Occurrence and ecological risk assessment of 2,2',4,4'-tetrabromodiphenyl ether and decabromodiphenyl ether in surface waters across China.

Polybrominated diphenyl ethers (PBDEs) are efficient brominated flame retardants and are released into various environmental media via usage, recycling and disposal. This study investigated the concentrations and ecological risks of two typical PBDEs, 2,2',4,4'-tetrabromodiphenyl ether (BDE-47) and decabromodiphenyl ether (BDE-209), in surface waters across China from 2011 to 2018. The results showed that the concentration of BDE-209 (8.25 ng L-1) was higher than that of BDE-47 (1.02 ng L-1), and the concentrations of BDE-47 and BDE-209 in the lakes (2.56 ng L-1 and 22.19 ng L-1, respectively) were higher than those in the rivers (0.58 ng L-1 and 7.05 ng L-1, respectively). In addition, the concentration of BDE-209 in the wet season (2.61 ng L-1) was lower than that in the dry season (10.83 ng L-1), whereas the concentration of BDE-47 in the wet season (0.24 ng L-1) was a little lower than that in the dry season (0.99 ng L-1). BDE-47 and BDE-209 concentrations showed a gradual decrease in surface waters across China during the eight-year period. Based on the species sensitivity distribution (SSD) models, the 5% hazardous concentration (HC5) and predicted no-effect concentration (PNEC) values were derived using the acute and chronic toxicity data of BDE-47 and BDE-209. Results showed that the PNEC values based on the acute and chronic toxicity data were 2.08 µg L-1 and 0.52 µg L-1 for BDE-47, respectively and 370 µg L-1 and 0.34 µg L-1 for BDE-209, respectively. The risk quotient (RQ) values of BDE-47 in surface waters across China were far smaller than 0.1 (low ecological risk). Similarly, the RQ values of BDE-209 were also smaller than 0.1, except for those at Baiyangdian Lake and Chaohu Lake, where the probability of 0.1 ≤ RQ < 1.0 (medium ecological risk) was approximately 10% based on 10,000 Monte Carlo simulations.

Assessment of heavy metal contamination of an electrolytic manganese metal industrial estate in northern China from an integrated chemical and magnetic investigation.

Heavy metal concentrations (Al, V, Mn, Fe, Co, Ni, Cu, Zn, and Pb) and the magnetic properties of soil and sediment samples in/around an electrolytic manganese metal (EMM) industrial estate in northern China were investigated. Potential enrichment of Mn, Zn, and Pb was found in/around the core area of the EMM industrial estate; however, the pollution load index (PLI) values did not indicate severely polluted levels. For adults, all hazard index (HI) values of noncarcinogenic risks in the soil samples were below the safe level of 1.00. For children, none of the HI values exceeded the safe level, except Mn (HI = 1.23) in one industrial estate sample. The particle size of magnetic materials was mostly in the range of stable single-domain, and coarser ferrimagnetic phases enhanced the magnetic parameters in the industrial estate soils. Highly positive correlations were found between magnetic parameters, heavy metal concentrations, and PLI values, demonstrating that the magnetic parameters are an efficient proxy for assessing heavy metal contamination. Enrichment of Mn, Zn, and Pb was mainly derived from the EMM industry. The data showed that the EMM industrial estate under cleaner production had limited adverse impacts on the adjacent environment from the perspective of heavy metal contamination.

A tiered probabilistic approach to assess antibiotic ecological and resistance development risks in the fresh surface waters of China.

Exposure to antibiotics can result in not only ecotoxicity on aquatic organisms but also the development of antibiotic resistance. In the study, the ecotoxicity data and minimum inhibitory concentrations of the antibiotics were screened to derive predicted no-effect concentrations of ecological (PNECeco) and resistance development risks (PNECres) for 36 antibiotics in fresh surface waters of China. The derived PNECeco and PNECres values were ranged from 0.00175 to 2351 µg/L and 0.037-50 µg/L, respectively. Antibiotic ecological and resistance development risks were geographically widespread, especially in the Yongding River, Daqing River, and Ziya River basins of China. Based on the risk quotients, 11 and 14 of 36 target antibiotics were at high ecological risks and high resistance development risks in at least one basin, respectively. The higher tiered assessments provided more detailed risk descriptions by probability values and ß-lactams (penicillin and amoxicillin) were present at the highest levels for ecological and resistance development risks. Although there was uncertainty based on the limited data and existing methods, this study can indicate the overall situation of the existing risk levels and provide essential insights and data supporting antibiotic management.

Tiered ecological risk assessment of nonylphenol and tetrabromobisphenol A in the surface waters of China based on the augmented species sensitivity distribution models.

The ecological risks of nonylphenol (NP) and tetrabromobisphenol A (TBBPA) have received continued attention owing to their large consumption, frequently detection, adverse effects on the reproductive fitness, and lack of risk assessment technical systems. The geometric mean of the median concentrations of NP in the 22 surface waters was 0.278 µg/L, and TBBPA in the seven surface waters was 0.014 µg/L in China. The species sensitivity distribution (SSD) models were augmented by extrapolated reproductive toxicity data of native species to reduce uncertainty. The SSD models and the hazardous concentrations for 5% of species exhibited good robustness and reliability using the bootstrap method and minimum sample size determination. The acute and reproductive predicted no-effect concentrations (PNECs) were derived as 9.88 and 0.187 µg/L for NP, and 56.6 and 0.0878 µg/L for TBBPA, respectively. The risk quotients indicated that 11 of 22 locations for NP, and 3 of 7 locations for TBBPA were at high ecological risk levels based on the reproductive PNECs. Furthermore, the higher tier ecological risk assessment (ERA) based on potential affected fraction and joint probability curves indicated that the ecological risks in the four of above locations needed further concern. The ERA based on both the acute and reproductive toxicity is essential for assessing the ecological risks of NP and TBBPA, otherwise using acute PNECs only may result in an underestimation of ecological risk. The developed tiered ERA method and its framework can provide accurate, detailed, quantitative, locally applicable, and economically technical support for ERA of typical endocrine-disrupting chemicals in China.

Mineral-modulated Co catalyst with enhanced adsorption and dissociation of BH4- for hydrogenation of p-nitrophenol to p-aminophenol.

Slow adsorption and dissociation kinetics of NaBH4 onto the catalyst surface limit the hydrogenation reduction of hazardous p-nitrophenol to worthy p-aminophenol. Herein, we design a mineral-modulated catalyst to facilitate the rate-limiting step. Carbon-coated etched attapulgite (EAtp@C) is obtained by HF treatment. Co/EAtp@C is fabricated via anchoring cobalt nanoparticles (CoNPs) on the carrier EAtp@C. Compared to pure Co, the anchored CoNPs are more electronegative and stable, which provides abundant and stable active sites and accelerates the BH4- adsorption and dissociation. Therefore, Co/EAtp@C leads to nearly 100% reduction of p-nitrophenol to p-aminophenol within 8 min and its apparent rate constant Kapp (0.69 min-1) is 4 times higher than that of pure Co. Thermodynamic calculations show a lower activation energy (37.92 kJ mol-1) of Co/EAtp@C catalyst than that of pure Co. Co/EAtp@C also shows magnetic separability and good stability by remaining 98.6% of catalytic conversion rate after six cycles. Significantly, we detect the active species Co-H, and reveal the electron transfer mechanism between catalysts, BH4-, and p-nitrophenol by electrochemical method. These results offer a fundamental insight into the catalytic mechanism of p-nitrophenol hydrogenation for rational design of efficient catalysts.

GSTP1 genetic polymorphism is associated with a higher risk of DNA damage in pesticide-exposed fruit growers.

Pesticide exposure is associated with various neoplastic diseases and congenital malformations. Animal studies also indicated that pesticides may be metabolized by cytochrome P450 3A5 (CYP3A5) enzymes, paraoxonases (PON1 and PON2), or glutathione S-transferases (GSTM1, GSTT1, and GSTP1). However, little is known about the genotoxicity of pesticides in people with various genetic polymorphisms of human CYP3A5, PON1, PON2, GSTM1, GSTT1, and GSTP1. Thus, this study was designed to investigate whether various metabolic genotypes are more susceptible to DNA damage in pesticide-exposed fruit growers. Using the Comet assay, the extent of DNA damage was evaluated in the peripheral blood of 91 fruit growers who experienced pesticide exposure and 106 unexposed controls. Questionnaires were administered to obtain demographic data, cigarette smoking habits, medical, and occupational histories. The genotypes for CYP3A5, PON1, PON2, GSTM1, GSTT1, and GSTP1 genes were identified by PCR. The results showed that subjects experiencing high or low pesticide exposure had a significantly greater DNA tail moment (DAN damage) than did controls. The multiple regression model also revealed that age (P < 0.01), high pesticide exposure (P < 0.01), low pesticide-exposure (P < 0.01), and CYP3A5 (P = 0.04) and GSTP1 (P = 0.02) genotypes were significantly associated with an increased DNA tail moment. Further analysis of environmental and genetic interactions revealed a significant interaction for GSTP1 genotypes to influence DNA tail moment for the high pesticide exposure group. These results suggest that individuals with susceptible metabolic GSTP1 genotypes may experience an increased risk of DNA damage elicited by pesticide exposure.