Diclofenac (DCF) has been recognized as an emerging contaminant in aquatic environments. Though many studies have investigated the toxic effects of DCF in human and mammals, limited information is available for the responses of genes associated with detoxification metabolisms in non-target aquatic organisms such as fish. In the present study, a small benthic fish Mugilogobius abei, was chosen as the test organism and the effects of DCF on detoxification-related genes at transcriptional level in M. abei were investigated. Partial cDNAs of pregnane-X-receptor (pxr), cytochrome P450 3A (cyp 3a) and alpha-gst were cloned firstly. The responses of cyp 1a, cyp 3a, alpha-gst and p-gp genes and associated microRNAs expressions were measured under different concentrations of DCF exposure (0.5, 5, 50, 500 μg/L) for 24 h and 168 h. Induction of cyp 1a, cyp 3a, alpha-gst, p-gp and pxr mRNA expressions was observed under DCF exposure for different time. Positive concentration-response relationships between DCF concentrations and cyp 1a as well as alpha-gst mRNA expression were observed under DCF exposure for 24 h. The similar trend between pxr mRNA expression and cyp 3a gene expression suggested the role of pxr in regulation of its downstream detoxification genes involved in DCF detoxification in M. abei. The negative correlation between miR-27a and p-gp expression under DCF exposure for 24 h indicated the role of miRNA in post transcriptional regulation on detoxification-related genes mRNAs in M. abei exposed to DCF. Overall, DCF exposure, even at environmental levels, may interrupt the responses of the detoxification genes in M. abei, which may affect the response of the exposed organism to other pollutants. This work provides implications on the bio-monitoring and risk assessment of DCF in aquatic ecosystems by using of local native fish species.

Effects of photochemical and microbial degradation on variations in composition and molecular-size of dissolved organic matter (DOM) from different sources (algal and soil) and the subsequent influence on Cu(II) binding were investigated using UV–Vis, fluorescence excitation-emission matrices coupled with parallel factor analysis, flow field-flow fractionation (FlFFF), and metal titration. The degradation processes resulted in an initial rapid decline in the bulk dissolved organic carbon and chromophoric and fluorescent DOM components, followed by a small or little decrease. Specifically, photochemical reaction decreased the aromaticity, humification and apparent molecular weights of all DOM samples, whereas a reverse trend was observed during microbial degradation. The FlFFF fractograms revealed that coagulation of both protein- and humic-like DOM induced an increase in molecular weights for algal-DOM, while the molecular weight enhancement for allochthonous soil samples was mainly attributed to the self-assembly of humic-like components. The Cu(II) binding capacity of algal-derived humic-like and fulvic-like DOM consistently increased during photo- and bio-degradation, while the soil-derived DOM exhibited a slight decline in Cu(II) binding capacity during photo-degradation but a substantial increase during microbial degradation, indicating source- and degradation-dependent metal binding heterogeneities. Pearson correlation analysis demonstrated that the Cu(II) binding potential was mostly related with aromaticity and molecular size for allochthonous soil-derived DOM, but was regulated by both DOM properties and specific degradation processes for autochthonous algal-derived DOM. This study highlighted the coupling role of inherent DOM properties and external environmental processes in regulating metal binding, and provided new insights into metal-DOM interactions and the behavior and fate of DOM-bound metals in aquatic environments.

In this study, we examined the removal of arsenite (As(III)) and arsenate (As(V)) by perilla leaf-derived biochars produced at 300 and 700 °C (referred as BC300 and BC700) in aqueous environments. Results revealed that the Langmuir isotherm model provided the best fit for As(III) and As(V) sorption, with the sorption affinity following the order: BC700-As(III) > BC700-As(V) > BC300-As(III) > BC300-As(V) (QL = 3.85–11.01 mg g⁻¹). In general, As removal decreased (76–60%) with increasing pH from 7 to 10 except for the BC700-As(III) system, where notably higher As removal (88–90%) occurred at pH from 7 to 9. Surface functional moieties contributed to As sequestration by the biochars examined here. However, significantly higher surface area and aromaticity of BC700 favored a greater As removal compared to BC300, suggesting that surface complexation/precipitation dominated As removal by BC700. Arsenic K-edge X-ray absorption near edge structure (XANES) spectroscopy demonstrated that up to 64% of the added As(V) was reduced to As(III) in BC700- and BC300-As(V) sorption experiments, and in As(III) sorption experiments, partial oxidation of As(III) to As(V) occurred (37–39%). However, XANES spectroscopy was limited to precisely quantify As binding with sulfur species as As2S3-like phase. Both biochars efficiently removed As from natural As-contaminated groundwater (As: 23–190 μg L⁻¹; n = 12) despite in the presence of co-occurring anions (e.g., CO3²⁻, PO4³⁻, SO4²⁻) with the highest levels of As removal observed for BC700 (97–100%). Overall, this study highlights that perilla leaf biochars, notably BC700, possessed the greatest ability to remove As from solution and groundwater (drinking water). Significantly, the integrated spectroscopic techniques advanced our understanding to examine complex redox transformation of As(III)/As(V) with biochar, which are crucial to determine fate of As on biochar in aquatic environments.

Micro-plastic particles in the world's oceans represent a serious threat to both human health and marine ecosystems. Once released into the aquatic environment plastic litter is broken down to smaller pieces through photo-degradation and the physical actions of waves, wind, etc. The resulting particles may become so small that they are readily taken up by fish, crustaceans and mollusks. There is mounting evidence for the uptake of plastic particles by marine organisms that form part of the human food chain and this is driving urgent calls for further and deeper investigations into this pollution issue.The present study aimed at investigating for the first time the occurrence, amount, typology of microplastic litter in the gastrointestinal tract of Solea solea and its spatial distribution in the northern and central Adriatic Sea. This benthic flatfish was selected as it is a species of high commercial interest within the FAO GFCM (General Fisheries Commission for the Mediterranean) area 37 (Mediterranean and Black Sea) where around 15% of the overall global Solea solea production originates.The digestive tract contents of 533 individuals collected in fall during 2014 and 2015 from 60 sampling sites were examined for microplastics. These were recorded in 95% of sampled fish, with more than one microplastic item found in around 80% of the examined specimens. The most commonly found polymers were polyvinyl chloride, polypropylene, polyethylene, polyester, and polyamide, 72% as fragments and 28% as fibers. The mean number of ingested microplastics was 1.73 ± 0.05 items per fish in 2014 and 1.64 ± 0.1 in 2015. PVC and PA showed the highest densities in the northern Adriatic Sea, both inshore and off-shore while PE, PP and PET were more concentrated in coastal areas with the highest values offshore from the port of Rimini.

Cyclophosphamide (CP) and Ifosfamide (IF) are two nitrogen mustard drugs widely prescribed in cancer therapy. They are continuously released via excreta into hospital and urban wastewaters reaching wastewater treatment plants. Although CP and IF, their metabolites and transformation products (TPs) residues have been found in the aquatic environment from few ng L⁻¹ to tens of μg L⁻¹, their environmental toxic effects are still not well known. The present study aimed to investigate the acute and chronic ecotoxicity of CP and IF and their commercially available human metabolites/TPs, i.e. carboxy-CP, Keto-CP and N-dechloroethyl-CP on different organisms of the aquatic trophic chain. The experiments were performed using the green alga Pseudokirchneriella subcapitata, the rotifer Brachionus calyciflorus and the crustaceans Thamnocephalus platyurus and Ceriodaphnia dubia. Moreover, to assess the treatment conditions in regards to parent compound removal and formation of new TPs, CP and IF were UV- irradiated for 6 h, 12 h, 24 h, 36 h and 48 h, followed by toxicity evaluation of treated samples by algae, rotifers and crustaceans. Between the parent compounds, IF resulted as more toxic drug under tested conditions, exerting both acute and chronic effects especially on C. dubia (LC50:196.4 mg L⁻¹, EC50:15.84 mg L⁻¹). Among the tested metabolites/TPs, only carboxy-CP inhibited the reproduction in the rotifer. However, LOEC and NOEC values were calculated for CP and IF for all organisms. In addition, despite a low degradation of CP (28%) and IF (36%) after 48 h UV-irradiation, statistically significant effect differences (p < 0.05) from not-irradiated and irradiated samples were observed in both acute and chronic assays, starting from 6 h UV-irradiation. Our results suggest that the toxic effects found in the aquatic organisms may be attributable to interactions between the parent compounds and their metabolites/TPs.

Recently, there has been a growing concern that climate change may rapidly and extensively alter global ecosystems with unknown consequences for terrestrial and aquatic life. While considerable emphasis has been placed on terrestrial ecology consequences, aquatic environments have received relatively little attention. Limited knowledge is available on the biological effects of increments of seawater temperature and pH decrements on key ecological species, i.e., primary producers and/or organisms representative of the basis of the trophic web. In the present study, we addressed the biological effects of global warming and ocean acidification on two model organisms, the microbenthic marine ciliate Euplotes crassus and the green alga Dunaliella tertiocleta using a suite of high level ecological endpoint tests and sub-lethal stress measures. Organisms were exposed to combinations of pH and temperature (TR1: 7.9[pH], 25.5 °C and TR2: 7.8[pH], 27,0 °C) simulating two possible environmental scenarios predicted to occur in the habitats of the selected species before the end of this century. The outcomes of the present study showed that the tested scenarios did not induce a significant increment of mortality on protozoa. Under the most severe exposure conditions, sub-lethal stress indices show that pH homeostatic mechanisms have energetic costs that divert energy from essential cellular processes and functions. The marine protozoan exhibited significant impairment of the lysosomal compartment and early signs of oxidative stress under these conditions. Similarly, significant impairment of photosynthetic efficiency and an increment in lipid peroxidation were observed in the autotroph model organism held under the most extreme exposure condition tested.

Numerous studies on microplastics (MPs; Ø < 5 mm) in the aquatic environment have been published, but knowledge about the occurrence and ecological risks of MPs is limited. This is in part because current data on the distribution of MPs are comparable only to a limited extent, due to the many different methods of investigation. In addition, sample preparation is often difficult such that standard procedures are lacking. The aim of this work was to simplify the preparation of different kinds of MP samples. Our method makes use of the electrostatic behavior of plastic particles to facilitate their separation from sample matter, with up to 99% of the original sample mass removed without any loss of MPs. To determine the efficacy of this approach, four different materials (quartz sand, freshwater suspended particulate matter, freshwater sediment, and beach sand) were spiked with MPs (size: 0.063–5 mm from the seven most common types of plastics, one bioplastic type, polyethylene fibers, and tire wear. A modified electrostatic metal/plastic separator was used to reduce the sample mass and concentrate the plastics based on their physical separation. The recovery achieved with this method was as high as nearly 100% for each type of material. The method was then tested on plastic particles of different shapes and types isolated from the Rhine River. These were successfully electroseparated from the four materials, which demonstrated the utility of this method. Its advantages include the simplified handling and preparation of different field samples as well as a much shorter processing time, because after the last separation step there is hardly any biological material remaining in the sample fraction.

In this study, a novel biochar-supported zero valent iron (BC-nZVI) was synthesized through a green method. A high performance on the simultaneous removal of Cu²⁺ and bisphenol A (BPA) by a combination of BC-nZVI with persulfate (BC-nZVI/PS) system was successfully achieved. The simultaneous efficiencies of Cu²⁺ and BPA could reach 96 and 98% within 60 min, respectively. Both HO• and SO₄•⁻ were two major reactive species in BC-nZVI/PS system, and SO₄•⁻ was primary radical responsible for the degradation of BPA. Four kinds of Cu species, such as Cu(OH)₂, CuO, Cu₂O and Cu⁰ were generated via the adsorption and reduction of the BC-nZVI, whereas six kinds of products of BPA including p-isopropenyl phenol and 4-isopropylphenol were generated via the combined oxidation of SO₄•⁻ and HO•. The possible reaction mechanism for the simultaneous removal of Cu²⁺ and BPA by BC-nZVI/PS system contained a synergistic effect between the reduction of Cu²⁺ and the oxidation of BPA. This is the first report on the feasibility of the remediation of coexistence of heavy metal and organic compound in aquatic environment using the BC-nZVI/PS system.

Chlorinated polyfluorinated ether sulfonate (Cl-PFESA) is a novel alternative compound for perfluorooctane sulfonate (PFOS), with its environmental risk not well known. The bioaccumulation and toxic effects of Cl-PFESA in the freshwater alga is crucial for the understanding of its potential hazards to the aquatic environment. Scenedesmus obliquus was exposed to Cl-PFESA at ng L⁻¹ to mg L⁻¹, with the exposure regime beginning at the environmentally relevant level. The total log BAF of Cl-PFESA in S. obliquus was 4.66, higher than the reported log BAF of PFOS in the freshwater plankton (2.2–3.2). Cl-PFESA adsorbed to the cell surface accounted for 33.5–68.3% of the total concentrations. The IC50 of Cl-PFESA to algal growth was estimated to be 40.3 mg L⁻¹. Significant changes in algal growth rate and chlorophyll a/b contents were observed at 11.6 mg L⁻¹ and 13.4 mg L⁻¹ of Cl-PFESA, respectively. The sample cell membrane permeability, measured by the fluorescein diacetate hydrolyzation, was increased by Cl-PFESA at 5.42 mg L⁻¹. The mitochondrial membrane potential, measured by Rh123 staining, was also increased, indicating the hyperpolarization induced by Cl-PFESA. The increasing ROS and MDA contents, along with the enhanced SOD, CAT activity, and GSH contents, suggested that Cl-PFESA caused oxidative damage in the algal cells. It is less possible that current Cl-PFESA pollution in surface water posed obvious toxic effects on the green algae. However, the bioaccumulation of Cl-PFESA in algae would contribute to its biomagnification in the aquatic food chain and its effects on membrane property could potentially increase the accessibility and toxicity of other coexisting pollutants.

Climbazole (CBZ) is an antibacterial and antifungal agent widely used in personal care products. In this study, we investigated the interactions between climbazole (CBZ) and freshwater microalgae Scenedesmus obliquus (S. obliquus). Dose-effect relationships between CBZ concentrations and growth inhibitions or chlorophyll a content were observed. After 12 days of incubation, the algae density and chlorophyll a content in 2 mg/L treatment group was 56.6% and 15.8% of those in the control group, respectively. Biotransformation was the predominant way to remove CBZ in the culture solution, whereas the contribution of bioaccumulation and bioadsorption were negligible. More than 88% of CBZ was removed by S. obliquus across all treatments after 12 days of incubation, and the biotransformation of CBZ followed the first order kinetic model with half-lives of approximately 4.5 days at different treatments. CBZ-alcohol (CBZ-OH) was the only biotransformation product identified in algal solution. Moreover, the toxicity of biotransformation products was much lower than its corresponding precursor compound (CBZ). The results of this study revealed that S. obliquus might have a great impact on the environmental fates of CBZ and could be further applied to remove organic pollutants in aquatic environment.