Elucidating the mechanisms of heavy metal (HM) adsorption on clay minerals is key to solving HM pollution in soil. In this study, the adsorption of four HM atoms (As, Cd, Cr, and Hg) on the illite(001) surface was investigated using density functional theory calculations. Different adsorption configurations were investigated and the electronic properties (i.e., adsorption energy (Eₐd) and electron transfer) were analyzed. The Eₐd values of the four HM atoms on the illite(001) surface were found to be As > Cr > Cd > Hg. The Eₐd values for the most stable adsorption configurations of As, Cr, Cd, and Hg were −1.8554, −0.7982, −0.3358, and −0.2678 eV, respectively. The As atoms show effective chemisorption at all six adsorption sites, while Cd, Cr, and Hg atoms mainly exhibited physisorption. The hollow and top (O) sites were more favorable than the top (K) sites for the adsorption of HM atoms. The Gibbs free energy results show that the illite(001) surface was energetically favorable for the adsorption of As and Cr atoms under the influence of 298 K and 1 atm. After adsorption, there was a redistribution of positions and reconfiguration of the chemical bonding of the surface atoms, with a non-negligible influence around the upper surface atoms. Bader charge analysis shows electrons were transferred from the surface to the HM atoms, and a strong correlation between the valence electron variations and the adsorption energy was observed. HM atoms had a high electronic state overlap with the surface O atoms near the Fermi energy level, indicating that the surface O atoms, though not the topmost atoms around the surface, significantly influence HM adsorption. The above results show illite(001) preferentially adsorbed As among all four investigated HM atoms, indicating that soils containing a high proportion of illite might be more prone to As pollution.

Bacteria are candidates for the biotransformation of environmental arsenic (As), while As metabolism in bacteria is not yet fully understood. In this study, we sequenced the genome of an As-resistant bacterium strain Stenotrophomonas maltophilia SCSIOOM isolated from the fish gut. After arsenate (As(V)) exposure, S. maltophilia transformed As(V) to organoarsenicals, along with the significant change of the expression of 40 genes, including the upregulation of arsH, arsRBC and betIBA. The heterogeneous expression of arsH and arsRBC increased As resistance of E. coli AW3110 by increasing As efflux and transformation. E. coli AW3110 (pET-betIBA) could transform inorganic As into dimethylarsinate (DMA) and nontoxic arsenobetaine (AsB), which suggested that AsB could be synthesized through the synthetic pathway of its analog-glycine betaine. In addition, the existence of arsRBC, betIBA and arsH reduced the reactive oxygen species (ROS) induced by As exposure. In total, these results demonstrated that S. maltophilia adopted an As metabolism strategy by reducing As accumulation and synthesizing less toxic As species. We first reported the production and potential synthetic pathway of AsB in bacteria, which improved our knowledge of As toxicology in microorganisms.

To date, knowledge of internal human exposure to BPA and its analogues (particularly bisphenol S and bisphenol F, etc.) remains limited. In the present study, a method involving dispersive solid-phase extraction and LC/MS was proposed to investigate the contamination levels of 28 precursor bisphenols and 9 major metabolites in serum. The critical variables of preparation method were screened out by Plackett-Burman design and further optimized by central composite design. Left in optimal conditions, a total of 286 samples consisting of 153 males and 133 females were analyzed. The results showed that BPA dominated over all the cases with the highest positive rate (82.2% of all the surveyed people), and totally four metabolites (BPA β-D-glucuronide, BPA monosulfate, BPA bis-(β-D-glucuronide) and BPS monosulfate) were detectable. The occurrence of BPA bis-(β-D-glucuronide) in serum is reported for the first time and its higher positive rate and contamination concentrations suggested that it may be a more important metabolite of BPA than others. Negligible potential risk of health effects to blood donors was observed, since the estimated exposure levels (mean 32.1 ng/kg bw/day, 95th 123.2 ng/kg bw/day) were well below far less than the temporary tolerable reference dose of BPA that recommended by the European Food Safety Authority (4 μg/kg bw/day by). The reference level of BPA for healthy population was determined to be 4.09 μg/L via the percentile method.

Antibiotic resistance genes (ARGs) are abundantly shed in feces. Thus, it is crucial to identify their host sources so that ARG pollution can be effectively mitigated and aquatic ecosystems can be properly conserved. Here, spatiotemporal variations and sources of ARGs in the Longjiang watershed of South China were investigated by linking them with microbial source tracker (MST) indicators. The most frequently detected ARGs (>90%) were sulI, sulII, blaTEM, tetW, ermF, and the mobile element intI1. Spatial distribution analyses showed that tributaries contributed significantly more sulI, sulII, and ermF contamination to the Longjiang watershed than the main channel. MST indicator analysis revealed that the Longjiang watershed was contaminated mainly by human fecal pollution. Livestock- and poultry-associated fecal pollution significantly declined after the swine fever outbreak. The occurrence of most ARGs is largely explained by human fecal pollution. In contrast, pig fecal pollution might account for the prevalence of tetO. Moreover, combined human-pig fecal pollution contributed to the observed blaNDM₋₁ distribution in the Longjiang watershed. Subsequent analysis of the characteristics of MST markers disclosed that the relatively lower specificities of BacHum and Rum-2-Bac may lead to inaccurate results of tracking ARG pollution source. The present study determined spatiotemporal variations and ARG origins in the Longjiang watershed by combining MST markers. It also underscored the necessity of using multiple MST markers simultaneously to identify and characterize ARG pollution sources accurately.

Antibiotics are widely applied to prevent and treat diseases occurred in mariculture. The often-open nature of mariculture production systems has led to antibiotic residue accumulation in the culturing and adjacent environments, which can adversely affect aquatic ecosystems, and even human. This review summarizes the occurrence, environmental behavior, and ecological effects of antibiotics in mariculture systems based on peer-reviewed papers. Forty-five different antibiotics (categorized into ten groups) have been detected in mariculture systems around the world, which is far greater than the number officially allowed. Indiscriminate use of antibiotics is relatively high among major producing countries in Asia, which highlights the need for stricter enforcement of regulations and policies and effective antibiotic removal methods. Compared with other environmental systems, some environmental characteristics of mariculture systems, such as high salinity and dissolved organic matter (DOM) content, can affect the migration and transformation processes of antibiotics. Residues of antibiotics favor the proliferation of antibiotic resistance genes (ARGs). Antibiotics and ARGs alter microbial communities and biogeochemical cycles, as well as posing threats to marine organisms and human health. This review may provide a valuable summary of the effects of antibiotics on mariculture systems.

Lead-zinc slag (LZS) is a solid waste product that is rich in silicon and aluminum and has enormous resource potential for functional environmental functional geopolymer materials. Unfortunately, the solidification mechanism of heavy metals in geopolymers is still unclear, which is detrimental to the heavy metal solidification of LZS. In this study, we comprehensively studied and demonstrated the solidification mechanisms of Pb and Zn in geopolymers, based on the preparation of high-performance LZS-based geopolymers (compressive strength up to 89.3 MPa, and Pb and Zn solidification efficiency up to 93.1% and 90.0%, respectively). Thereafter, the solidification mechanism differences between Pb and Zn were explained by electronegativity and ion potential. Due to the ionic potential order of Zn²⁺> Pb²⁺> Na⁺, both Zn²⁺ and Pb²⁺ could exchange with Na⁺ in the geopolymer. In addition, due to the electronegativity order of Pb > Si > Zn, Pb could attack the [SiO₄] structure and form covalent bonds in the Pb–O structure, while Zn did not (shown by Raman spectroscopy). As a result, Pb simultaneously solidified in the geopolymer through covalent bonding and ion exchange, while Zn was solidified mainly by ion exchange. Thus, this work provides new perspectives and ideas for the solidification mechanisms of heavy metals in geopolymers.

Plant growth regulators (PGRs) assisted phytoextraction was investigated as a viable phytoremediation technology to increase the phytoextraction efficiency in contaminated soils. This study aimed to evaluate the cadimum (Cd)/lead (Pb)/zinc (Zn) phytoextraction efficiency by a hyperaccumulator Sedum alfredii Hance (S. alfredii) treated with 9 PGRs, including indole-3-acetic acid (IAA), gibberellin (GA₃), cytokinin (CKs), abscisic acid (ABA), ethylene (ETH), brassinosteroid (BR), salicylic acid (SA), strigolactones (SL) and jasmonic acid (JA), in slightly or heavily contaminated (SC and HC, respectively) soil. Results demonstrated that PGRs were able to improve S. alfredii biomass, the most significant increases were observed in GA₃ and SL for HC soil, while for SC soil, IAA and BR exhibited positive effects. The levels of Cd, Pb and Zn in the shoots of S. alfredii treated with ABA and SL were noticeably greater than in the CK treatment in HC soil, while the uptake of metals were increased by IAA and CKs in SC soil. Combined with the results of biomass and metal contents in shoots, we found that ABA showed the highest Cd removal efficiency and the maximum Pb and Zn removal efficiency was observed with GA₃, which was 62.99%, 269.23%, and 41.18%, respectively higher than the control in HC soil. Meanwhile, compared to control, the maximum removal efficiency of Cd by IAA treatment (52.80%), Pb by JA treatment (165.1%), and Zn by BR treatment (44.97%) in the SC soil. Overall, our results suggested that these PGRs, especially, ABA, SL, IAA, BR and GA₃ had great potential in improving phytoremediation efficiency of S. alfredii grown in contaminated soils.

Lead concentrations in hard antlers of adult European roebucks (Capreolus capreolus) were analyzed to assess lead exposure of roe deer roaming the floodplain of the Innerste River, a river system contaminated due to historical metal ore mining, processing, and smelting in its upper reaches. Antler lead concentrations of roebucks culled in the period 1939–2018 within or close to the Innerste floodplain ranged between <0.17 mg Pb/kg (limit of detection) and 51.5 mg Pb/kg (air-dry weight). Median lead concentration in antlers of roebucks culled within the floodplain was 11.1 mg Pb/kg, compared to 2.3 mg Pb/kg in antlers of bucks culled in the floodplain vicinity (P < 0.01). Sampling year had no significant effect on antler lead concentrations (P = 0.748). Lead isotope ratios of antlers from the Innerste downstream area (²⁰⁶Pb/²⁰⁷Pb: 1.179–1.181; ²⁰⁸Pb/²⁰⁶Pb: 2.083–2.085) fell within the range of those reported for hydrothermal vein deposits from the upper catchment area of the Innerste River in the Harz Mountains. Our study demonstrates the long-lasting impact of the historical metal ore mining, processing, and smelting in the Harz Mountains on lead pollution in floodplains of rivers draining this area and the lead exposure of wild herbivores inhabiting the floodplains. Furthermore, it highlights the suitability of roe deer antlers for monitoring environmental lead levels and the usefulness of lead isotope signatures in antlers for source apportionment of lead pollution.

The increasing microplastics (MPs) pollution and continuous acid rain coincide in many areas of the world. However, how MPs interact with acid rain is still unclear. Herein, we conducted a microcosm experiment to decipher the combined effect of polyethylene (PE) MPs (1%, 5%, and 10%) and acid rain (pH 4.0) on the agricultural soil ecosystem of Southern China, in which edaphic property, microbial community, enzymatic activity and CO₂ emission were investigated. The results showed that PE MPs significantly decreased soil water retention and nitrate nitrogen content regardless of acid rain. Soil total nitrogen significantly decreased under the co-exposure of 10% PE MPs and acid rain. However, PE MPs did not alter soil microbial biomass, i.e., the content of microbial biomass carbon, total phospholipid fatty acids, with or without acid rain. 10% PE MPs and acid rain treatment significantly increased the activity of catalase and soil CO₂ emission. PE MPs addition did not affect the temperature sensitivity (Q₁₀) of soil CO₂ emission regardless of acid rain. These findings suggest that MPs may interact with acid rain to affect soil ecosystems, thus underscoring the necessity to consider the interaction between MPs and ambient environmental factors when exploring the impact of MPs on the soil biodiversity and function.