Benzotriazole ultraviolet stabilizers (BUVSs) are prominent chemicals widely used in industrial and consumer products to protect against ultraviolet radiation. They are becoming contaminants of emerging concern since their residues are frequently detected in multiple environmental matrices and their toxicological implications are increasingly reported. We herein investigated the antiandrogenic activities of eight BUVSs prior to and after human CYP3A4-mediated metabolic activation/deactivation by the two-hybrid recombinant human androgen receptor yeast bioassay and the in vitro metabolism assay. More potent antiandrogenic activity was observed for the metabolized UV-328 in comparison with UV-328 at 0.25 μM ((40.73 ± 4.90)% vs. (17.12 ± 3.00)%), showing a significant metabolic activation. In contrast, the metabolized UV-P at 0.25 μM resulted in a decreased antiandrogenic activity rate from (16.08 ± 0.95)% to (6.91 ± 2.64)%, indicating a metabolic deactivation. Three mono-hydroxylated (OH) and three di-OH metabolites of UV-328 were identified by ultra-performance liquid chromatography quadrupole time of flight mass spectrometry (UPLC-Q-TOF-MS/MS), which were not reported previously. We further surmised that the hydroxylation of UV-328 occurs mainly at the alicyclic hydrocarbon atoms based on the in silico prediction of the lowest activation energies of hydrogen abstraction from C-H bond. Our results for the first time relate antiandrogenic activity to human CYP3A4 enzyme-mediated hydroxylated metabolites of BUVSs. The biotransformation through hydroxylation should be fully considered during the health risk assessment of structurally similar analogs of BUVSs and other emerging contaminants.

Benzotriazole UV stabilizers (BUVSs) are widely applied in plastics to prevent discoloration and to enhance product stability. This study describes for the first time the occurrence of nine different lipophilic BUVSs (UV-326, UV-320, UV-329, UV-350, UV-328, UV-327, UV-928, UV-234 and UV-360) in sediment, suspended particulate matter (SPM) and bream liver samples of German rivers. All investigated BUVSs were detected in sediments and SPM at concentrations in the low ng/g dry weight (dw) range. The so far rarely analyzed compound UV-360 as well as UV-326 were the predominant BUVSs in sediments and SPM from the river Rhine reaching maximum concentrations of 62 and 44 ng/g dw, respectively. Five BUVSs were also confirmed to bioaccumulate in bream liver, but neither UV-360 nor UV-326 was detected above the limit of quantification (LOQ). In contrast, highest concentrations in bream liver were determined for UV-327 (65 ng/g dw) and UV-328 (40 ng/g dw).A retrospective time trend analysis of BUVSs in SPM from two sites (river Rhine, 2005 to 2013; river Saar, 2006 to 2013) revealed increasing contamination levels of UV-329 and decreasing levels of UV-320 and UV-350. At one site (river Rhine) time trends of BUVS concentrations were also investigated in bream liver (1995–2013) and supported a considerably reduced exposure to UV-350.A first assessment of the environmental fate of BUVSs by sediment-water batch systems revealed a rapid partitioning into the sediment and no considerable degradation within 100 d.

High-arsenic wastewater derived from the metallurgical industry of nonferrous minerals is one of the most dangerous arsenic (As) sources that usually follow the emission of massive hazardous arsenic-bearing wastes. Considering the properties of red mud (RM), we propose an alternative and environmentally friendly method for the efficient remediation of high-arsenic wastewater using RM through formation of AlAsO₄@silicate precipitate, aiming at ''zero-emission of hazardous solid waste''. The results show nearly 100% of arsenic could be stepwisely removed from high-arsenic wastewater and reduce the arsenic concentration from 6100 mg/L to 40 μg/L using RM at room temperature. The highest arsenic removal capacity of RM reaches 101.5 mg/g at a RM-to-wastewater ratio of 40 g/L due to the superior arsenic adsorption and the co-precipitation of arsenate and Al³⁺ to form insoluble aluminum arsenate. The silicate shell of arsenic-loaded RM created at an alkaline condition acts as an arsenic stabilizer, resulting in a leached arsenic concentration of 1.2 mg/L in TCLP tests. RM acts as a highly effective arsenic remover and stabilizer for the disposal of high-arsenic wastewater. It shows great potential for the remediation of wastewater containing heavy metals with varying concentrations to produce clean water available for industrial purpose.

Antibiotics are commonly used in livestock and poultry breeding along with organic arsenic. Through long-term accumulation, they can enter into the surrounding soil through various pathways and contaminate the soil. In this paper, tetracycline antibiotics (TCs) and roxarsone (ROX) contaminated soil were used as the representatives of the two kinds of veterinary drugs contaminated soil, respectively, to study the thermal desorption behavior and arsenic stabilization process. Different parameters like heating temperatures, heat duration, stabilizer type and dosage were optimized for effective removal of TCs and ROX. Furthermore, TCs and ROX removal path and ROX stabilization mechanism were explored. Results of the study showed that over 98% of tetracycline antibiotics and roxarsone were effectively removed at 300 °C for 60 min. The heat treatment process of TCs contaminated soil was controlled by the first-order kinetics. Based on the detection of degradation products and thermogravimetric analysis, the possible thermal degradation path of TCs and ROX was proposed. Addition of FeSO₄.7H₂O (10% by weight) as stabilizer during the heat treatment process yielded 96.7% stabilization rate. Through the analysis of arsenic fractions, valence and the characterization of soil samples collected after the heat treatment, mechanism of arsenic stabilization in ROX was explored. The results show that thermal treatment combined with chemical stabilization technology can not only degrade TCs and ROX efficiently and completely, but also convert organic arsenic into inorganic state, which is conducive to better stabilization, and finally achieve effective and safe remediation of this kind of contaminated soil.

Benzotriazole ultraviolet stabilizers (BUVSs) are widely used additives in industrial materials and personal care products that protect products from ultraviolet damage. Due to their high production volume and potential to bioaccumulate, BUVSs are an environmental pollutant of concern. In this study, juvenile zebrafish (Danio rerio) were exposed to 4 BUVSs (UV-234, UV-326, UV-329, and UV-P) at 10 and 100 μg/L for 28 d. BUVSs induced hepatic vacuolization and nuclei pyknosis in the liver following 100 μg/L UV-234 and UV-329 exposure. Transcriptomic analysis in the liver uncovered pathways related to inflammation that were affected by BUVSs. Based upon these data, we measured the expression levels of 9 genes involved in AHR-IL17/IL22 pathway in zebrafish larvae exposed to each BUVSs at one dose of either 10 or 100 μg/L for 6 days in a second set experiment. Transcript levels of interleukins il17a and il22 were decreased, while il6 mRNA was increased with exposure to UV-234, UV-329, and UV-P. No change to targeted transcripts was observed with UV-326 treatments. Moreover, cyp1a1 and ahr2 levels were increased in larvae treated with 100 μg/L UV-329 or UV-P. Consistent with expression data, protein abundance of IL22 was decreased by 29% with exposure to 100 μg/L UV-P. Taken together, these results demonstrate that exposure to different benzotriazole congeners may be associated with immunotoxicity in zebrafish through the AHR-IL17/IL22 pathway, and this may be associated with hepatic damage with prolonged exposures. This study provides new insight into unique pathways perturbed by specific BUVSs congeners.

Solvent stabilizer 1,4-dioxane, an emerging recalcitrant groundwater contaminant, was commonly added to chlorinated solvents such as trichloroethene (TCE), and the impact of co-disposal on contaminant transport processes remains uncertain. A series of batch equilibrium experiments was conducted with variations of 1,4-dioxane and TCE composition to evaluate aqueous dissolution of the two components and their sorption to aquifer sediments. The solubility of TCE increased with increasing amounts of 1,4-dioxane, indicating that 1,4-dioxane acts as a cosolvent causing solubility enhancement of co-contaminants. The solubilization results compared favorably with predictions using the log-linear cosolvency model. Equilibrium sorption coefficients (Kd and Kf) were also measured for different 1,4-dioxane and TCE compositions, and the findings indicate that both contaminants adsorb to aquifer sediments and TCE Kd values increased with increasing organic matter content. However, the Kd for TCE decreased with increases in 1,4-dioxane concentration, which was attributed to cosolvency impacts on TCE solubility. These findings further advance our understanding of the mass-transfer processes controlling groundwater plumes containing 1,4-dioxane, and also have implications for the remediation of 1,4-dioxane contamination.

Organic UV stabilizers and UV filters are applied to industrial materials and cosmetics worldwide. In plastics they prevent photo-induced degradation, while in cosmetics they protect human skin against harmful effects of UV radiation. This study reports on the occurrence and distribution of organic UV stabilizers and UV filters in the surface sediment of the Chinese Bohai and Yellow Seas for the first time. In total, 16 out of 21 analyzed substances were positively detected. Concentrations ranged from sub-ng/g dw to low ng/g dw. The highest concentration of 25 ng/g dw was found for octocrylene (OC) in the Laizhou Bay. In the study area, characteristic composition profiles could be identified. In Korea Bay, the dominating substances were OC and ethylhexyl salicylate (EHS). All other analytes were below their method quantification limit (MQL). Around the Shandong Peninsula, highest concentrations of benzotriazole derivatives were observed in this study with octrizole (UV-329) as the predominant compound, reaching concentrations of 6.09 ng/g dw. The distribution pattern of UV-329 and bumetrizole (UV-326) were related (Pearson correlation coefficient r > 0.98, p « 0.01 around the Shandong Peninsula), indicating an identical input pathway and similar environmental behavior.

Understanding of the interaction of graphene with natural polysaccharides (e.g., alginate) is crucial to elucidate its environmental fate. We investigated the impact of alginate on the agglomeration and stability of ¹⁴C-labeled few-layer graphene (FLG) in varying concentrations of monovalent (NaCl) and divalent (CaCl₂) electrolytes. Enhanced agglomeration occurred at high CaCl₂ concentrations (≥5 mM) due to the alginate gel networks formation in the presence of Ca²⁺. FLG enmeshed within extended alginate gel networks was observed under transmission electron microscope and atomic force microscope. However, background Na⁺ competition for binding sites with Ca²⁺ at the alginate surfaces shielded the gelation of alginate. FLG was readily dispersed by alginate under environmentally relevant ionic strength conditions (i.e., <200 mM Na⁺ and <5 mM Ca²⁺). In comparison with the bare FLG, the slow sedimentation of the alginate-stabilized FLG (158 μg/L) caused continuous exposure of this nanomaterial to freshwater snails, which ingested 1.9 times more FLG through filter-feeding within 72 h. Moreover, surface modification of FLG by alginate significantly increased the whole-body and intestinal levels of FLG, but reduced the internalization of FLG to the intestinal epithelial cells. These findings indicate that alginate will act as a stabilizing agent controlling the transport of FLG in aqueous systems. This study also provides the first evidence that interaction of graphene with natural polysaccharides affected the uptake of FLG in the snails, which may alter the fate of FLG in aquatic environments.

Bauxite extraction by-products (red mud) were used to evaluate their potential ability to stabilize trace elements from dredged and aerated/humidified marine sediment. The investigated by-products were: bauxaline®(BX) that is a press-filtered red mud; bauxsol™(BS) that is a press-filtered red mud previously washed with excess of seawater, and gypsum neutralized bauxaline® (GBX). These materials were separately mixed to dredged composted sediment sample considering 5% and 20% sediment: stabilizer ratios. For pilot experiments, rainfall events were regularly simulated for 3 months. Concentrations of As, Mo, Cd, Cr, Zn, Cu, and Ni were analyzed in collected leachates as well as toxicity. Results showed that Cd, Mo, Zn, and Cu were efficiently stabilized in the solid matrix when 20% of BX, BS, and GBX was applied. Consequently, toxicity of leachates was lower than for the untreated sediment, meaning that contaminants mobility was reduced. A 5% GBX was also efficient for Mo, Zn and Cu stabilization. In all scenarios, As stabilization was not improved. Compared to all other monitored elements, Mo mobility seemed to depend upon temperature-humidity conditions during pilot experiments suggesting the need of further investigations.

Sun-blocking agents including eight UV filters (UVF) and 10 UV light stabilizers (UVLS) were measured in water and sediment collected from 22 rivers, four sewage treatment plant effluents (STPE) and three lakes in Japan. Total sun blocking agents levels ranged from N.D. to 4928ng/L and from 2.0 to 3422μg/kg dry wt in surface water and in sediment, respectively. Benzyl salicylate, benzophenone-3, 2-ethyl hexyl-4-methoxycinnamte (EHMC) and octyl salicylate were dominant in surface water receiving wastewater effluents and STPE, although UV-328, benzophenone and EHMC were dominant in other surface water except background sites. Three UVF and nine UVLS were observed from all sediment and their compositions showed similar patterns with UV-328 and UV-234 as the most prevalent compounds. Homosalate, octocrylene, UV-326, UV-327, UV-328 and UV-234 were significantly correlated with Galaxolide® in sediments. Concentrations of UV-327 and UV-328 also had strong correlation between those of UV-326 in sediment.