplied drinking water treatment plants (DWTPs) represent an opportunity. In DWTPs, suspended solids from thousands of cubic metres of raw water are continuously removed over several hours and enriched in coagulation/flocculation and filtration processes. Our hypothesis was that MP is also removed to a full extent, like suspended solids, and that an integrative approach for identification and quantification in raw water can be derived from the analysis of MP in the treatment sludge. To prove this hypothesis, treatment sludge from a riverside DWTP (Warnow river, North-Eastern Germany) was analysed for MP > 50 μm. A sample purification protocol overcoming potential matrix effects caused by coagulants and flocculants was developed and validated. MP was analysed using micro-Raman spectroscopy. MP occurrence determined for the Warnow river was compared with in situ reference sampling using an established pumping and filtration system at relatively stable flow conditions. As result, the number of MP particles derived from treatment sludge was extrapolated to 196 ± 42 m⁻³ for the Warnow river and is statistically insignificantly different from 233 ± 36 m⁻³ identified by conventional water sampling. In addition, the polymer distribution and particles shape indicated the validity of the integrative concept. Consequently, the determination of MP abundance for freshwater systems based on DWTP treatment sludge represents an adequate method to estimate MP concentrations in flowing waters in an integrative way.

The Pearl River Estuary (PRE) is the largest estuary in southern China and under high metal stress. In the present study, we employed an integrated method of transcriptomics and proteomics to investigate the ecotoxicological effects of trace metals on the Hong Kong oyster Crassostrea hongkongensis. Three oyster populations with distinct spatial distributions of metals were sampled, including the Control (Station QA, the lowest metal levels), the High Cd (Station JZ, the highest Cd), and the High Zn–Cu–Cr–Ni (Station LFS, with the highest levels of zinc, copper, chromium, and nickel). Dominant metals in oysters were differentiated by principal component analysis (PCA), and theirgene and protein profiles were studied using RNA-seq and iTRAQ techniques. Of the 2250 proteins identified at both protein and RNA levels, 70 proteins exhibited differential expressions in response to metal stress in oysters from the two contaminated stations. There were 8 proteins altered at both stations, with the potential effects on mitochondria and endoplasmic reticulum by Ag. The genotoxicity, including impaired DNA replication and transcription, was specifically observed in the High Cd oysters with the dominating influence of Cd. The structural components (cytoskeleton and chromosome-associated proteins) were impaired by the over-accumulated Cu, Zn, Cr, and Ni at Station LFS. However, enhanced tRNA biogenesis and exosome activity might help the oysters to alleviate the toxicities resulting from their exposure to these metals. Our study provided comprehensive information on the molecular changes in oysters at both protein and RNA levels in responding to multi-levels of trace metal stress.

Transformation products (TPs) of micropollutants contaminating our water resources have become an emerging issue due to the potential threats they pose to environmental and human health. This study investigated the transformation chemistry, toxicity, physicochemical properties and environmental behavior resulting from photocatalytic transformation of organic UV filters as model micropollutants. 3-Benzylidene camphor (3-BC), 4-hydroxybenzophenone (4-HB) and octocrylene (OC) were effectively degraded by UV-A/TiO₂ treatment, with TPs identified and characterized with high resolution mass spectrometry. Nitrated-TPs were observed to be formed in the presence of nitrite and nitrate for 3-BC and 4-HB, suggesting that the transformation process could be altered by components in the water matrix. Vibrio fischeri bioluminescence inhibition assay revealed an increase in toxicity of TPs derived from photocatalytic treatment, with quantitative structure-activity relationship model (ECOSAR) predicted an enhanced toxicity of individual TPs' after transformation. Assessment of physicochemical properties and environmental behavior suggested that TPs as compared to parent organic UV filters, may represent even greater hazards due to their increased water solubility, persistence and mobility – in addition to retaining the parent organic UV filter's toxicity. The results provide important information relevant to the potential risks for the selected organic UV filters, and their corresponding transformation products.

The present study explores the immobilization of ligninolytic enzyme-laccase on the surface of rice straw biochar and evaluates its application for anthracene biodegradation. The rice straw biochar was acid-treated to generate carboxyl functionality on its surface, followed by detailed morphological and chemical characterization. The surface area of functionalized biochar displayed a two-fold increase compared to the untreated biochar. Laccase was immobilized on functionalized biochar, and an immobilization yield of 66% was obtained. The immobilized enzyme demonstrated operational stability up to six cycles while retaining 40% of the initial activity. Laccase immobilization was further investigated by performing adsorption and kinetic studies, which revealed the highest immobilization concentration of 500 U g⁻¹ at 25 °C. The adsorption followed the Langmuir isotherm model at equilibrium, and the kinetic study confirmed pseudo-second-order kinetics. The equilibrium rate constant (K₂) at 25 °C and 4 °C were 3.6 × 10⁻³ g U⁻¹ min⁻¹ and 4 × 10⁻³ g U⁻¹ min⁻¹ respectively for 100 U g⁻¹ of enzyme loading. This immobilized system was applied for anthracene degradation in the aqueous batch mode, which resulted in complete degradation of 50 mg L⁻¹ anthracene within 24 h of interaction exposure.

The effects of biological activated carbon treatment using Fe₂O₃ modified coconut shell-based activated carbon (Fe/CAC) were investigated on the occurrence of opportunistic pathogens (OPs) and formation of disinfection by-products (DBPs) in simulated drinking water distribution systems (DWDSs) with unmodified CAC as a reference. In the effluent of annular reactor (AR) with Fe/CAC, the OPs growth and DBPs formation were inhibited greatly. Based on the differential pulse voltammetry and dehydrogenase activity tests, it was verified that extracellular electron transfer was enhanced in the attached biofilms of Fe/CAC, hence improving the microbial metabolic activity and biological removal of organic matter especially DBPs precursors. Meanwhile, the extracellular polymeric substances (EPS) on the surface of Fe/CAC exhibited stronger viscosity, higher flocculating efficiency and better mechanical stability, avoiding bacteria or small-scale biofilms falling off into the water. Consequently, the microbial biomass and EPS substances amount decreased markedly in the effluent of Fe/CAC filter. More importantly, Fe/CAC did significantly enhance the shaping role on microbial community of downstream DWDSs, continuously excluding OPs advantage and inhibiting EPS production. The weakening of EPS in DWDSs resulted in decrease of microbial chlorine-resistance ability and EPS-derived DBPs precursors supply. Therefore, the deterioration of water quality in DWDSs was inhibited greatly, sustainably maintaining the safety of tap water. Our findings indicated that optimizing biological activated carbon treatment by interface modification is a promising method for improving water quality in DWDSs.

Cadmium (Cd) is a harmful heavy metal that can cause many health problems, while selenium (Se) is an essential nutrient for organisms that can protect them from heavy metal-induced damage. To explore the effects of Se on Cd-induced mitophagy in the liver, forty 3-month-old New Zealand white rabbits (2–2.5 kg), half male and half female, were randomly divided into four groups: the Control group, the Se (0.5 mg/kg body weight (BW)) group, the Cd (1 mg/kg BW) group and the Se+Cd group. After 30 days, the toxicity from Cd in the liver was assessed in terms of the nuclear xenobiotic receptor (NXR) response, oxidative stress and mitophagy. It was found that Cd decreased the activities of CYP450 enzymes and antioxidant enzymes and increased the contents of malondialdehyde (MDA) and hydrogen peroxide (H₂O₂) and also increased the consumption of reduced glutathione (GSH). Moreover, the mRNA levels of NXRs (CAR, PXR, AHR and Nrf2), some mitochondrial function factors (PGC-1α, Sirt1, Sirt3, Nrf1 and TFAM) and mitochondrial fusion factors (Mfn1, Mfn2 and OPA1) were downregulated, but the mRNA levels of other mitochondrial function factors (VDAC1, Cyt C and PRDX3), mitochondrial fission factors (Fis1 and MFF) and those in the PINK1/Parkin-mediated mitophagy pathway (p62, Bnip3 and LC3) were upregulated under Cd exposure. The protein expression levels of Nrf2, SOD2, PGC-1α, PINK1 and Parkin were consistent with the mRNA expression levels in the Cd group. Se alleviated the changes in the abovementioned factors induced by Cd. In conclusion, the results indicate that Cd can cause oxidative stress in rabbit livers by inhibiting NXRs and the antioxidation response leading to mitophagy, and these harmful changes caused by Cd can be alleviated by Se.

Fish embryos, as an endogenous system, strictly regulate an energy metabolism that is particularly sensitive to environmental pressure. This study used orange-spotted grouper embryos and stable isotope ⁶⁷Zn to test the hypothesis that waterborne Zn exposure had a significant effect on energy metabolism in embryos. The fish embryos were exposed to a gradient level of waterborne ⁶⁷Zn, and then sampled to quantify ⁶⁷Zn bioaccumulation and mRNA expressions of key genes involved glucose metabolism. The results indicated that the bioaccumulated ⁶⁷Zn generally increased with increasing waterborne ⁶⁷Zn concentrations, while it tended to be saturated at waterborne ⁶⁷Zn > 0.7 mg L⁻¹. As we hypothesized, the expression of PK and PFK gene involved glycolysis pathway was significantly up-regulated under waterborne ⁶⁷Zn exposure >4 mg L⁻¹. Waterborne ⁶⁷Zn exposure >2 mg L⁻¹ significantly suppressed PCK and G6PC gene expression involved gluconeogenesis pathway, and also inhibited the AKT2, GSK-3beta and GLUT4 genes involved Akt signaling pathway. Our findings first characterized developmental stage-dependent Zn uptake and genotoxicity in fish embryos. We suggest fish embryos, as a small-scale modeling biosystem, have a large potential and wide applicability for determining cytotoxicity/genotoxicity of waterborne metal in aquatic ecosystem.

In Europe, emerging organic compounds (EOCs) in groundwater is a growing research area. Prioritisation for monitoring EOCs in Europe was formalised in 2019 through the development of the first voluntary groundwater watch list (GWWL). Despite this, groundwater occurrence data in the peer reviewed literature for Europe has not been reviewed to date. Questions surrounding the effect, toxicity, movement in the subsurface and unsaturated zone make the process of regulating EOC use difficult. The aim in Europe is to develop a unified strategy for the classification, and prioritisation of EOCs to be monitored in groundwater. This paper compiles evidence from the recent published studies from across Europe, since 2012, when the last major literature global review of EOCs in groundwater took place. A total of 39 studies were identified for review based on specific selection criteria (geography, publication date, sample size>10, inclusion of EOCs data). Data on specific compounds, and associated meta-data, are compiled and reviewed. The two most frequently detected EOCs, carbamazepine and caffeine, occurred in groundwater at concentrations of up to 2.3 and 14.8 μg/L, respectively.The most frequently reported category of compounds were ‘Pharmaceuticals’; a highly studied group with 135 compounds identified within 31 of the 39 studies. In Europe, the majority of reviewed studies (23) were at a regional scale, looking specifically at EOCs in a specific city or aquifer. The use of analytical methods is not uniform across Europe, and this inevitably influences the current assessment of EOCs in groundwater. A correlation between the number of compounds analysed for, and the number detected in groundwater highlights the need for further studies, especially larger-scale studies throughout Europe. For the development of EU and national regulation, further work is required to understand the occurrence and impacts of EOCs in groundwater throughout Europe and elsewhere.

Antifouling paint particles (APPs) and associated metals have been identified in sediments around boatyards and marinas globally, but the effects of APPs on benthic organisms are largely unknown. Sub-lethal endpoints were measured following laboratory exposures of the harbour ragworm (Hediste diversicolor) and the common cockle (Cerastoderma edule) to environmentally relevant concentrations of biocidal (‘modern’ and ‘historic’) and biocide-free (‘silicone’) APPs added to clean estuarine sediment. Further, the 5-day median lethal concentrations (LC₅₀) and effects concentrations (EC₅₀) for modern biocidal APPs were calculated. For ragworms, significant decreases in weight (15.7%; p < 0.01) and feeding rate (10.2%; p < 0.05) were observed in the modern biocidal treatment; burrowing behaviour was also reduced by 29% in this treatment, but was not significant. For cockles, the modern biocidal treatment led to 100% mortality of all replicates before endpoints were measured. In cockles, there was elevated levels of metallothionein-like protein (MTLP) in response to both modern and historic biocidal treatments. Ragworms had a higher tolerance to modern APPs (5-day LC₅₀:19.9 APP g L⁻¹; EC₅₀: 14.6 g L⁻¹) compared to cockles (5-day LC₅₀: 2.3 g L⁻¹ and EC₅₀: 1.4 g L⁻¹). The results of this study indicate that modern biocidal APPs, containing high Cu concentrations, have the potential to adversely affect the health of benthic organisms at environmentally relevant concentrations. The findings highlight the need for stricter regulations on the disposal of APP waste originating from boatyards, marinas and abandoned boats.

The annual production of sludges is significant all over the world, and large amounts of sludges have been improperly disposed by random dumping. The contaminants in these sludges may leak into the surrounding soils, surface and groundwater, or be blown into the atmosphere, thereby causing adverse effects to human health. In this study, the (anti-)androgenic activities in organic extracts of sludges produced from both industrial and domestic wastewater treatment plants (WWTPs) were examined using reporter gene assay based on MDA-kb2 cell lines and the potential (anti-)androgenic risks were assessed using hazard index (HI) based on bioassays. Twelve of the 18 samples exhibited androgen receptor (AR) antagonistic activities, with AR antagonistic equivalents ranging from 1.2 × 10² μg flutamide/g sludge to 1.8 × 10⁴ μg flutamide/g sludge; however, no AR agonistic activity was detected in any of the tested samples. These 12 sludges were all from chemical WWTPs; no sludges from domestic WWTPs displayed AR antagonistic activity. Aside from wastewater source, treatment scale and technology could also influence AR antagonistic potencies. The HI values of all the 12 sludges exceeded 1.0, and the highest HI value was above 3.0 × 10³ for children; this indicates that these sludges might cause adverse effects to human health and that children are at a greater risk than adults. The anti-androgenic potencies and risks of the subdivided fractions were also determined, and medium-polar and polar fractions were found to have relatively high detection rates and contribution rates to the AR antagonistic potencies and risks of the raw sample extracts.