Dioxybenzone is widely used in cosmetics and personal care products and frequently detected in multiple environmental media and human samples. However, the current understanding of the metabolic susceptibility of dioxybenzone and the potential endocrine disruption through its metabolites in mimicking human estrogens remains largely unclear. Here we investigated the in vitro metabolism of dioxybenzone, detected the residue of metabolites in rats, and determined the estrogenic disrupting effects of these metabolites toward estrogen receptor α (ERα). In vitro metabolism revealed two major metabolites from dioxybenzone, i.e., M1 through the demethylation of methoxy moiety and M2 through hydroxylation of aromatic carbon. M1 and M2 were both rapidly detected in rat plasma upon exposure to dioxybenzone, which were then distributed into organs of rats in the order of livers > kidneys > uteri > ovaries. The 100 ns molecular dynamics simulation revealed that M1 and M2 formed hydrogen bond to residue Leu387 and Glu353, respectively, on ERα ligand binding domain, leading to a reduced binding free energy. M1 and M2 also significantly induced estrogenic effect in comparison to dioxybenzone as validated by the recombinant ERα yeast two-hybrid assay and uterotrophic assay. Overall, our study revealed the potential of metabolic activation of dioxybenzone to induce estrogenic disrupting effects, suggesting the need for incorporating metabolic evaluation into the health risk assessment of benzophenones and their structurally similar analogs.

As agriculture expands to provide food and wellbeing to the world’s growing population, there is a simultaneous increasing concern about the use of agrochemicals, which can harm non-target organisms, mainly in the aquatic environment. The fungicide Mancozeb (MZ) has been used on a large-scale and is a potent inducer of oxidative stress. Therefore, there is an urgent need for the development of more sensitive biomarkers designed to earlier biomonitoring of this compound. Here we tested the hypothesis that behavioral changes induced by sublethal MZ concentrations would occur first as compared to biochemical oxidative stress markers. Embryos at 4 h post-fertilization (hpf) were exposed to Mancozeb at 5, 10 and 20 μg/L. Controls were kept in embryo water only. Behavioral and biochemical parameters were evaluated at 24, 28, 72, and 168 hpf after MZ exposure. The results showed that MZ significantly altered spontaneous movement, escape responses, swimming capacity, and exploratory behavior at all exposure times. However, changes in ROS steady-stead levels and the activity of antioxidant enzymes were observable only at 72 and 168 hpf. In conclusion, behavioral changes occurred earlier than biochemical alterations in zebrafish embryos exposed to MZ, highlighting the potential of behavioral biomarkers as sensitive tools for biomonitoring programs.

Ambient carbon monoxide (CO) and particulate matters (PMs) are two important air pollutants in urban areas with known impacts on fetuses. Hence, this study measured some biochemistry factors of 200 neonates with birth dates from January 19 to October 12, 2020, including the birth weight and height and the serum levels of ALT, AST, ALP, GGT, and TSH. The Support Vector Machine-fitted land-use regression approach was used to predict the spatio-temporal variability of intra-urban PM 2.5 and CO concentrations by month during the pregnancy period of the cases employing 5 variables of Digital Elevation Model (DEM), slope, and distance from Compressed Natural Gas (CNG) stations, Bus Rapid Transit (BRT) stations, and mines and industries. Spearman correlation analysis (p < 0.05) was performed between the neonate indices and mean monthly PM 2.5 and CO concentrations at the exact residential address of maternal cases and their nearby areas in 250, 500, 1000, 1500, and 2000 m-radius buffer rings. All modeling efforts succeeded in predicting CO and PM 2.5 levels with acceptable adjusted r² values. Northern Isfahan had relatively higher CO and PM 2.5 concentrations due to its adjacency to low-vegetated open lands and its high traffic load as compared to southern areas. The correlation results between the neonate biochemistry indices and mean PM 2.5 and CO concentrations were mostly positive in most buffer rings, especially in the >500 m-radius buffer rings for PM 2.5 and in the 2000 m-radius rings for CO. Although the correlation results of PM 2.5 followed a detectable trend in the buffer rings, the associations between CO and the neonate biochemistry indices differed significantly between the buffer rings. Results showed that increasing mean monthly concentration of CO and PM 2.5 may stimulate further production of liver enzymes while decreasing the birth weight and height.

Ambient fine particulate matter (PM₂.₅) is a worldwide environmental problem and is posing a serious threat to human health. Until now, the molecular toxicological mechanisms and the crucial toxic components of PM₂.₅ remain to be clarified. This study investigated the whole transcriptomic changes in THP-1 derived macrophages treated with different types of PM₂.₅ extracts using RNA sequencing technique. Bioinformatics analyses covering biological functions, signal pathways, protein networks and node genes were performed to explore the candidate pathways and critical genes, and to find the potential molecular mechanisms. Results of Gene Ontology (GO), Kyoto Encyclopedia of Genes and Genomes pathway (KEGG), and protein-protein interaction (PPI) networks revealed that water extracts (WEs) of PM₂.₅ obviously influenced genes and molecular pathways responded to oxidative stress and inflammation. Dichloromethane extracts (DEs) specifically affected genes and signal cascades related to cell cycle progress process. Furthermore, compared with WEs collected in heating season, non-heating season WEs induced much higher expression levels of Ca-associated genes (including phosphodiesterase 4B and cyclooxygenase-2), which may consequently result in more severe inflammatory responses. While, for DEs exposure, the heating season (DH) group showed extensive induction of deferentially expressed genes (DEGs) related to cell cycle pathway, which may be caused by the higher polycyclic aromatic hydrocarbons (PAHs) contents in DH samples than those from non-heating season. In conclusion, the oxidative stress and inflammation response are closely correlated with cellular responses in THP-1 derived macrophages induced by water soluble components of PM₂.₅, and cell cycle dysregulation may play an important role in biological effects induced by organic components. The different transcriptomic changes induced by seasonal PM₂.₅ extracts may partially depend on the contents of PAHs and metal ions, respectively.

Dichloromethane (DCM) is a volatile halogenated hydrocarbon with teratogenic, mutagenic and carcinogenic effects. Biodegradation is generally regarded as an effective and economical approach of pollutant disposal. In this study, a novel strain was isolated and its cytochrome P450 was heterologously expressed for DCM degradation. The isolate, Microbacterium keratanolyticum ZY, was characterized as a Gram-positive, rod-shaped and flagella-existed bacterium without spores (GenBank No. SUB8814364; CCTCC M 2019953). After successive whole-genome sequencing, assembly and annotation, eight identified functional genes (encoding cytochrome P450, monooxygenase, dehalogenase and hydrolase) were successfully cloned and expressed in Escherichia coli BL21 (DE3). The recombinant strain expressing cytochrome P450 presented the highest degradation efficiency (90.6%). Moreover, the specific activity of the recombinant cytochrome P450 was more than 1.2 times that of the recombinant dehalogenase (from Methylobacterium rhodesianum H13) under their optimum conditions. The kinetics of DCM degradation by recombinant cytochrome P450 was well fitted with the Haldane model and the value of maximum specific degradation rate was determined to be 0.7 s⁻¹. The DCM degradation might occur through successive hydroxylation, dehydrohalogenation, dechlorination and oxidation to generate gem-halohydrin, formyl chloride, formaldehyde and formic acid. The study helps to comprehensively understand the DCM dechlorination process under the actions of bacterial functional enzymes (cytochrome P450 and dehalogenase).

The Clean Air Action implemented by the Chinese government in 2013 has greatly improved air quality in the North China Plain (NCP). In this work, we report changes in the chemical components of atmospheric fine particulate matter (PM₂.₅) at four NCP sampling sites from 2012/2013 to 2017 to investigate the impacts and drivers of the Clean Air Action on aerosol chemistry, especially for secondary inorganic aerosols (SIA). During the observation period, the concentrations of PM₂.₅ and its chemical components (especially SIA, organic carbon (OC), and elemental carbon (EC)) and the frequency of polluted days (daily PM₂.₅ concentration ≥ 75 μg m⁻³) in the NCP, declined significantly at all four sites. Asynchronized reduction in SIA components (large decreases in SO₄²⁻ with stable or even increased NO₃⁻ and NH₄⁺) was observed in urban Beijing, revealing a shift of the primary form of SIA, which suggested the fractions of NO₃⁻ increased more rapidly than SO₄²⁻ during PM₂.₅ pollution episodes, especially in 2016 and 2017. In addition, unexpected increases in the sulfur oxidation ratio (SOR) and the nitrogen oxidation ratio (NOR) were observed among sites and across years in the substantially decreased PM₂.₅ levels. They were largely determined by secondary aerosol precursors (i.e. decreased SO₂ and NO₂), photochemical oxidants (e.g. increased O₃), temperature, and relative humidity via gas-phase and heterogeneous reactions. Our results not only highlight the effectiveness of the Action Plan for improving air quality in the NCP, but also suggest an increasing importance of SIA in determining PM₂.₅ concentration and composition.

The abnormal elevation of cyanobacterial density and total phosphorus concentration after the reduction of exogenous pollutants in Lake Taihu is still an open question. An in-situ light-dark bottle method was used to investigate the spatiotemporal differences of phosphorus release potential of bloom-forming cyanobacteria (BFC) in Lake Taihu. Generalized additive model analysis (GAM) of field data revealed that the phosphorus release potential of BFC increased with the upregulation of Chlorophyll a (Chl-a) content per cell, which was further validated by the laboratory experiment results. We deduced that the accumulation of Chl-a content per cell might be an essential index of high phosphorus release potential of BFC. The phosphorus release potential of BFC was much higher in summer and autumn than that in spring and winter, while the phosphorus absorption potential increased with the rising of temperature. The distinct physiological status of BFC at different seasons brought about their variation in phosphorus release potential. Additionally, high phosphorus release potential of BFC region mainly concentrated in the eastern and the central, northwest, western, and the south of Lake Taihu in spring, summer, autumn, and winter, respectively. Further studies showed that the spatial differences in phosphorus release potential of BFC were most probably due to the horizontal drift of BFC driven by the prevailing wind. Collectively, the synergism of BFC’s physiological status and horizontal drift determined the spatiotemporal differences of phosphorus release potential of BFC in Lake Taihu. Moreover, apparent spatiotemporal differences in phosphorus release potential of BFC were essential factors that induced the distinct distribution of total phosphorus in Lake Taihu. This study provides insight for exploring the reason for the constant increase of total dissolved phosphorus concentration and cyanobacterial density in Lake Taihu for the past 5 years.

This study investigates the occurrence and distribution of microplastics in water, sediment, and crayfish samples within pond and rice-crayfish co-culture breeding modes in Jianli prefecture, China. Microplastics in environmental and biological samples were systematically extracted by CaCl₂ solution, digested by H₂O₂ and KOH, and identified by μ-FTIR. A cleansing treatment for crayfish was performed in pure water before dissection and microplastic accumulation in different tissues (gill, stomach, gut, and flesh) of non-cleansed and cleansed crayfish were compared. The average microplastic abundances were 1.3 ± 0.1–2.5 ± 0.1 particles/L, 0.03 ± 0.01–0.04 ± 0.02 particles/g, and 0.17 ± 0.07–0.92 ± 0.19 particles/individual in water, sediment, and crayfish samples, respectively. Microplastics were detected in all studied crayfish tissues, except the flesh. There were no significant differences in microplastic abundances in water (P = 0.82), sediment (P = 0.90), and crayfish (P = 0.47 for non-cleansed samples; P = 0.30 for cleansed samples) between two breeding modes despite the detection of relatively higher microplastic abundances in the samples from the pond breeding mode. Microplastic accumulation in non-cleansed crayfish stomachs and guts (0.71 ± 0.18 particles/individual) was higher (P < 0.01) than that recorded in their gills (0.13 ± 0.06 particles/individual). Moreover, microplastics present in the stomachs and guts of cleansed crayfish were significantly less abundant (P < 0.01) than in non-cleansed crayfish, although this was not observed in the gills (P = 0.99). The majority of microplastic particles in this study had fiber-like shapes, blue and transparent colors, a size smaller than 1 mm, and polymer types of PP:PE and PE. The results demonstrate that microplastics in the environment can accumulate in the internal tissues of crayfish, which may pose a potential risk to humans through food consumption without the removal of the gills, stomach, and guts. This study provides valuable information for understanding microplastic accumulation in the different tissues of crayfish and the potential risk of human exposure to microplastics from crayfish as a food supplement.

Nitrate is the most common contaminant in groundwater in Korea, as well as across the world. Reduction of nitrate to ammonia is one of the options available to remediate groundwater. In this study, nitrate in groundwater was removed using a zero-valent iron (ZVI) containing biochar synthesized by co-pyrolyzing iron oxide and sawdust biomass. Among the various biogases generated during the pyrolysis of biomass, CO and H₂ act as reducing agents to transform iron oxides to ZVI. Approximately 71% of nitrate was reduced to ammonium by ZVI-biochar at initial pH 2.0, and the reduction decreased sharply by the increase in pH. The mass of nitrate-N decreased is exactly same with the mass of ammonia-N formed. However, ammonium remained in the aqueous phase after reduction by ZVI-biochar, and the total nitrogen was not lowered. Acid-washed zeolite adsorbed most ammonium reduced by the ZVI-biochar and maintained the pH to acidic condition to facilitate the reduction of nitrate. The results of this study imply that nitrate-contaminated groundwater can be properly treated within the guidelines of water quality by synthesized ZVI-containing biochar.

As the largest tributary flowing into Chaohu Lake, China, the Hangbu–Fengle River (HFR) has an important impact on the aquatic environment security of the lake. However, existing information on the potential risks of heavy metals (HMs) in HFR sediments was insufficient due to the lack of bioavailability data on HMs. Hence, geochemical fractionation, bioavailability, and potential risk of five HMs (Cr, Cu, Zn, Cd, and Pb) in HFR sediments were investigated by the combined use of the diffusive gradient in thin-films (DGT), sequential extraction (BCR), as well as the physiologically based extraction test (PBET). The average contents of Cd and Zn in the HFR Basin were more than the background values in the sediments of Chaohu Lake. A large percentage of BCR-extracted exchangeable fraction was found in Cd (8.69%), Zn (8.12%), and Cu (8.05%), suggesting higher bioavailability. The PBET-extracted fractions of five HMs were all almost closely positively correlated with their BCR-extracted forms. The pH was an important factor affecting the bioavailability of HMs. The average DGT-measured contents of Zn, Cd, Cr, Cu, and Pb were 28.07, 7.7, 3.69, 2.26, 0.5 μg/L, respectively. Only DGT-measured Cd significantly negatively correlated with Eh, indicating that Cd also had a high release risk under reducing conditions, similar to the risk assessment results. Our results could provide a reference for evaluating the potential bioavailabilities and ecological hazards of HMs in similar study areas.