The concentration and speciation of heavy metals (Cu, Co, Ni, Zn, Cr, Pb and Cd) were studied in surface sediment from the Yangtze River(YR)to the East China Sea (ECS) shelf. The results showed that high contents of metals were found in the YR estuary (YRE) and in the nearshore muddy area, while lower concentrations were found in the YR channel and the ECS shelf. However, after standardization, the total content of most heavy metals from the YR showed little change or slightly increased during the transport process from the river to the estuary but decreased significantly outside the estuary, especially in the sediments of the ECS shelf. The residual fraction is the dominant fraction for all the metals, while the oxidizable and reducible fractions are the most important forms of the nonlithogenic fractions. The total amount of heavy metals from the YR to the continental shelf is mainly affected by the filtration of the estuary and the barrier impacts of the coastal current in the ECS. The environmental physicochemical conditions that vary significantly in the turbidity zone greatly influence the associated forms of metals. The metals in the acid-soluble fraction are mostly affected by the pH change in the sediment and the discharge of human activities, while the reducible fraction is significantly affected by the bottom water DO. The oxidizable fraction was affected by oxidation-reduction potential (ORP), primary productivity, as well as OM content. Therefore, with changes in the physicochemical conditions of the environment, the metals have undergone significant changes in their speciation from the YR to the ECS shelf. Various complex effects in the estuary area have not only a large filtration effect on the total amount of metals but also a major impact on the geochemical forms of the metals.

Abandoned nonferrous metal(loid) tailings sites are anthropogenic, and represent unique and extreme ecological niches for microbial communities. Tailings contain elevated and toxic content of metal(loid)s that had negative effects on local human health and regional ecosystems. Microbial communities in these typical tailings undergoing natural attenuation are often very poorly examined. The diversity and inferred functions of bacterial communities were examined at seven nonferrous metal(loid) tailings sites in Guangxi (China), which were abandoned between 3 and 31 years ago. The acidity of the tailings sites rose over 31 years of site inactivity. Desulfurivibrio, which were always coupled with sulfur/sulfide oxidation to dissimilate the reduction of nitrate/nitrite, were specific in tailings with 3 years abandonment. However, genus beneficial to plant growth (Rhizobium), and iron/sulfur-oxidizing bacteria and metal(loid)-related genera (Acidiferrobacter and Acidithiobacillus) were specific within tailings abandoned for 23 years or more. The increased abundance of acid-generating iron/sulfur-oxidizing and metal(loid)-related bacteria and specific bacterial communities during the natural attenuation could provide new insights for understanding microbial ecosystem functioning in mine tailings. OTUs related to Sulfuriferula, Bacillus, Sulfurifustis, Gaiella, and Thiobacillus genera were the main contributors differentiating the bacterial communities between the different tailing sites. Multiple correlation analyses between bacterial communities and geochemical parameters indicated that pH, TOC, TN, As, Pb, and Cu were the main drivers influencing the bacterial community structures. PICRUSt functional exploration revealed that the main functions were related to DNA repair and recombination, important functions for bacterial adaptation to cope with the multi-contamination of tailings. Such information provides new insights to guide future metagenomic studies for the identification of key functions beyond metal-transformation/resistance. As well, our results offers novel outlooks for the management of bacterial communities during natural attenuation of multi-contaminated nonferrous metal(loid) tailings sites.

To investigate the removal characteristics of ammonium-nitrogen (NH₄⁺-N), nitrite-nitrogen (NO₂⁻-N), nitrate-nitrogen (NO₃⁻-N), and total nitrogen from groundwater by a degradable composite active medium, kinetics, thermodynamics, and equilibrium adsorption, experiments were performed using scoria and degrading bacteria immobilized on scoria. Removal of NH₄⁺-N, NO₂⁻-N, and NO₃⁻-N was conducted in adsorption experiments using different times, initial concentrations, pH values, and groundwater chemical compositions (Ca²⁺, Mg²⁺, HCO₃⁻, CO₃²⁻, Fe²⁺, Mn²⁺, and SO₄²⁻). The results showed that the removal of nitrogen by the composite active medium was obviously better than that of scoria alone. The removal rates of NH₄⁺-N (C₀ = 5 mg/L), NO₂⁻-N (C₀ = 5 mg/L), and NO₃⁻-N (C₀ = 100 mg/L) by the composite active medium within 1 h were 96.05%, 82.40%, and 83.16%, respectively. The adsorption kinetics were well fitted to a pseudo-second order model, whereas the equilibrium adsorption agreed with the Freundlich model. With changes in the pH, variation in the removal could be attributed to the combined effect of hydrolysis and competitive ion adsorption, and the optimum pH was 7. Different concentration conditions, hardness, alkalinity, anions, and cations showed different promoting and inhibiting effects on the removal of nitrogen. A careful examination of ionic concentrations in adsorption batch experiments suggested that the sorption behavior of nitrogen onto the immobilized medium was mainly controlled by ion exchange. The degrading bacteria on the scoria surface were eluted and analyzed by metagenomic sequencing. There were significant differences in the number of operational taxons, relative abundances, and community diversity among degrading bacteria after adsorption of the three forms of nitrogen. The relative abundance of degrading bacteria was highest after NO₃⁻-N removal, and the diversity was highest after NO₂⁻-N removal. Pseudomonas and Serratia were the dominant genera that could efficiently remove NH₄⁺-N and NO₂⁻-N.

Abiotic reduction represents an attractive technology to control U(VI) contamination. In this work, an abiotic route of U(VI) reduction with humic acid at mineral surfaces is proposed and reaction mechanisms are addressed by periodic density functional theory calculations. Different influencing factors such as ligand effect, content of CO₃²⁻ ligands and substituent effect are inspected. The coordination chemistry of uranyl(VI) surface complexes relies strongly on substrates and ligands, and the calculated results are in good agreements with experimental observations available. For the OH⁻ ligand, two competitive mechanisms co-exist that respectively produce the U(IV) and U(V) species, and the former is significantly preferred because of lower energy barriers. Instead, the NO₃⁻ ligand leads to the formation of U(V) while for the Cl⁻ ligand, the U(VI) surface complex remains very stable and is not likely to be reduced because of very high energy barriers. The U(V) and U(IV) complexes are the predominant products for low and high CO₃²⁻ contents, respectively. Accordingly, the abiotic reduction processes with humic acid are efficient to manage U(VI) contamination and become preferred under basic conditions or at higher CO₃²⁻ contents. The U(VI) reduction is further promoted by introduction of electron-donating rather than electron-withdrawing substituents to humic acid. Electronic structure analyses and vibrational frequency assignments are calculated for the various uranium surface complexes of the reduction processes, serving as a guide for future experimental and engineered studies. The molecular-level understanding given in this work offers an abiotic route for efficient reduction of U(VI) and remediation of U(VI)-contaminated sites at ambient conditions.

Due to the lack of substantial and reliable evidence on the relationship between prenatal cadmium (Cd) exposure and cognitive development of offspring, we conducted the present systematic review. Leading electronic databases—including Pubmed, Embase, Web of Science, the Cochrane Library, PsycINFO, PsycARTICLES, and the Psychology and Behavioral Sciences Collection—were searched on February 14, 2019. There was no date, study design or language limit imposed in our search. All of the included studies satisfied our predetermined study population (pregnant mothers and their offspring), exposure (prenatal Cd exposure), and outcome measurements (adverse effects on cognitive development). The quality assessment for the included studies was conducted with the Newcastle-Ottawa Scale (NOS). Nine prospective cohort studies met the inclusion criteria, and six of them were assessed to be of high quality based on the NOS (NOS score ≥ 7). The prenatal Cd exposure was tested in maternal blood samples (4/9), umbilical cord blood samples (4/9), or maternal urinary samples (3/9). Among the nine studies included, six reported at least one inverse association between prenatal Cd exposure and the cognitive development of offspring, mainly in terms of language development (4/8), performance ability development (3/5), and general cognitive development (3/8). Furthermore, among six studies with high methodological quality (NOS score ≥ 7), prenatal Cd exposure was reported to be associated with language development in three studies (3/5), performance ability development in three studies (3/4), and general cognitive development in three studies (3/5). This systematic review provides convincing evidence that prenatal exposure to Cd is inversely associated with neurodevelopment of offspring. Larger prospective studies using standardized criteria and assessments of cognitive development are needed to confirm the dose-response effect and gender difference of prenatal Cd exposure on cognitive development of offspring.

Emission from manufacturing facilities to the surrounding environment is one of the important input source of pollutants. However, no information on the levels of organophosphate esters (OPEs) contamination in the environmental media around the manufacturing facility is available to date. In this study, samples from various environmental media, including sediments, water, surface soils, and tree bark, were obtained near an OPE manufacturing plant in Hengshui, Hebei Province, North China. The three main congeners, detected were tris(2-chloroethyl) phosphate (TCEP), tris(2-chloroisopropyl) phosphate (TCIPP), and triphenyl phosphate (TPHP), with the summed OPE concentrations (∑OPEs) ranging from 340 to 270,000 μg kg⁻¹ dry weight (d.w.), 7100 to 33,000 ng L⁻¹, not detected (N.D.) to 14,000 ng kg⁻¹ d.w., and 5300 to 19,000 ng g⁻¹ lipid weight in the sediments, water, soils, and tree bark, respectively. These findings suggest that point sources of OPEs could have widespread effects on its surrounding environments. Sediment and water concentrations of TCEP and TCIPP measured in this study were among the highest concentrations yet reported in the world. Meanwhile, the concentration ranges of TCEP and TCIPP in surface soils were significantly lower than those in the sediment and water, and among the lowest concentrations yet reported in soil data worldwide. This suggests that the manufacturing facility influenced the OPE distribution in different environmental media in different ways. Furthermore, TCEP and TCIPP might have been transported within the water stream from roots into the aboveground plants and then accumulated in tree barks.

Natural dissolved organic matter (DOM) produced in algal blooms and overgrowths of macrophyte changes the elimination and ecotoxicity of estrogens in freshwater lakes. The complexation of 17α-ethinylestradiol (EE2) and various DOMs, including the water- and sediment-derived DOMs from the algal-dominant zone in Lake Taihu (TW and TS, respectively) and the macrophyte-dominant zone in Poyang Lake (PW and PS, respectively), and the humic acid (HA), was investigated along with the subsequent effects on EE2 biodegradation. Dialysis equilibrium experiments showed that binding to DOM significantly decreased the freely soluble concentrations of EE2. The binding capacity of the five DOMs followed the order of PW < TW < PS ≈ TS < HA. A negative correlation was found between the organic-carbon-normalized sorption coefficient (logKDOC) and the absorption ratio (E₂/E₃) of DOM, indicating that the large sized, aromatic molecules were involved in the complexation. The reduced freely soluble concentrations of EE2 did not inhibit its biodegradation by an EE2-degrading strain, Rhodobacter blasticus. Conversely, the autochthonous-dominated water-derived DOMs stimulated a more extensive biodegradation of EE2 than the sediment-derived DOMs, and the existence of HA resulted in the smallest increase in EE2 biodegradation. The promoting effect was associated with the increased concentration, activity, and transforming rate of R. blasticus by the bioavailable components in DOM. The present study suggests that the significant impact of natural DOM should be fully considered when assessing the fate and ecological risks of estrogens in eutrophic waters.

Agriculture is one of major emission sources of nitrous oxide (N₂O), an important greenhouse gas dominating stratospheric ozone destruction. However, indirect N₂O emissions from agriculture watershed water surfaces are poorly understood. Here, surface-dissolved N₂O concentration in water bodies of the agricultural watershed in Eastern China, one of the most intensive agricultural regions, was measured over a two-year period. Results showed that the dissolved N₂O concentrations varied in samples taken from different water types, and the annual mean N₂O concentrations for rivers, ponds, reservoir, and ditches were 30 ± 18, 19 ± 7, 16 ± 5 and 58 ± 69 nmol L⁻¹, respectively. The N₂O concentrations can be best predicted by the NO3−-N concentrations in rivers and by the NH4+-N concentrations in ponds. Heavy precipitation induced hot moments of riverine N₂O emissions were observed during farming season. Upstream waters are hot spots, in which the N₂O production rates were two times greater than in non-hotspot locations. The modeled watershed indirect N₂O emission rates were comparable to direct emission from fertilized soil. A rough estimate suggests that indirect N₂O emissions yield approximately 4% of the total N₂O emissions yield from N-fertilizer at the watershed scale. Separate emission factors (EF) established for rivers, ponds, and reservoir were 0.0013, 0.0020, and 0.0012, respectively, indicating that the IPCC (Inter-governmental Panel on Climate Change) default value of 0.0025 may overestimate the indirect N₂O emission from surface water in eastern China. EF was inversely correlated with N loading, highlighting the potential constraints in the IPCC methodology for water with a high anthropogenic N input.

Cyanobacterial blooms are of global concern due to the multiple harmful risks they pose towards aquatic ecosystem and human health. However, information on the fate of organic pollutants mediated by cyanobacterial blooms in eutrophic water remains elusive. In the present study, endocrine disruptive potentials of phytoplankton samples were evaluated throughout a year-long surveillance in a large and eutrophic freshwater lake. Severe cyanobacterial blooms persisted during our sampling campaigns. Estrogenic agonistic, anti-estrogenic, anti-androgenic, and anti-glucocorticogenic effects were observed in the phytoplankton samples using in vitro reporter gene bioassays. 27 endocrine disrupting chemicals (EDCs) of different modes of action were detected in the samples via UPLC-MS/MS system. Results from mass balance analysis indicated that the measured estrogenic activities were greater than the predicted estrogenic potencies from chemical analysis, demonstrating that chemical analysis of targeted EDCs is unable to fully explain the compounds responsible for the observed estrogenicities. Results from Spearman's correlation analysis concluded that the concentrations of ten EDCs in phytoplankton samples were negatively correlated with cyanobacterial biomass, suggesting the potential occurrence of biomass bio-dilution effects of EDCs due to the huge biomass of cyanobacteria during bloom seasons. The present study provided complementary information about the potential endocrine disruptive risks of cyanobacterial blooms, which is important for understanding and regulating EDCs in eutrophic lakes.

The imprints of fireworks displays on the adjacent water body were investigated from the perspective of cogeneration of black carbon, metals and perchlorate (ClO₄⁻). In particular, the mixing and dissipation of ClO₄⁻ were studied at Oak Lake, Lincoln, Nebraska, following fireworks displays in 2015 and 2016. Following the display, ClO₄⁻ concentration in the water increased up to 4.3 μg/L and 4.0 μg/L in 2015 and 2016, respectively. A first-order model generally provided a good fit to the measured perchlorate concentrations from which the rate of dissipation was estimated as 0.07 d⁻¹ in 2015 and 0.43 d⁻¹ in 2016. SEM images show imprints of soot and metal particles in aerosol samples. EDS analysis of the lake sediment confirmed the presence of Si, K, Ca, Zn and Ba, most of which are components of fireworks. The δ¹³C range of −7.55‰ to −9.19‰ in the lake water system closely resembles fire-generated carbon. Cogeneration of black carbon and metal with perchlorate was established, indicating that ClO₄⁻ is an excellent marker of fireworks or a burning event over all other analyzed parameters. Future microcosmic, aggregation and column-based transport studies on black carbon in the presence of perchlorate and metals under different environmental conditions will help in developing transport and fate models for perchlorate and black carbon particles.