Effects of contamination on aquatic organisms have been investigated and employed as biomarkers in environmental quality assessment for years. A commonly referenced aquatic organism, mollusks represent a group of major interest in toxicological studies. Both gastropods and bivalves have external mineral shells that protects their soft tissue from predation and desiccation. These structures are composed of an organic matrix and an inorganic matrix, both of which are affected by environmental changes, including exposure to hazardous chemicals. This literature review evaluates studies that propose mollusk shell alterations as biomarkers of aquatic system quality. The studies included herein show that changes to natural variables such as salinity, temperature, food availability, hydrodynamics, desiccation, predatory pressure, and substrate type may influence the form, structure, and composition of mollusk shells. However, in the spatial and temporal studies performed in coastal waters around the world, shells of organisms sampled from multi-impacted areas were found to differ in the form and composition of both organic and inorganic matrices relative to shells from less contaminated areas. Though these findings are useful, the toxicological studies were often performed in the field and were not able to attribute shell alterations to a specific molecule. It is known that the organic matrix of shells regulates the biomineralization process; proteomic analyses of shells may therefore elucidate how different contaminants affect shell biomineralization. Further research using approaches that allow a clearer distinction between shell alterations caused by natural variations and those caused by anthropogenic influence, as well as studies to identify which molecule is responsible for such alterations or to determine the ecological implications of shell alterations, are needed before any responses can be applied universally.

The overuse and misuse of antibiotics could promote the emergence of antibiotic resistance genes (ARGs) and pose a potential risk to human health and the ecological environment. In this study, fifteen antibiotics and their corresponding ARGs in water, sediment and sewage treatment plant (STP) effluent were analysed to investigate their occurrence and correlation in the Yangtze River (Jiangsu section) for the first time. The concentrations of erythromycin-H₂O (EM-H₂O) (2.08–30 ng L⁻¹) and ofloxacin (OFL) (290–8400 ng kg⁻¹) were the highest in the water and sediment, respectively, and EM-H₂O and clarithromycin (CLA) posed the highest risks to aquatic organisms. The concentrations of antibiotics in STP effluent were significantly higher (p < 0.05) than those in the water. Norfloxacin (NOR) was the most predominant antibiotic, with low removal efficiency (−38%-51%), in STPs; the concentration of NOR in the STP effluent was 4–6 orders of magnitude higher than that in the water. Moreover, the concentrations of antibiotics and their corresponding ARG abundance in downstream were higher than those in upstream, suggesting that STPs with high concentration levels might be an important source of river contamination. Additionally, the concentrations of antibiotics and the abundance of ARGs might increase after the sewage treatment process. The results also showed the prevalence of sul1 and sul2 in all the sampling sites. Significant correlations (p < 0.0001) were detected between int1 and sul1 and sul2, which resulted from the contribution of int1 to the propagation of ARGs. Overall, this study demonstrated the prevalence of antibiotics and ARGs and their inconsistent correlations in the Yangtze River (Jiangsu section) and provides support for further investigation of the occurrence and spread of antibiotics and ARGs.

In freshwater ecosystems with frequent cyanobacterial blooms, the cyanobacteria toxin pollution is becoming increasingly serious. Nodularin (NOD), which has strong biological toxicity, has emerged as a new pollutant and affects the normal growth, development and reproduction of aquatic organisms. However, little information is available regarding this toxin. In this study, a graphene oxide material modified by L-cysteine was synthesized and used to immobilize microcystin-LR (MC-LR)-degrading enzyme (MlrA) to form an immobilized enzyme nanocomposite, CysGO-MlrA. Free-MlrA was used as a control. The efficiency of NOD removal by CysGO-MlrA was investigated. Additionally, the effects of CysGO-MlrA and the NOD degradation product on zebrafish lymphocytes were detected to determine the biological toxicity of these two substances. The results showed the following: (1) There was no significant difference in the degradation efficiency of NOD between CysGO-MlrA and free-MlrA; the degradation rate of both was greater than 80% at 1 h (2) The degradation efficiency of the enzyme could retain greater than 81% of the initial degradation efficiency after the CysGO-MlrA had been reused 7 times. (3) CysGO-MlrA retained greater than 50% of its activity on the 8th day when preserved at 0 °C, while free-MlrA lost 50% of its activity on the 4th day. (4) CysGO-MlrA and the degradation product of NOD showed no obvious cytotoxicity to zebrafish lymphocytes. Therefore, CysGO-MlrA might be used as an efficient and ecologically safe degradation material for NOD.

Both microplastics and persistent organic pollutants (POPs) are ubiquitously present in natural water environment, posing a potential threat to aquatic organisms. While it has been suggested that the immune responses of aquatic organisms could be hampered by exposure to microplastics and POPs, the synergistic immunotoxic impact of these two types of pollutants remain poorly understood. In addition, little is known about the mechanism behind the immunotoxic effect of microplastics. Therefore, in the present study, the immunotoxicity of microplastics and two POPs, benzo[a]pyrene (B[a]P) and 17β-estradiol (E2), were investigated alone or in combination in a bivalve species, Tegillarca granosa. Evident immunotoxicity, as indicated by alterations of haemocyte count, blood cell composition, phagocytic activity, intracellular content of ROS, concentration of Ca²⁺ and lysozyme, and lysozyme activity, was revealed for both microplastics and the two POPs examined. In addition, the expression of six immune-, Ca²⁺ signalling-, and apoptosis-related genes was significantly altered by exposure of clams to the contaminants studied. Furthermore, the toxicity of POPs was generally aggravated by smaller microplastics (500 nm) and mitigated by larger ones (30 μm). This size dependent effect on POP toxicity may result from size dependent interactions between microplastics and POPs. Data obtained in this study also indicate that similar to exposure to B[a]P and E2, exposure to microplastics may hamper the immune responses of clams through a series of interdependent physiological and molecular processes.

Total concentrations of hydrophobic organic contaminants (HOCs) in sediment present a poor quality assessment parameter for aquatic organism exposure and environmental risk because they do not reflect contaminant bioavailability. The bioavailability issue of HOCs in sediments can be addressed by application of multi-ratio equilibrium passive sampling (EPS). In this study, riverbed sediment samples were collected during the Joint Danube Survey at 9 locations along the Danube River in 2013. Samples were ex-situ equilibrated with silicone passive samplers. Desorption isotherms were constructed, yielding two endpoints: pore water (CW:₀) and accessible (CAS:₀) concentration of polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs), polycyclic aromatic hydrocarbons (PAHs) and polybrominated diphenyl ethers in sediment. CW:₀ concentrations of DDT and its breakdown products exhibited elevated levels in the low Danube, with the maximum in the river delta. Other investigated HOCs did not show any clear spatial trends along the river, and only a moderate CW:₀ variability. CAS:₀ in sediment ranged from 10 to 90% of the total concentration in sediment. CW:₀ was compared with freely dissolved concentration in the overlaying surface water, measured likewise by passive sampling. The comparison indicated potential compound release from sediment to the water phase for PAHs with less than four aromatic rings, and for remaining HOCs either equilibrium between sediment and water, or potential compound deposition in sediment. Sorption partition coefficients of HOC to organic carbon correlated well with octanol-water partition coefficients (KOW), showing stronger sorption of PAHs to sediment than that of PCBs and OCPs having equal logKOW. Comparison of CW:₀ values with European environmental quality standards indicated potential exceedance for hexachlorobenzene, fluoranthene and benzo[a]pyrene at several sites. The study demonstrates the utility of passive sampling as an innovative approach for risk-oriented monitoring of HOCs in river catchments.

Triclocarban (TCC) is used as a broad-spectrum antimicrobial agent, the intensive detection of TCC in aquatic environments and its potential risks to aquatic organisms are concerned worldwide. In this study, 8 Chinese resident aquatic organisms from 3 phyla and 8 families were used for the toxicity tests, and four methods were employed to derive the aquatic life criteria (ALC). A criterion maximum concentration (CMC) of 1.46 μg/L and a criterion continuous concentration (CCC) of 0.21 μg/L were derived according to the USEPA guidelines. The acute predicted no effect concentrations (PNECs) derived by species sensitivity distribution (SSD) methods based on log-normal, log-logistic and Burr Type Ⅲ models were 2.64, 1.88 and 3.09 μg/L, respectively. The comparisons of ALCs derived with resident and non-resident species showed that the CMC and CCC of TCC derived with Chinese resident species could provide a sufficient protection for non-resident species. The higher toxicity of TCC on aquatic organisms was found compared with other antimicrobial agents (except for Clotrimazole) in aquatic environment. The strong positive linear correlation was observed between the TCC and TCS concentrations in aquatic environment with a correlation coefficient (R²) of 0.8104, it is of great significance in environmental monitoring and risk assessment for TCC and TCS. Finally, the ecological risk assessment showed that the TCC in Yellow River basin and Pearl River basin had higher risk with the mean potential affected fractions (PAFs) of 9.27% and 7.09%, and 22.10% and 15.00% waters may pose potential risk for 5% aquatic organisms, respectively. In general, the risk of TCC in Asian waters was higher than that in Europe and North America.

β-Blockers (BB) are one of the most commonly prescribed pharmaceuticals used for treating cardiovascular and acute anxiety-related disorders. This class of drugs inhibit β-adrenoceptor signalling and given their growing, widespread use, BB are routinely detected in surface waters at nM concentrations. This is concerning as trace levels of BB impart developmental and reproductive dysfunction in non-target aquatic organisms, with potential for ecological risks. To date, environmental pharmaceutical risks to non-target animals are not part of the monitoring framework due to the lack of bioassays for assessing their biological effects. Behavioral endpoints have the advantage of a systems-level integration of multiple sensory signals and motor responses for toxicity screening; however, they are not currently used for risk assessment of environmental contaminants. The zebrafish (Danio rerio) embryo photomotor response (zfPMR) has been used in high-throughput behavioral screenings for neuroactive drug effects at high, therapeutic concentrations. Our objective here was to examine if we could utilize the zfPMR for screening environmental levels of BB. Embryos were placed into 96-well plates, exposed to chemicals and/or municipal wastewater effluent (MWWE), and their zfPMRs were measured with video-analysis. To specifically target BB, embryos were co-treated with isoproterenol, a β-adrenergic agonist that stimulates the zfPMR, and the inhibition of isoproterenol-induced response was used as a biomarker of BB exposure. Our results reveal that the inhibition of isoproterenol-stimulated zfPMRs can be used as a biosensor capable of detecting BB in the parts-per-billion to parts-per-trillion in water samples, including diluted MWWE. The method developed detects BB in spite of the presence of other neuroactive compounds in water samples. This systems level approach of rapid screening for BB effects provides the most promising evidence to date that behavioral neuromodulation can be potentially applied for environmental effects monitoring of pharmaceuticals.

Microplastics (MPs) are now one of the major environmental problems due to the large amount released in aquatic and terrestrial ecosystems, as well as their diffuse sources and potential impacts on organisms and human health. Still the molecular and cellular targets of microplastics’ toxicity have not yet been identified and their mechanism of actions in aquatic organisms are largely unknown. In order to partially fill this gap, we used a mass spectrometry based functional proteomics to evaluate the modulation of protein profiling in zebra mussel (Dreissena polymorpha), one of the most useful freshwater biological model. Mussels were exposed for 6 days in static conditions to two different microplastic mixtures, composed by two types of virgin polystyrene microbeads (size = 1 and 10 μm) each one. The mixture at the lowest concentration contained 5 × 105 MP/L of 1 μm and 5 × 105 MP/L of 10 μm, while the higher one was arranged with 2 × 106 MP/L of 1 μm and 2 × 106 MP/L of 10 μm.Proteomics’ analyses of gills showed the complete lack of proteins’ modulation after the exposure to the low-concentrated mixture, while even 78 proteins were differentially modulated after the exposure to the high-concentrated one, suggesting the presence of an effect-threshold. The modulated proteins belong to 5 different classes mainly involved in the structure and function of ribosomes, energy metabolism, cellular trafficking, RNA-binding and cytoskeleton, all related to the response against the oxidative stress.

Antibiotics in water and soil are persistent, bioaccumulative and toxic to aquatic organisms and human health. To address it, as one of the new technologies, green synthesized magnetic Fe₃O₄ nanoparticles by Excoecaria cochinchinensis extract used to remove rifampicin (RIF) was investigated in this study. Results showed the adsorption efficiency of RIF reached 98.4% and the maximum adsorption capacity is 84.8 mg/g when 20 mL of RIF at a concentration of 20 M was adsorbed by 10 mg Fe₃O₄ at a temperature of 303 K. The morphology of the green Fe₃O₄ characterized by SEM demonstrated the dimensions ranging from 20 to 30 nm. The N₂ adsorption/desorption isotherms revealed that the surface area of Fe₃O₄ was 111.8 m²/g. In addition, adsorption studies indicated that the kinetics fitted the pseudo second-order and isothermal adsorption conformed to the Langmuir isotherm. Furthermore, due to their magnetic properties, the Fe₃O₄ nanoparticles were easily separated and reused and the mechanism for removing RIF occurred through adsorption rather than chemical redox reaction. Finally, the reusability of Fe₃O₄ for adsorption of RIF showed that the removal efficiency decreased to 61.5% after five cycles.

The ecological impacts of insecticides in aquatic areas around agricultural lands have long been ignored in the regulation scheme of pesticides in Japan. Upon the scheme, the predicted concentration of an insecticide in the main stream of a river is the only parameter considered, suggesting that the ecological impacts of insecticides on local biodiversity around agricultural fields are underestimated. To fill this knowledge gap, we measured insecticide concentrations in surface water and sediment in aquatic areas around paddy fields at 35 locations across Japan. Among the 18 insecticides considered, 15 were detected somewhere in Japan and their concentrations were generally higher in the southwestern region in Japan (e.g. Hiroshima, Saga, or Kagoshima prefectures). Most insecticides were accumulated at higher concentrations in sediment than in surface water, consistent with previous studies. We also detected insecticides applied to nursery boxes at high concentrations in surrounding aquatic areas, although such application is generally considered to have low environmental risks. In addition, derivatives of fipronil, which have similar toxicity as that of fipronil, were often detected in sediment at higher concentrations than fipronil itself. Concentrations of dinotefuran in water at two sampling points were higher than the 5% hazardous concentration (HC5), indicating a possibility of a risk of acute toxicity to aquatic organisms. Our findings indicate that ecological risk assessments of insecticides and their derivatives should be expanded to include concentrations in sediment and water around paddy fields as well.