Significant concerns have been raised regarding to the pollution of antibiotics in recent years due to the abuse of antibiotics and their high detection rate in water. Herein, a novel super adsorbent, boronic acid-modified bacterial cellulose microspheres with a size of 415 μm in diameter was prepared through a facile water-in-oil emulsion method. The adsorbent was characterized by atomic force microscopy, scanning electron microscopy, and fourier transform infrared spectroscopy analyses to confirm its properties. The microspheres were applied as packing materials for the adsorption of tetracycline (TC) from an aqueous solution and hoggery sewer via the reversible covalent interaction between cis-diol groups in TC molecules and the boronic acid ligand. TC adsorption performance had been systemically investigated under various conditions, including the pH, temperature, TC concentration, contact time, and ionic strength. Results showed that the adsorption met pseudo-second-order, Elovich kinetic model and Sips, Redlich-Peterson isothermal models. And the adsorption process was spontaneous and endothermic, with the maximum TC adsorption capacity of 614.2 mg/g. After 18 adsorption-desorption cycles, the adsorption capacity remained as high as 84.5% compared with their original adsorption capacity. Compared with other reported adsorption materials, the microspheres had high adsorption capacity, a simple preparation process, and excellent recovery performance, demonstrating great potential in application on TC removal for water purification and providing new insights into the antibiotic's adsorption behavior of bacterial cellulose-based microspheres.

Contaminant vulnerability in the critical zones like groundwater (GW)-seawater (SW) continuum along the entire Gujarat coast was investigated for the first time through an extensive water monitoring survey. The prime focus of the study was to evaluate whether or not: i) seawater intrusion induced metal load translates to toxicity; ii) in the coastal groundwater, metal distribution follows the pattern of other geogenic and anthropogenic contaminants like NO₃- and F-; and iii) what future lies ahead pertaining to metal fate in association with saturation conditions of the coastal aquifers. The spatial distribution of contaminants depicts that the Gulf of Khambhat area is highly contaminated. Ecological risk assessment (ERA) indicates that the Gujarat coast is experiencing a high ecological risk compared to the southeast coast of India. Investigation results revealed that metals, pH, NO₃, and CO₃ are more vulnerable at the SW-GW mixing interface. An increase in pH is reflected in fewer ionic species of metals in the GW. Salinity ingress due to seawater intrusion (SWI) reduces the toxicities of all trace metals except Cu, attributed to the increase of Ca in GW, leading to dissociation of CuCO₃. Reactive species are dominant for Zn and Cd; and M-CO₃ ligands are dominant for Cu and Pb owing to the undersaturation of dolomite and calcite in the aquifer system. SWI tends to increase the metal load but the toxicity of metals varies with the density of industries, anthropogenic activities, changes in the mixing-induced saturation conditions, and intensive salt production across the coast. Multivariate analysis confirmed that the hydrogeochemical processes change due to GW-SW mixing and dictates over natural weathering. The ecological risk index (ERI) for the Arabian sea is experiencing moderate (300 ≥ ERI>150) to high ecological risk (ERI >600). Children population is likely to encounter a high health risk through ingestion and dermal exposure than adults. Overall, the study emphasizes the complexity of toxicity-related health impacts on coastal communities and suggests the dire need for frequent water monitoring along the coastal areas for quick realization of sustainable development goals.

Bacteria and their secreted extracellular polymeric substances (EPS) are widely distributed in ecosystems and have high capacity for heavy metal immobilization. The knowledge about the molecular-level interactions with heavy metal ions is essential for predicting the behavior of heavy metals in natural and engineering systems. This comprehensive study using potentiometric titration, Fourier-transform infrared (FTIR) spectroscopy, isothermal titration calorimetry (ITC) and X-ray absorption fine structure (XAFS) was able to reveal the functional diversity and adsorption mechanisms for Pb onto bacteira and the EPS in greater detail than ever before. We identified mono-carboxylic, multi-carboxylic, phosphodiester, phosphonic and sulfhydryl sites and found the partitioning of Pb to these functional groups varied between gram-negative and gram-positive bacterial strains, the soluble and cell-bound EPS and Pb concentrations. The sulfhydryl and phosphodiester groups preferentially complexed with Pb in P. putida cells, while multifunctional carboxylic groups promoted Pb adsorption in B. subtilis cells and the protein fractions in EPS. Though the functional site diversity, the adsorption of Pb to organic ligands occurred spontaneously through a universal entropy increase and inner-sphere complexation mechanism. The functional group scale knowledge have implications for the modeling of heavy metal behavior in the environment and application of these biological resources.

It has been shown that chemical modification of chitosan with sulfur (S) functional groups could significantly enhance its chelating capability with heavy metals included Cd(II). However, a molecular level understanding has been lacking. Here, we carried out X-ray absorption fine structure (XAFS) and Fourier transformed infrared (FTIR) spectra studies to bridge this knowledge gap. The results indicate that both Cd–O/N and Cd–S bonds exist in the complex of Cd(II) with dithiocarbamate chitosan (DTC-CTS). S functional groups (dithiocarbamate) in DTC-CTS play the major role in complexation with Cd(II) and S content affects the adsorption mechanism. At low S content, Cd(II) is mainly adsorbed on DTC-CTS as an outer-sphere complex with two monodentate amino groups and two water molecules in tetrahedral configuration. At high S content, Cd adsorption dominantly occurs by formation of an inner-sphere complex with two bidentate mononuclear S ligands in tetrahedral configuration. This investigation provides information on the effectiveness and mechanisms of Cd(II) removal that is critical for evaluating modified chitosan applications for stabilization of Cd(II) in surface water, groundwater, soils and sediments.

Exposure to environmental endocrine disrupting chemicals (EDCs) is highly suspected in prostate carcinogenesis. Though, estrogenicity is the most studied behavior of EDCs, the androgenic potential of most of the EDCs remains elusive. This study investigates the androgen mimicking potential of some common EDCs and their effect in androgen-dependent prostate cancer (LNCaP) cells. Based on the In silico interaction study, all the 8 EDCs tested were found to interact with androgen receptor with different binding energies. Further, the luciferase reporter activity confirmed the androgen mimicking potential of 4 EDCs namely benzo[a]pyrene, dichlorvos, genistein and β-endosulfan. Whereas, aldrin, malathion, tebuconazole and DDT were reported as antiandrogenic in luciferase reporter activity assay. Next, the nanomolar concentration of androgen mimicking EDCs (benzo[a]pyrene, dichlorvos, genistein and β-endosulfan) significantly enhanced the expression of AR protein and subsequent nuclear translocation in LNCaP cells. Our In silico studies further demonstrated that androgenic EDCs also bind with epigenetic regulatory enzymes namely DNMT1 and HDAC1. Moreover, exposure to these EDCs enhanced the protein expression of DNMT1 and HDAC1 in LNCaP cells. These observations suggest that EDCs may regulate proliferation in androgen sensitive LNCaP cells by acting as androgen mimicking ligands for AR signaling as well as by regulating epigenetic machinery. Both androgenic potential and epigenetic modulatory effects of EDCs may underlie the development and growth of prostate cancer.

Because the pollutants produced by human activities have destroyed the ecological balance of natural water environment, and caused severe impact on human life safety and environmental security. Hence the task of water environment restoration is imminent. Metal-organic frameworks (MOFs), structured from organic ligands and inorganic metal ions, are notable for their outstanding crystallinity, diverse structures, large surface areas, adsorption performance, and excellent component tunability. The water stability of MOFs is a key requisite for their possible actual applications in separation, catalysis, adsorption, and other water environment remediation areas because it is necessary to safeguard the integrity of the material structure during utilization. In this article, we comprehensively review state-of-the-art research progress on the promising potential of MOFs as excellent nanomaterials to remove contaminants from the water environment. Firstly, the fundamental characteristics and preparation methods of several typical water-stable MOFs include UiO, MIL, and ZIF are introduced. Then, the removal property and mechanism of heavy metal ions, radionuclide contaminants, drugs, and organic dyes by different MOFs were compared. Finally, the application prospect of MOFs in pollutant remediation prospected. In this review, the synthesis methods and application in water pollutant removal are explored, which provide ways toward the effective use of water-stable MOFs in materials design and environmental remediation.

6:2 Cl-PFESA is a polyfluoroalkyl ether with high environmental persistence that has been confirmed to have significant adverse effects on animals. In this study, 6-week-old female C57BL/6 mice were exposed to 0, 1, 3 and 10 μg/L 6:2 Cl-PFESA for 10 weeks to estimate the hepatotoxicity of 6:2 Cl-PFESA and explore its underlying molecular mechanism. The results indicated that 6:2 Cl-PFESA preferentially bioaccumulated in the liver and induced hepatic cytoplasmic vacuolation and hepatomegaly in mice. In addition, serum metabolic profiling showed that 6:2 Cl-PFESA exposure caused an abnormal increase in amino acids and an abnormal decrease in acyl-carnitine, which interfered with fatty acid transport and increased the risk of metabolic diseases. Further experiments showed that 6:2 Cl-PFESA formed more hydrogen bonds with PPAR-γ than PFOS, Rosi and GW9662, and the binding affinity of 6:2 Cl-PFESA toward PPAR-γ was the highest among the ligands. 6:2 Cl-PFESA promoted the differentiation of 3T3-L1 cells by increasing PPAR-γ expression. Therefore, our results showed that 6:2 Cl-PFESA has the potential to induce liver damage and dysfunction in female mice, and this effect was achieved through PPAR-γ. This study is the first to reveal the hepatic toxicity of 6:2 Cl-PFESA in female mammals and provides new insights for subsequent in-depth research.

Polychlorinated biphenyls (PCBs) in the air are predominantly the less chlorinated congeners. Non-dioxin-like (NDL) low-chlorinated PCBs are more neurotoxic, and cause neurodevelopmental and neurobehavioral alterations in humans. However, the underlying mechanisms for this neurodevelopmental toxicity remain unknown. In the present study, Wistar rats were treated by gavage with PCB52 (1 mg/kg body weight) or corn oil from gestational day 7 to postnatal day 21. Both the body lengths and weights of the suckling rats at birth were significantly decreased by PCB52 treatment, suggesting developmental toxicity. Although no obvious histopathological changes were observed in the brain, using RNA-sequencing, 208 differentially expressed genes (DEGs) were identified in the striatum of PCB52-treated male offspring, while just 13 DEGs were identified in female offspring, suggesting sex-specific effects. Furthermore, using Gene Ontology enrichment analysis, neurodevelopmental processes, neurobehavioral alterations, and neurotransmission changes were enriched from the 208 DEGs in male offspring. Similarly, using Kyoto Encyclopedia of Genes and Genomes enrichment analysis, neuroactive ligand receptor interactions and multiple synapse pathways were enriched in male offspring, implying dysfunction of the neurotransmission system. Reductions in the protein expressions of these ligand receptors were also identified in the striatum, cerebral cortex, and hippocampus using western blotting methods. Taken together, our findings indicate that PCB52 exposure during gestation and lactation results in the abnormal expression of neurotransmission ligand-receptors in male offspring with a sex bias, and that this may contribute to neurodevelopmental toxicity.

Humic acid (HA) plays vital roles in regulating the environmental behaviors of metals and thus their toxicity to biota. However, the inner relation between metal bioavailability to soil organisms and the presence of HA with different molecular weight (Mw) is not well documented. In this study, we separated HAs into four fractions with Mw range of 5-30k Da, and discussed their ability to alleviating the toxicity of Cd and Pb to earthworm. The bioaccumulation capacities (Cₘₐₓ) increased in order of: UF1<UF2<UF3<UF4, which is in line with the variations of bioavailable concentrations of Cd and Pb in soil. Variations of Mw and binding capacities of HA determine the accumulation behavior in soil solution. The unsatisfactory of biotic ligand model fitting and the differences in fractions of the total biotic ligand sites (f) in earthworm bound by Cd and Pb suggested that only free species of Cd could be considered as biological available to earthworm, while the Pb–HAs complexes have potential ability to interact with earthworm membrane. Antioxidant enzymes are effective biomarkers, and HA with lower Mw play more important roles in restricting the toxicity of soil Cd and Pb to earthworm. These results reveal the different mechanism for HA controlling metal bioavailability between Cd and Pb in soil environment.

In this study, the YH consortium, an ethene-producing culture, was used to evaluate the effect of vitamin B₁₂ (VB₁₂) on trichloroethene (TCE) dechlorination by transferring the original TCE-reducing culture with or without adding exogenous VB₁₂. Ultra-high performance liquid chromatography - tandem mass spectrometry (UPLC-MS/MS) was applied to detect the concentrations of VB₁₂ and its lower ligand 5,6-dimethylbenzimidazole (DMB) in the cultures. After three successive VB₁₂ starvation cycles, the dechlorination of TCE stopped mostly at cis-dichloroethene (cDCE), and no ethene was found; methane production increased significantly, and no VB₁₂ was detected. Results suggest that the co-cultured microbes may not be able to provide enough VB₁₂ as a cofactor for the growth of Dehalococcoides in the YH culture, possibly due to the competition for corrinoids between Dehalococcoides and methanogens. The relative abundances of 16 S rRNA gene of Dehalococcoides and reductive dehalogenase genes tceA or vcrA were lower in the cultures without VB₁₂ compared with the cultures with VB₁₂. VB₁₂ limitation changed the microbial community structures of the consortia. In the absence of VB₁₂, the microbial community shifted from dominance of Chloroflexi to Proteobacteria after three consecutive VB₁₂ starvation cycles, and the dechlorinating genus Dehalococcoides declined from 42.9% to 13.5%. In addition, Geobacter, Clostridium, and Desulfovibrio were also present in the cultures without VB₁₂. Furthermore, the abundance of archaea increased under VB₁₂ limited conditions. Methanobacterium and Methanosarcina were the predominant archaea in the culture without VB₁₂.