Pharmaceuticals are increasingly detected in environmental matrices, but information on their trophic transfer in aquatic food webs is insufficient. This study investigated the bioaccumulation and trophic transfer of 23 pharmaceuticals in Taihu Lake, China. Pharmaceutical concentrations were analyzed in surface water, sediments and 14 aquatic species, including plankton, invertebrates and fish collected from the lake. The median concentrations of the detected pharmaceuticals ranged from not detected (ND) to 49 ng/L in water, ND to 49 ng/g dry weight (dw) in sediments, and from ND to 130 ng/g dw in biota. Higher concentrations of pharmaceuticals were found in zoobenthos relative to plankton, shrimp and fish muscle. In fish tissues, the observed pharmaceutical contents in the liver and brain were generally higher than those in the gills and muscle. Both bioaccumulation factors (median BAFs: 19–2008 L/kg) and biota−sediment accumulation factors (median BSAFs: 0.0010–0.037) indicated a low bioaccumulation potential for the target pharmaceuticals. For eight of the most frequently detected pharmaceuticals in food webs, the trophic magnification factors (TMFs) were analyzed from two different regions of Taihu Lake. The TMFs for roxithromycin, propranolol, diclofenac, ibuprofen, ofloxacin, norfloxacin, ciprofloxacin and tetracycline in the two food webs ranged from 0.28 to 1.25, suggesting that none of these pharmaceuticals experienced trophic magnification. In addition, the pharmaceutical TMFs did not differ significantly between the two regions in Taihu Lake.

Global warming and chemical pollution are key anthropogenic stressors with the potential to interact. While warming can change the impact of pollutants and pollutants can change the sensitivity to warming, both interaction pathways have never been integrated in a single experiment. Therefore, we tested the effects of warming and multiple pesticide pulses (allowing accumulation) of chlorpyrifos on upper thermal tolerance (CTmax) and associated physiological traits related to aerobic/anaerobic energy production in the damselfly Ischnura elegans. To also assess the role of latitude-specific thermal adaptation in shaping the impact of warming and pesticide exposure on thermal tolerance, we exposed larvae from replicated high- and low-latitude populations to the pesticide in a common garden rearing experiment at 20 and 24 °C, the mean summer water temperatures at high and low latitudes. As expected, exposure to chlorpyrifos resulted in a lower CTmax. Yet, this pesticide effect on CTmax was lower at 24 °C compared to 20 °C because of a lower accumulation of chlorpyrifos in the medium at 24 °C. The effects on CTmax could partly be explained by reduction of the aerobic scope. Given that these effects did not differ between latitudes, gradual thermal evolution is not expected to counteract the negative effect of the pesticide on thermal tolerance. By for the first time integrating both interaction pathways we were not only able to provide support for both of them, but more importantly demonstrate that they can directly affect each other. Indeed, the warming-induced reduction in pesticide impact generated a lower pesticide-induced climate change sensitivity (in terms of decreased upper thermal tolerance). Our results indicate that, assuming no increase in pesticide input, global warming might reduce the negative effect of multiple pulse exposures to pesticides on sensitivity to elevated temperatures.

The specific area between biochar and soil surfaces is termed the “charosphere”, which is analogous to the rhizosphere between plant roots and soil. Physicochemical properties of charosphere soil differ from natural soil. A double-layer mesh bag experiment was conducted to separate the charosphere soil (>2 mm) from biochar (derived from manure pyrolyzed at 300, 500, 700 °C) and the bulk soil. A 95-day experiment determined the availability, total concentration and speciation of Cd in charosphere soil and the total and available Cd in biochar. The availability of Cd decreased in the charosphere soils. Total Cd concentration increased in the biochars but decreased in charosphere soil, suggesting that Cd might transfer from charosphere soil to biochar. Cd in the acid soluble fraction decreased by 25–40% in different biochars while it increased in residue fraction, indicating that Cd tends to be more stable in charosphere soil. Instrumental analysis using SEM, FTIR were performed to provide further evidence of the transport of Cd and to enable interpretation of the mechanisms involved. The phenomena that Cd concentrations change markedly in the charosphere inspires a novel research perspective towards the study of transport and transformation of heavy metals in soil after biochar application.

In the study, the capability of Paecilomyces lilacinus XLA (CCTCC: M2012135) to reduce Cr6+ and its main antagonistic mechanisms to Cr6+ were experimentally evaluated. Activated growing fungus XLA efficiently reduced over 90% Cr6+ in the media with Cr6+ concentration below 100 mg L−1 at pH 6 after 14 days. After 1-day exposure to 100 mg L−1 Cr6+, nearly 50% of Cr6+ was reduced. Moreover, SO42− stimulated Cr6+ reduction, whereas other interferential ions inhibited Cr6+ reduction. The interaction mechanisms between XLA and Cr6+ mainly involve biotransformation, biosorption, and bioaccumulation, as detected by electron microscopy and chemical methods. The lower concentrations of Cr6+ (5 and 50 mg L−1) stimulated the activities of superoxide dismutase (SOD), catalase (CAT) and glutathione (GSH) level in XLA, respectively, but the higher concentration of Cr6+ (150 mg L−1) decreased the enzymatic activities and GSH concentration. The results implied that SOD, CAT and GSH were defensive guards to the oxidant stress produced by Cr6+. All these extracellular/intracellular defense systems endowed XLA with the ability to resist and detoxify Cr6+ by transforming its valent species. The fungus XLA could efficiently reduce Cr6+ under different environmental conditions (pH, interferential ions, and concentration). Moreover, XLA could endure the high concentration of Cr6+ probably due to its high biotransformation capability of Cr6+ and intracellular antioxidant systems for the detoxification of ROS generated by external Cr6+. All these results suggested that the fungus XLA can be applied to remediation of Cr6+-contaminated environments.

This study sought to evaluate the toxicological effects of graphene oxide (GO) through tests with Danio rerio (zebrafish) embryos, considering the influence of the base washing treatment and the interaction with natural organic matter (i.e., humic acid, HA). A commercial sample of GO was refluxed with NaOH to remove oxidation debris (OD) byproducts, which resulted in a base washed GO sample (bw-GO). This process decreased the total oxygenated groups in bw-GO and its stability in water compared to GO. When tested in the presence of HA, both GO and bw-GO stabilities were enhanced in water. Although the embryo exposure showed no acute toxicity or malformation, the larvae exposed to GO showed a reduction in their overall length and acetylcholinesterase activity. In the presence of HA, GO also inhibited acid phosphatase activity. Our findings indicate a mitigation of material toxicity after OD removal. The difference in the biological effects may be related to the materials’ bioavailability and biophysicochemical interactions. This study reports for the first time the critical influence of OD on the GO material biological reactivity and HA interaction, providing new data for nanomaterial environmental risk assessment and sustainable nanotechnology.

Biochar-supported nanoscale zero-valent iron (nZVI) produced under different temperatures was studied to evaluate the effect of the nZVI-biochar composite on the removal of hexavalent chromium (Cr(VI)) in solution. The structure of biochar-supported nZVI and its roles in Cr(VI) removal were investigated by X-Ray Diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR) and batch experiments. The XRD revealed that the removal rate of Cr(VI) for the nZVI supported by rice straw pyrolyzed at 400 °C (RS400) was much greater than that for other supporting biochar, and the FTIR further indicated that the carboxyl groups and silicon mineral within the biochar served as dual support sites for nZVI. NZVI-RS400 exhibited the highest removal amount of Cr(VI) at approximately 40.0 mg/g under an initial pH of 4.0, possibly due to both the reduction and adsorption processes. Therefore, the RS400-supported nanoscale zero-valent iron could be a preferable material for Cr(VI)-contaminated groundwater.

A systematic grid sampling method and geostatistics were employed to investigate the spatial distribution, inventory, and potential ecological and human health risks of the residues of hexachlorobenzene (HCB) and chlorinated cyclodiene pesticides in soils of the Campanian Plain, Italy, and explore their relationship with the soils properties. The geometric mean (Gmean) concentrations of HCB and cyclodiene compounds followed the order CHLs (heptachlor, heptachlor epoxide, trans-chlordane, and cis-chlordane) > DRINs (aldrin, dieldrin, and endrin) > SULPHs (α-endosulfan, β-endosulfan, and endosulfan sulfate) > HCB. The residual levels of most cyclodienes in agricultural soils were generally higher than those of corresponding counterparts in the other land uses. Significant differences in the concentration of HCB and cyclodienes in the soils across the region are observed, and the Acerra-Marigliano conurbation (AMC) and Sarno River Basin (SRB) areas exhibit particularly high residual concentrations. Some legacy cyclodienes in the Campanian Plain may be attributed to a secondary distribution. The Gmean inventory of HCB, SULPHs, CHLs, and DRINs in the soil is estimated to be 0.081, 0.41, 0.36, and 0.41 metric tons, respectively. The non-cancer and cancer risks of HCB and cyclodienes for exposed populations are deemed essentially negligible, however, endosulfan poses significant ecological risks to some terrestrial species.

2,4,6-Tribromophenol (TBP), an intermediate of brominated flame retardants, can easily release to environment and recalcitrant to degradation. Previously, Bacillus sp. GZT, a pure aerobic strain capable of simultaneously debrominating and mineralizing TBP, was successfully isolated by us. To further obtain a practical application and dig up its TBP degradation mechanism, a total of 46.7-fold purification of a novel dehalogenase with a final specific activity of 18.9 U mg−1 and a molecular mass of 63.4 kDa was achieved. Under optimal conditions (35 °C and 200 rpm), up to 80% degradation efficiencies were achieved within 120 min. Adding H2O2, NADPH, Mn2+ and Mg2+ promoted enzyme reaction effectively; while EDTA, methyl viologen, Ni2+, Cu2+, Ca2+ and Fe2+ strongly inhibited reaction activities. The debromination of TBP was catalyzed by the enzyme at a Km of 78 μM and a Vmax of 0.65 min−1 mg protein−1, which indicated that this dehalogenase could specifically eliminate TBP with a high efficiency and stability. Based on MALDI-TOF/TOF analysis, the dehalogenase shared 98% identity with peptide ABC transporter substrate-binding protein. One open reading frame (ORF) encoding this peptide was found in Strain GZT genome, subjected to clone and expressed in Escherichia coli (E. coli) to characterize the encoding gene. Result showed that this recombinant strain could also remove as similar amount of TBP as Bacillus sp. GZT under the identical condition. Based on these results, we suggest that this newly-isolated TBP dehalogenase highlights a new approach for remediating TBP pollution.

Benzotriazole ultraviolet stabilizers (BUVSs) are prominent chemicals widely used in industrial and consumer products to protect against ultraviolet radiation. They are becoming contaminants of emerging concern since their residues are frequently detected in multiple environmental matrices and their toxicological implications are increasingly reported. We herein investigated the antiandrogenic activities of eight BUVSs prior to and after human CYP3A4-mediated metabolic activation/deactivation by the two-hybrid recombinant human androgen receptor yeast bioassay and the in vitro metabolism assay. More potent antiandrogenic activity was observed for the metabolized UV-328 in comparison with UV-328 at 0.25 μM ((40.73 ± 4.90)% vs. (17.12 ± 3.00)%), showing a significant metabolic activation. In contrast, the metabolized UV-P at 0.25 μM resulted in a decreased antiandrogenic activity rate from (16.08 ± 0.95)% to (6.91 ± 2.64)%, indicating a metabolic deactivation. Three mono-hydroxylated (OH) and three di-OH metabolites of UV-328 were identified by ultra-performance liquid chromatography quadrupole time of flight mass spectrometry (UPLC-Q-TOF-MS/MS), which were not reported previously. We further surmised that the hydroxylation of UV-328 occurs mainly at the alicyclic hydrocarbon atoms based on the in silico prediction of the lowest activation energies of hydrogen abstraction from C-H bond. Our results for the first time relate antiandrogenic activity to human CYP3A4 enzyme-mediated hydroxylated metabolites of BUVSs. The biotransformation through hydroxylation should be fully considered during the health risk assessment of structurally similar analogs of BUVSs and other emerging contaminants.

Glyphosate is one of the most used herbicides in agricultural lands worldwide. Wind-eroded sediment and dust, as an environmental transport pathway of glyphosate and of its main metabolite aminomethylphosphonic acid (AMPA), can result in environmental- and human exposure far beyond the agricultural areas where it has been applied. Therefore, special attention is required to the airborne transport of glyphosate and AMPA. In this study, we investigated the behavior of glyphosate and AMPA in wind-eroded sediment by measuring their content in different size fractions (median diameters between 715 and 8 μm) of a loess soil, during a period of 28 days after glyphosate application. Granulometrical extraction was done using a wind tunnel and a Soil Fine Particle Extractor. Extractions were conducted on days 0, 3, 7, 14, 21 and 28 after glyphosate application. Results indicated that glyphosate and AMPA contents were significantly higher in the finest particle fractions (median diameters between 8 and 18 μm), and lowered significantly with the increase in particle size. However, their content remained constant when aggregates were present in the sample. Glyphosate and AMPA contents correlated positively with clay, organic matter, and silt content. The dissipation of glyphosate over time was very low, which was most probably due to the low soil moisture content of the sediment. Consequently, the formation of AMPA was also very low. The low dissipation of glyphosate in our study indicates that the risk of glyphosate transport in dry sediment to off-target areas by wind can be very high. The highest glyphosate and AMPA contents were found in the smallest soil fractions (PM10 and less), which are easily inhaled and, therefore, contribute to human exposure.