The occurrence of 17 target PFAA analytes was determined in surface sediments (n = 37) of the East China Sea and potential influencing factors were examined. ΣPFAAs ranged from 0.41 ng/g dw to 3.06 ng/g dw, with perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) as the most abundant perfluorocarboxylic acid and perfluoroalkyl sulfonate, respectively. PFAAs in the sediments were strongly influenced by terrigenous input. Analysis of the relationship between dynamic influence factors and PFAA concentrations showed that the characteristics of PFAA distribution were rather complex. ΣPFAA concentrations and TOC were positively correlated (p < 0.0001). Circumfluence also influenced the whole PFAA distribution and seasonal variation. In addition, correlation analysis suggested that log Koc values increased with increasing perfluoroalkyl chain length. Given the rapid economic development of eastern coastal cities of China, the environmental hazards of land source pollution cannot be ignored.

Benzene is a well-known occupational and environmental toxicant associated with cytopenia, which is characterized by a disorder in the peripheral blood cell counts. However, no effective preventive strategy has been developed yet to tackle the exposure to benzene in daily life. The aim of this study was to evaluate the protective effects of diallyl trisulfide (DATS) on benzene-induced haematopoietic damage and to reveal its potential mechanisms of action. In our study, male Sprague-Dawley rats were divided into six groups. Rats were administered with benzene (1.3 g/kg BW by gavage) to establish the benzene poisoning model, while the DATS treatment groups were treated with benzene plus DATS (15 mg/kg, 30 mg/kg, 45 mg/kg, respectively, by gavage) for 28 days. Our results demonstrated that the counts of peripheral blood WBC and RBC decreased to 31.0% and 79.2%, respectively, in the benzene poisoning model group compared to the control. However, blood cell counts were restored by DATS treatment (30 mg/kg, 45 mg/kg). The apoptosis rates of peripheral blood mononuclear cells (PBMCs) and bone marrow cells (BMCs) were increased to 274% and 284%, respectively, following benzene exposure. Furthermore, expression levels of Bcl-2, PI3K and p-Akt were downregulated and those of Bax were upregulated in both cell types. Moreover, the oxidative parameters (oxygen species, malonaldehyde) were significantly increased, while the non-enzymatic GSH/GSSG ratios and the activities of enzymatic antioxidants (superoxide dismutase, glutathione peroxidase and catalase) were decreased. Interestingly, DATS treatment can restore the WBC number by 267.1% and 304.8% while RBC number by 108.6% and 117.7% in 30,45 mg/k DATS treated groups. In summary, we demonstrated that benzene-induced cytopenia was related to the apoptosis of PBMCs and BMCs, and DATS treatment could prevent benzene-induced cytopenia by suppressing oxidative stress-mediated cell apoptosis via the PI3K/Akt pathway.

Concentrations of 19 PFASs in riverwater, coastal wastewater and effluents from WWTPs which were directly discharged into the Bohai Sea of China were measured and their inputs to this sea area were calculated accordingly. For riverwater samples, the total PFAS concentrations ranged from 13.1 to 69 238 ng/L. PFAS levels in riverwater collected from Liaoning Province were comparable to those from Shandong Province, while they were two orders of magnitude greater than those from Hebei Province and the city of Tianjin. The dominant PFAS patterns were spatially different. PFBS and PFOA were the predominant PFASs in riverwater samples at sites where fluorochemical industry parks are located in Liaoning Province and Shandong Province, respectively. For other sites, PFOA and PFOS were the most abundant PFASs. In contrast, the total PFAS concentrations in coastal wastewater and effluent samples ranged from 16.7 to 7 522 ng/L and from 13.1 to 319 ng/L, respectively. PFOA was dominant in these samples. Inputs of PFASs to the Bohai Sea via riverine flow, discharge of coastal wastewater and effluents were estimated to be 87.3 tons per year. As compared with coastal wastewater and effluent discharge, riverine input was a major source for the PFAS pollution in the Bohai Sea except for PFBS.

Microplastics (MPs) represent a matter of growing concern for the marine environment. Their ingestion has been documented in several species worldwide, but the impact of specific anthropogenic activities remains largely unexplored. In this study, MPs were characterized in different benthic fish sampled after 2.5 years of huge engineering operations for the parbuckling project on the Costa Concordia wreck at Giglio Island. Fish collected in proximity of the wreck showed a high ingestion of microplastics compared to both fish from a control area and values reported worldwide. Also the elevated percentage of nylon, polypropylene lines and the presence of polystyrene are quite unusual for marine organisms sampled in natural field conditions, thus supporting the possible relationship of ingested microplastics with maritime operations during wreck removal. On the other hand, the use of transplanted mussels revealed a lower frequency of ingested MPs, and did not discriminate differences between the wreck and the control area. Some variations were observed in terms of typology and size of particles between surface- and bottom-caged mussels highlighting the influence of a different distribution of MPs along the water column. In conclusion, this study demonstrated that MPs pollution in the area of Costa Concordia was more evident on benthonic environment than on seawater column, providing novel insights on the possibility of using appropriate sentinel organisms for monitoring specific anthropogenic sources of MPs pollution in the marine environment.

Disruption of non-reproductive endocrine systems in wildlife by chemicals has received little attention but represents a potentially significant problem. Nitrate is a major anthropogenic contaminant in the freshwater aquatic environment and has been identified as a potential disrupter of endocrine function in aquatic animals. This study was conducted to investigate the relationship between the function of the neuroendocrine stress axis in fish and inorganic N loading along reaches of rivers receiving cumulative point source and diffuse chemical inputs. To accomplish this, the responsiveness of the stress axis, quantified as the rate of release of cortisol to water across the gills during exposure to a standardised stressor, was measured in three-spined sticklebacks (Gasterosteus aculeatus L.) resident at three sites on each of four rivers in north-west England. The magnitude of the stress response in fish captured at the sites furthest downstream on all rivers was more than twice that of fish captured at upstream sites. Site-specific variation in stress axis reactivity was better explained by between-site variation in concentrations of dissolved nitrate, nitrite, and ammonia than by the concentration of wastewater treatment works effluent. An increase in the magnitude of the stress response was seen among sticklebacks at sites where long-term averaged concentrations of NH3-N, NO3-N and NO2-N exceeded 0.6, 4.0 and 0.1 mg/L respectively. These data suggest that either (i) inorganic N is a better surrogate than wastewater effluent concentration for an unknown factor or factors affecting stress axis function in fish, or (ii) dissolved inorganic N directly exerts a disruptive influence on the function of the neuroendocrine stress axis in fish, supporting concerns that nitrate is an endocrine-modulating chemical.

The effects of wastewater irrigation and sewage sludge on the dissipation behavior of the fungicide benalaxyl and its primary metabolite benalaxyl acid in soil were studied on an enantiomeric level during a 148-day exposure experiment. Chiral separation and analysis of the two pairs of enantiomers were achieved using HPLC-MS/MS with a chiralpak IC chiral column. Benalaxyl decreased with half-life of 16.1 days in soil under tap water irrigation with preferential residue of S-benalaxyl. Benalaxyl acid was formed with great preference of R-enantiomer before 21 days while enriched in S-enantiomer afterwards. The degradation of benalaxyl was restrained by both wastewater and treated wastewater irrigation, but the enantioselectivity in S-benalaxyl residue was enhanced. Benalaxyl acid was also formed with similar enantioselectivity as in tap water irrigation. Sewage sludge could accelerate benalaxyl degradation with shorter half-life. Surprisingly, the enantioselectivity with preference degradation of S-enantiomer in sewage sludge was opposite to that in soil. More benalaxyl acid was generated with EF values always lower than 0.5 and remained longer in sewage sludge than in soil. A sterilization experiment indicated that the conversion of benalaxyl to benalaxyl acid and the enantioselectivity were determined by the microorganisms in soil or sewage sludge. Farming practices like wastewater irrigation and sewage sludge application might not only influence the fate of pesticide, but also the enantioselectivity of chiral pesticide enantiomers and thus the risks of pesticide residues posed to the environment.

Due to concerns regarding the release of pharmaceuticals into the environment and the understudied impact of stereochemistry of pharmaceuticals on their fate and biological potency, we focussed in this paper on stereoselective transformation pathways of selected chiral pharmaceuticals (16 pairs) at both microcosm (receiving waters and activated sludge wastewater treatment simulating microcosms) and macrocosm (wastewater treatment plant (WWTP) utilising activated sludge technology and receiving waters) scales in order to test the hypothesis that biodegradation of chiral drugs is stereoselective. Our monitoring programme of a full scale activated sludge WWTP and receiving environment revealed that several chiral drugs, those being marketed mostly as racemates, are present in wastewater and receiving waters enriched with one enantiomeric form (e.g. fluoxetine, mirtazapine, salbutamol, MDMA). This is most likely due to biological metabolic processes occurring in humans and other organisms. Both activated sludge and receiving waters simulating microcosms confirmed our hypothesis that chiral drugs are subject to stereoselective microbial degradation. It led, in this research, to preferential degradation of S-(+)-enantiomers of amphetamines, R-(+)-enantiomers of beta-blockers and S-(+)-enantiomers of antidepressants. In the case of three parent compound – metabolite pairs (venlafaxine – desmethylvenlafaxine, citalopram – desmethylcitalopram and MDMA - MDA), while parent compounds showed higher resistance to both microbial metabolism and photodegradation, their desmethyl metabolites showed much higher degradation rate both in terms of stereoselective metabolic and non-stereoselective photochemical processes. It is also worth noting that metabolites tend to be, as expected, enriched with enantiomers of opposite configuration to their parent compounds, which might have significant toxicological consequences when evaluating the metabolic residues of chiral pollutants.

China produces approximately 20%–30% of the total global chlorinated paraffins (CPs). The establishment of a short-chain CP (SCCP) emission inventory is a significant step toward risk assessment and regulation of SCCPs in China and throughout the globe. This study developed a gridded SCCPs emission inventory with a 1/4° longitude by 1/4° latitude resolution from 2008 to 2012 for China, which was based on the total annual CPs emissions for the nation. The total national SCCPs emission during this 5-year period was 5651.5 tons. An additive in metal cutting fluids was a major emission source in China, contributing 2680.2 tons to the total atmospheric emissions of SCCPs from 2008 to 2012, followed by the production of CPs (2281.8 tons), plasticizers (514.3 tons), flame retardants (108.6 tons), and net import (66.6 tons). Most of these emission sources are located along the eastern seaboard of China and southern China. A coupled atmospheric transport model was employed to simulate environmental contamination by SCCPs using the gridded emission inventory of SCCPs from 2008 to 2012 as the model initial conditions. Simulated atmospheric and soil concentrations were compared with field monitoring data to validate the emission inventory. The results showed good consistency between modeled and field sampling data, supporting the reliability and credibility of the gridded SCCPs emission inventory that was developed in the present study.

Knowledge of the heterogeneous distribution of humic substances (HS) reactivities along a continuum of molecular weight (MW) is crucial for the systems where the HS MW is subject to change. In this study, two dimensional correlation spectroscopy combined with size exclusion chromatography (2D-CoSEC) was first utilized to obtain a continuous and heterogeneous presence of copper binding characteristics within bulk HS with respect to MW. HS solutions with varying copper concentrations were directly injected into a size exclusion chromatography (SEC) system with Tris-HCl buffer as a mobile phase. Several validation tests confirmed neither structural disruption of HS nor competition effect of the mobile phase used. Similar to batch systems, fluorescence quenching was observed in the chromatograms over a wide range of HS MW. 2D-CoSEC maps of a soil-derived HS (Elliot soil humic acid) showed the greater fluorescence quenching degrees with respect to the apparent MW on the order of 12500 Da > 10600 Da > 7000 Da > 15800 Da. The binding constants calculated based on modified Stern-Volmer equation were consistent with the 2D-CoSEC results. More heterogeneity of copper binding affinities within bulk HS was found for the soil-derived HS versus an aquatic HS. The traditional fluorescence quenching titration method using ultrafiltered HS size fractions failed to delineate detailed distribution of the copper binding characteristics, exhibiting a much shorter range of the binding constants than those obtained from the 2D-CoSEC. Our proposed technique demonstrated a great potential to describe metal binding characteristics of HS at high MW resolution, providing a clear picture of the size-dependent metal-HS interactions.

Nostoc sp. PCC 7120 (Nostoc), a typical filamentous cyanobacterium ubiquitous in aquatic system, is recognized as a model organism to study prokaryotic cell differentiation and nitrogen fixation. In this study, Nostoc cells incubated with arsenite (As(III)) for two weeks were extracted with dichloromethane/methanol (DCM/MeOH) and the extract was partitioned between water and DCM. Arsenic species in aqueous and DCM layers were determined using high performance liquid chromatography - inductively coupled plasma mass spectrometer/electrospray tandem mass spectrometry (HPLC-ICPMS/ESIMSMS). In addition to inorganic arsenic (iAs), the aqueous layer also contained monomethylarsonate (MAs(V)), dimethylarsinate (DMAs(V)), and the two arsenosugars, namely a glycerol arsenosugar (Oxo-Gly) and a phosphate arsenosugar (Oxo-PO4). Two major arsenosugar phospholipids (AsSugPL982 and AsSugPL984) were detected in DCM fraction. Arsenic in the growth medium was also investigated by HPLC/ICPMS and shown to be present mainly as the inorganic forms As(III) and As(V) accounting for 29%–38% and 29%–57% of the total arsenic respectively. The total arsenic of methylated arsenic, arsenosugars, and arsenosugar phospholipids in Nostoc cells with increasing As(III) exposure were not markedly different, indicating that the transformation to organoarsenic in Nostoc was not dependent on As(III) concentration in the medium. Our results provide new insights into the role of cyanobacteria in the biogeochemical cycling of arsenic.