RESUMO
Heterogeneous crystallization is a common occurrence during the formation of solid wastes. It leads to the encapsulation of valuable/hazardous metals within the primary phase, presenting significant challenges for waste treatment and metal recovery. Herein, we proposed a novel method involving the in-situ formation of a competitive substrate during the precipitation of jarosite waste, which is an essential process for removing iron in zinc hydrometallurgy. We observed that the in-situ-formed competitive substrate effectively inhibits the heterogeneous crystallization of jarosite on the surface of anglesite, a lead-rich phase present in the jarosite waste. As a result, the iron content on the anglesite surface decreases from 34.8% to 1.65%. The competitive substrate was identified as schwertmannite, characterized by its loose structure and large surface area. Furthermore, we have elucidated a novel mechanism underlying this inhibition of heterogeneous crystallization, which involves the local supersaturation of jarosite caused by the release of ferric and sulfate ions from the competitive substrate. The local supersaturation promotes the preferential heterogeneous crystallization of jarosite on the competitive substrate. Interestingly, during the formation of jarosite, the competitive substrate gradually vanished through a dissolution-recrystallization process following the Ostwald rule, where a metastable phase slowly transitions to a stable phase. This effectively precluded the introduction of impurities and reduced waste volume. The goal of this study is to provide fresh insights into the mechanism of heterogeneous crystallization control, and to offer practical crystallization strategies conducive to metal separation and recovery from solid waste in industries.
Assuntos
Cristalização , Compostos Férricos , Compostos Férricos/química , Sulfatos/química , Compostos de Ferro/química , Ferro/química , Eliminação de Resíduos/métodosRESUMO
Secondary iron-sulfate minerals such as jarosite, which are easily formed in acid mine drainage, play an important role in controlling metal mobility. In this work, the typical iron-oxidizing bacterium Acidithiobacillus ferrooxidans ATCC 23270 was selected to synthesize jarosite in the presence of antimony ions, during which the solution behavior, synthetic product composition, and bacterial metabolism were studied. The results show that in the presence of Sb(V), Fe2+ was rapidly oxidized to Fe3+ by A. ferrooxidans and Sb(V) had no obvious effect on the biooxidation of Fe2+ under the current experimental conditions. The presence of Sb(III) inhibited bacterial growth and Fe2+ oxidation. For the group with Sb(III), products with amorphous phases were formed 72 hr later, which were mainly ferrous sulfate and pentavalent antimony oxide, and the amorphous precursor was finally transformed into a more stable crystal phase. For the group with Sb(V), the morphology and structure of jarosite were changed in comparison with those without Sb. The biomineralization process was accompanied by the removal of 94% Sb(V) to form jarosite containing the Fe-Sb-O complex. Comparative transcriptome analysis shows differential effects of Sb(III) and Sb(V) on bacterial metabolism. The expression levels of functional genes related to cell components were much more downregulated for the group with Sb(III) but much more regulated for that with Sb(V). Notably, cytochrome c and nitrogen fixation-relevant genes for the A.f_Fe2+_Sb(III) group were enhanced significantly, indicating their role in Sb(III) resistance. This study is of great value for the development of antimony pollution control and remediation technology.
Assuntos
Acidithiobacillus , Antimônio , Sulfatos , Acidithiobacillus/metabolismo , Acidithiobacillus/efeitos dos fármacos , Sulfatos/metabolismo , Compostos Férricos , Oxirredução , Mineração , Ferro/metabolismoRESUMO
The environmental threat posed by stibnite is an important geoenvironmental issue of current concern. To better understand stibnite oxidation pathways, aerobic abiotic batch experiments were conducted in aqueous solution with varying δ18OH2O value at initial neutral pH for different lengths of time (15-300 days). The sulfate oxygen and sulfur isotope compositions as well as concentrations of sulfur and antimony species were determined. The sulfur isotope fractionation factor (Δ34SSO4-stibnite) values decreased from 0.8 to -2.1 during the first 90 days, and increased to 2.6 at the 180 days, indicating the dominated intermediate sulfur species such as S2O32-, S0, and H2S (g) involved in Sb2S3 oxidation processes. The incorporation of O into sulfate derived from O2 (â¼100%) indicated that the dissociated O2 was only directly adsorbed on the stibnite-S sites in the initial stage (0-90 days). The proportion of O incorporation into sulfate from water (27%-52%) increased in the late stage (90-300 days), which suggested the oxidation mechanism changed to hydroxyl attack on stibnite-S sites promoted by nearby adsorbed O2 on stibnite-Sb sites. The exchange of oxygen between sulfite and water may also contributed to the increase of water derived O into SO42-. The new insight of stibnite oxidation pathway contributes to the understanding of sulfide oxidation mechanism and helps to interpret field data.
Assuntos
Oxirredução , Isótopos de Oxigênio , Sulfatos , Isótopos de Enxofre , Isótopos de Enxofre/análise , Sulfatos/química , Isótopos de Oxigênio/análise , Antimônio/química , Modelos Químicos , Aerobiose , Oxigênio/química , Poluentes Químicos da Água/análise , Poluentes Químicos da Água/química , ÓxidosRESUMO
As an important component of secondary aerosols, sulfate plays a crucial role in regulating atmospheric radiative balance and influencing the secondary formation of ozone (O3). In real atmosphere, atmospheric oxidants NO2 and O3 can promote the oxidation of SO2 to form sulfate (SO42-) through multiphase chemistry that occur at different time scales. Due to the combined impact of meteorology, pollution sources, atmospheric chemistry, etc., time-scale dependence of SO2-SO42- conversion makes the impact of NO2/O3 on it more complex. In this study, based on long-term time series (2013-2020) of air pollution variables from seven stations in Hong Kong, the Multifractal Detrended Cross-Correlation Analysis (MFDCCA) method has been employed to quantify the cross-correlations between SO2 and SO42- in real atmosphere at different time scales, for examining the time-scale dependence of SO2-SO42- conversion efficiency. Furthermore, the Pearson correlation analysis has been used to study the influence of NO2/O3 on SO2-SO42- conversion, and the regional and seasonal differences have been analyzed by considering factors such as meteorology, pollution sources, and regional transport. Changes in the main components of secondary aerosols are closely linked with the co-control of regional PM2.5 and O3. Therefore, the exploration of the impact of co-existing NO2/O3 gases on the secondary formation of sulfates in real atmosphere is significant.
Assuntos
Poluentes Atmosféricos , Atmosfera , Monitoramento Ambiental , Dióxido de Nitrogênio , Ozônio , Sulfatos , Ozônio/química , Sulfatos/química , Sulfatos/análise , Atmosfera/química , Poluentes Atmosféricos/análise , Dióxido de Nitrogênio/análise , Hong Kong , Aerossóis/análise , Poluição do Ar/estatística & dados numéricos , Dióxido de Enxofre/análise , Dióxido de Enxofre/químicaRESUMO
Persulfate (PS) is a widely used oxidant for the chemical oxidation of organic pollutants. The accurate measurement of PS concentration is crucial for the practical application process. The iodometry is the most recommended method for PS determination, and its principle is based on the redox reaction between S2O82- and iodide ions. However, hydrogen peroxide (H2O2), an important intermediate product in the process of PS use, often leads to abnormally high determination concentrations of PS. Given this, a novel method was developed for the determination of PS based on the principle of the oxidation of chloride ion (Cl-). The concentration of PS is calculated according to the consumption of Cl- concentration, which is not disturbed by H2O2. The optimized test conditions were explored as: C(H+) = 2 mol/L, T = 80â, C(Cl-):C(PS) = 4:1 and t = 30 min. Under the optimized conditions, the limit of detection and the limit of quantification of PS concentration determined by this method were 0.26 and 0.85 g/L, respectively. And the linear range of the PS determination was 1-100 g/L with an error of 0.53%-12.06%. The spike recovery rate for determining PS concentration in the actual wastewater ranged from 94.07%-109.52%. Interfering factors such as H2O2, Fe3+, MnO2 and natural organic matter had almost no effect on the results. This method could not only accurately determine the concentration of PS in industrial wastewater, but also determine the purity of PS industrial products.
Assuntos
Cloretos , Peróxido de Hidrogênio , Oxirredução , Sulfatos , Poluentes Químicos da Água , Sulfatos/análise , Sulfatos/química , Poluentes Químicos da Água/análise , Poluentes Químicos da Água/química , Cloretos/análise , Cloretos/química , Peróxido de Hidrogênio/química , Peróxido de Hidrogênio/análise , Águas Residuárias/químicaRESUMO
Sulphate-reducing microorganisms, or SRMs, are crucial to organic decomposition, the sulphur cycle, and the formation of pyrite. Despite their low energy-yielding metabolism and intense competition with other microorganisms, their ability to thrive in natural habitats often lacking sufficient substrates remains an enigma. This study delves into how Desulfovibrio desulfuricans G20, a representative SRM, utilizes photoelectrons from extracellular sphalerite (ZnS), a semiconducting mineral that often coexists with SRMs, for its metabolism and energy production. Batch experiments with sphalerite reveal that the initial rate and extent of sulphate reduction by G20 increased by 3.6 and 3.2 times respectively under light conditions compared to darkness, when lactate was not added. Analyses of microbial photoelectrochemical, transcriptomic, and metabolomic data suggest that in the absence of lactate, G20 extracts photoelectrons from extracellular sphalerite through cytochromes, nanowires, and electron shuttles. Genes encoding movement and biofilm formation are upregulated, suggesting that G20 might sense redox potential gradients and migrate towards sphalerite to acquire photoelectrons. This process enhances the intracellular electron transfer activity, sulphur metabolism, and ATP production of G20, which becomes dominant under conditions of carbon starvation and extends cell viability in such environments. This mechanism could be a vital strategy for SRMs to survive in energy-limited environments and contribute to sulphur cycling.
Assuntos
Desulfovibrio desulfuricans , Oxirredução , Sulfatos , Sulfetos , Sulfatos/metabolismo , Sulfetos/metabolismo , Desulfovibrio desulfuricans/metabolismo , Desulfovibrio desulfuricans/genética , Biofilmes/crescimento & desenvolvimento , Elétrons , Enxofre/metabolismo , Transporte de Elétrons , Compostos de ZincoRESUMO
Nanomaterials, with their small size, surface characteristics, and antibacterial properties, are extensively employed across environmental, energy, biomedical, agricultural, and other industries. This study examined the antibacterial efficacy of magnesium hydroxide (Mg(OH)2) nanoparticles (NPs) against sulfate-reducing bacteria (SRB) within sediments. The inhibitory effects of two types of Mg(OH)2 NPs with distinct particle sizes (20.3 and 29.6 nm) and concentrations (0-10.0 mg/mL) were examined under optimal treatment conditions. The antibacterial mechanisms of Mg(OH)2 NPs through direct contact and dissolution effects were determined. The results revealed a correlation between the concentration, particle size, and inhibitory activity, with the smallest NPs (20.3 nm) at the highest concentration (10.0 mg/mL) substantially reducing SRB counts from 8.77 ± 0.18 to 6.48 ± 0.13 log10 colony forming units/mL after 6 h treatment. Treatment with high concentrations of Mg(OH)2 NPs induced cellular damage, reduced intracellular lactate dehydrogenase activity, and elevated intracellular catalase activity and H2O2 content, suggesting that the contact effect of NPs stimulated SRB. This leads to oxidative stress response and structural damage to the cell membrane, which has emerged as the primary driver of the antibacterial action of Mg(OH)2 NPs. This study presents a novel nanomaterial that can inhibit and control SRB in natural sedimentary environments.
Assuntos
Antibacterianos , Sedimentos Geológicos , Hidróxido de Magnésio , Sulfatos , Hidróxido de Magnésio/química , Hidróxido de Magnésio/farmacologia , Antibacterianos/farmacologia , Antibacterianos/química , Sedimentos Geológicos/microbiologia , Sulfatos/química , Sulfatos/farmacologia , Nanopartículas/química , Peróxido de Hidrogênio/farmacologia , Tamanho da Partícula , Bactérias/efeitos dos fármacos , Nanopartículas Metálicas/química , Testes de Sensibilidade MicrobianaRESUMO
This study presents novel composites of biochar (BC) derived from spinach stalks and zinc oxide (ZnO) synthesized from water hyacinth to be used for the first time in a hybrid system for activating persulfate (PS) with photocatalysis for the degradation of bromothymol blue (BTB) dye. The BC/ZnO composites were characterized using innovative techniques. BC/ZnO (2:1) showed the highest photocatalytic performance and BC/ZnO (2:1)@(PS + light) system attained BTB degradation efficiency of 89.47% within 120 min. The optimum operating parameters were determined as an initial BTB concentration of 17.1 mg/L, a catalyst dosage of 0.7 g/L, and a persulfate initial concentration of 8.878 mM, achieving a BTB removal efficiency of 99.34%. The catalyst showed excellent stability over five consecutive runs. Sulfate radicals were the predominant radicals involved in the degradation of BTB. BC/ZnO (2:1)@(PS + light) system could degrade 88.52%, 84.64%, 81.5%, and 77.53% of methylene blue, methyl red, methyl orange, and Congo red, respectively. Further, the BC/ZnO (2:1)@(PS + light) system effectively activated PS to eliminate 97.49% of BTB and 85.12% of dissolved organic carbon in real industrial effluents from the textile industry. The proposed degradation system has the potential to efficiently purify industrial effluents which facilitates the large-scale application of this technique.
Assuntos
Carvão Vegetal , Corantes , Poluentes Químicos da Água , Óxido de Zinco , Óxido de Zinco/química , Carvão Vegetal/química , Catálise , Corantes/química , Poluentes Químicos da Água/química , Sulfatos/química , Fotólise , Spinacia oleracea , Compostos Azo/química , Alimentos , Química Verde/métodos , Perda e Desperdício de AlimentosRESUMO
This study explored Mason pine-derived hydrochar (MPHC) as an effective adsorbent and persulfate (PS) activator for degrading bisphenol A (BPA). Increasing MPHC dosage from 0.25 to 2.0 g L-1 raised BPA removal from 42% to 87%. Similarly, at the same MPHC dosage range and fixed PS concentration (8 mM), BPA removal by MPHC/PS increased from 66% to 91%. Additionally, at a fixed MPHC dosage (1.0 g L-1), higher PS concentrations (2-32 mM) resulted in an overall BPA removal increase from 78% to 99%. The optimal pH for BPA removal by MPHC was at pH 3, while for MPHC/PS was at pH 9. BPA degradation by MPHC was optimal at pH 3, whereas MPHC/PS was at pH 3 and pH 9. Additionally, pH 7 favored BPA adsorption for both MPHC and MPHC/PS. The study also considered the influence of coexisting anions and humic acid (HA). PO43- and NO3- influence adsorption on MPHC, but these anions' effect on MPHC/PS is limited. Furthermore, the existence of HA had minimal influence on BPA removal by MPHC/PS. The contributions of different reactive species by MPHC for BPA degradation are as follows: electron-hole (h+) 2%, singlet oxygen (1O2) 7%, superoxide radicals (O2â¢-) 13%, electron (e-) 2%, hydroxyl radical (â¢OH) 3%, whereas the remaining 48% removal was the contribution of adsorption. For MPHC/PS, adsorption accounted for 39 %, more reactive species were involved in degradation, and the donations are (h+) 3%, sulfate radicals (SO4â¢-) 3%, (1O2) 19%, (O2â¢-) 15%, (e-) 2%, and (â¢OH) 2%. Additionally, the performance of MPHC remains stable after three operational cycles. The preparation cost of MPHC is 3.01 kg-1. These results highlight the potential of MPHC as an environmentally friendly material for activating PS and removing organic pollutants, suggesting its promising application in future environmental remediation efforts.
Assuntos
Compostos Benzidrílicos , Fenóis , Sulfatos , Poluentes Químicos da Água , Compostos Benzidrílicos/química , Fenóis/química , Poluentes Químicos da Água/química , Sulfatos/química , Adsorção , Concentração de Íons de Hidrogênio , Substâncias Húmicas , Recuperação e Remediação Ambiental/métodos , Purificação da Água/métodosRESUMO
Herein, a novel graphite/sulfur iron tailing composite was applied as a peroxydisulfate (PDS) activator for rhodamine B (RhB) degradation in the water. The superior catalytic efficiency of graphite/sulfur iron tailing was achieved through radical (SO4â¢- and â¢OH) and non-radical (1O2) processes according to the radical quenching experiments and electron paramagnetic resonance analysis. The carbonyl group and Fe species were the main active sites on the surface of graphite/sulfur iron tailing, which was demonstrated by combining Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), and reaction kinetic experiments, and a possible degradation mechanism was also proposed. Overall, activated with 0.30 g/L of C-1, PDS achieved a 94.8% removal rate for RhB and maintained a removal rate of over 85% even after five consecutive operation cycles, and this study will benefit the application of iron/carbon composite materials in practical water treatment.
Assuntos
Grafite , Ferro , Rodaminas , Poluentes Químicos da Água , Rodaminas/química , Grafite/química , Ferro/química , Catálise , Poluentes Químicos da Água/química , Purificação da Água/métodos , Enxofre/química , Cinética , Espectroscopia de Infravermelho com Transformada de Fourier , Sulfatos/químicaRESUMO
The dramatical increase of sulfur concentration in eutrophic lakes, especially sulfate (SO42-), has brought attention to the impact on the lake ecosystem; however, the mechanisms driving the intensification of eutrophication and the role of SO42- concentrations remain poorly understood. To assess the impact of eutrophication on SO42- dynamics in lakes, this study monitored SO42- concentrations in water and sediments across seven lakes with varying trophic statuses on a spatial scale, and in the eutrophic Lake Taihu over one year on a temporal scale, as well as a series of microcosms with different initial SO42- concentrations. Exogenous sulfur input is the primary driver of increased SO42- concentrations in lakes, the highest SO42- concentration in overlying water was 100 mg/L, as well as which reached 310.9 mg/L in sediment. The concurrent input of nutrients such as nitrogen and phosphorus exacerbated eutrophication, resulting in the destabilization of the sulfur cycle. Eutrophication promoted the SO42- concentration on the spatio-temporal scale, especially in sediment, and trophic lake index (TLI) showed a positive correlation with the SO42- in sediments (R2 = 0.99; 0.88). The SO42- concentration in water and TLI showed a nonlinear correlation on the temporal scale (R2 = 0.44), and showed a positive correlation on the spatial scale (R2 = 0.49). Microscopic experiments demonstrate that the anaerobic environment created by cyanobacteria decomposition induced sulfate reduction and significantly reduces SO42- concentrations. Concurrently, the anaerobic environment facilitates the coupling of iron reduction with sulfate reduction, leading to a substantial increase in Acid Volatile Sulfides (AVS) in the sediment. These findings reveal that eutrophication has a dual effect on the dynamic change of SO42- concentrations in overlying water, which is helpful to accurately evaluate and predict the change of SO42- concentrations in lakes.
Assuntos
Monitoramento Ambiental , Eutrofização , Lagos , Sulfatos , Poluentes Químicos da Água , Lagos/química , Poluentes Químicos da Água/análise , Sulfatos/análise , China , Fósforo/análise , Sedimentos Geológicos/químicaRESUMO
Acetochlor residues can contaminate anoxic habitats where anaerobic microbial transformation dominates. Herein, a highly efficient anaerobic acetochlor-degrading consortium ACT6 was enriched using sulfate and acetochlor as selection pressures. The acclimated consortium ACT6 showed an 8.7-fold increase in its ability to degrade acetochlor compared with the initial consortium ACT1. Two degradation pathways of acetochlor were found: reductive dechlorination and thiol-substitution dechlorination in the chloroacetyl group, in which the latter dominated. Acclimation enhanced the abundances of Desulfovibrio, Proteiniclasticum, and Lacrimispora from 0.7 to 28.0% (40-fold), 4.7 to 18.1% (4-fold), and 2.3 to 12.3% (5-fold), respectively, which were positively correlated with sulfate concentrations and acetochlor degradation ability. Three acetochlor-degrading anaerobes were isolated from the acclimated consortium ACT6, namely Cupidesulfovibrio sp. SRB-5, Proteiniclasticum sp. BAD-10, and Lacrimispora sp. BAD-7. This study provides new insights into the anaerobic catabolism of acetochlor and the anaerobic treatment of acetochlor in wastewater.
Assuntos
Biodegradação Ambiental , Herbicidas , Sulfatos , Toluidinas , Herbicidas/metabolismo , Herbicidas/química , Toluidinas/metabolismo , Toluidinas/química , Anaerobiose , Sulfatos/metabolismo , Sulfatos/química , Consórcios Microbianos , Halogenação , Bactérias/metabolismo , Bactérias/genética , Bactérias/classificação , Bactérias/isolamento & purificaçãoRESUMO
Elevated sulfate levels in eutrophic lakes have been observed to induce the release of endogenous phosphorus. While previous studies have predominantly examined its impact on iron-bound phosphorus (FeP), the influence on organic phosphorus (OP), a crucial active phosphorus component in sediments, remains poorly understood. In this study, mesocosms were established with lactate supplementation and varying sulfate concentrations to explore sulfate reduction and its impacts on phosphorus mobilization in freshwater sediments. Lactate addition induced hypoxia and provided substrates, thereby stimulating sulfate reduction with a decline of sulfate levels, an increase of sulfide concentrations, and fluctuations of sulfate-reducing bacteria. Meanwhile, concentrations of total dissolved phosphorus and phosphate were dramatically promoted during lactate decomposition, with a higher sulfate concentration associated with greater phosphorus elevation, correlating with the decrease of total phosphorus in sediment. The increase in phosphorus of the overlying water was partly attributed to FeP release from the sediment, confirmed by a decrease in its sediment content. FeP release was ascribed to dissimilatory reduction of iron oxides or chemical reduction mediated by sulfides in anoxic sediments, leading to the desorption and subsequent release of phosphorus. Evidences included the proliferation of iron-reducing bacteria, a decrease in Fe(II) concentrations in sediment pore- water, and the continuous accumulation of solid iron sulfides in surface sediments. Furthermore, OP mineralization in sediment also contributed to the increase in phosphorus in water columns, confirmed by a reduction in its content and the abundance of fermentation bacteria in surface sediment. Notably, the decrease in OP content accounted for >80 % of the total phosphorus reduction in surface sediment in the end. Thus, sulfur cycling plays a critical role in iron and phosphorus cycling, significantly stimulating not only the mobilization of FeP but also OP in sediments, with OP mineralization potentially being the primary contributor to endogenous phosphorus release.
Assuntos
Eutrofização , Sedimentos Geológicos , Lagos , Fósforo , Sulfatos , Poluentes Químicos da Água , Fósforo/análise , Lagos/química , Sedimentos Geológicos/química , Sulfatos/análise , Poluentes Químicos da Água/análise , Monitoramento Ambiental , FerroRESUMO
The release of synthetic dyes into water bodies poses many environmental issues, and their removal is a necessity. Advanced oxidation processes (AOPs) can be employed for removal, in many of which a catalyst is used. graphene oxide (GO) is a viable catalyst due to its distinctive structural properties; however, it is reportedly incapable of effectively activating persulfate. Thus, this study delves for the first time into the influence of doping silica on enhancing GO's catalytic performance to activate persulfate for decolorizing Acid Blue 25 (AB25). Based on the results, an equal weight proportion of GO to silica was selected as the most efficient ratio. In addition, pH had no significant effect on removal efficiency, while temperature had the highest impact. Within 150 min with 0.075 gr/L of GO-SiO2 as the catalyst and 1 gr/L of Na2S2O8 as the oxidant, the investigated process removed Acid Blue 25 up to 82%, which was 9% higher than when GO alone was used as the catalyst. As for COD removal, the contribution of doping silica was more significant and led to 37% COD removal, which was 17% higher than when GO alone was used.
Assuntos
Grafite , Dióxido de Silício , Grafite/química , Dióxido de Silício/química , Catálise , Poluentes Químicos da Água/química , Oxirredução , Sulfatos/química , Corantes/químicaRESUMO
Myricetin (MYR) and ampelopsin (AMP, or dihydromyricetin) are flavonoid aglycones found in certain plants and dietary supplements. During the presystemic biotransformation of flavonoids, mainly sulfate and glucuronide derivatives are produced, which are the dominant metabolites in the circulation. In this study, we tested the interactions of MYR, myricetin-3'-O-sulfate (M3'S), AMP, and ampelopsin-4'-O-sulfate (A4'S) with human serum albumin (HSA), cytochrome P450 enzymes (CYPs), and organic anion-transporting polypeptides (OATPs) using in vitro models, including the recently developed method for measuring flavonoid levels in living cells. M3'S and MYR bound to albumin with high affinity, and they showed moderate displacing effects versus the Site I marker warfarin. MYR, M3'S, AMP, and A4'S exerted no or only minor inhibitory effects on CYP2C9, CYP2C19, and CYP3A4 enzymes. M3'S and MYR caused considerable inhibitory actions on OATP1B1 at low micromolar concentrations (IC50 = 1.7 and 6.4 µM, respectively), while even their nanomolar levels resulted in strong inhibitory effects on OATP2B1 (IC50 = 0.3 and 0.4 µM, respectively). In addition, M3'S proved to be a substrate of OATP1B1 and OATP2B1. These results suggest that MYR-containing dietary supplements may affect the OATP-mediated transport of certain drugs, and OATPs are involved in the tissue uptake of M3'S.
Assuntos
Flavonoides , Transportador 1 de Ânion Orgânico Específico do Fígado , Transportadores de Ânions Orgânicos , Humanos , Flavonoides/farmacologia , Transportadores de Ânions Orgânicos/metabolismo , Transportador 1 de Ânion Orgânico Específico do Fígado/metabolismo , Citocromo P-450 CYP3A/metabolismo , Flavonóis/farmacologia , Sulfatos/metabolismo , Albumina Sérica/metabolismo , Citocromo P-450 CYP2C9/metabolismo , Sistema Enzimático do Citocromo P-450/metabolismoRESUMO
The increased difference in the sulfur isotopic compositions of sedimentary sulfate (carbonate-associated sulfate: CAS) and sulfide (chromium-reducible sulfur: CRS) during the Ediacaran Shuram excursion is attributed to increased oceanic sulfate concentration in association with the oxidation of the global ocean and atmosphere. However, recent studies on the isotopic composition of pyrites have revealed that CRS in sediments has diverse origins of pyrites. These pyrites are formed either in the water column/shallow sediments, where the system is open with respect to sulfate, or in deep sediments, where the system is closed with respect to sulfate. The δ34S value of sulfate in the open system is equal to that of seawater; on the contrary, the δ34S value of sulfate in the closed system is higher than that of seawater. Therefore, obtaining the isotopic composition of pyrites formed in an open system, which most likely retain microbial sulfur isotope fractionation, is essential to reconstruct the paleo-oceanic sulfur cycle. In this study, we carried out multiple sulfur isotope analyses of CRS and mechanically separated pyrite grains (>100 µm) using a fluorination method, in addition to secondary ion mass spectrometry (SIMS) analyses of in situ δ34S values of pyrite grains in drill core samples of Member 3 of the Ediacaran Doushantuo Formation in the Three Gorges area, South China. The isotope fractionation of microbial sulfate reduction (MSR) in the limestone layers of the upper part of Member 3 was calculated to be 34ε = 55.7 and 33λ = 0.5129 from the δ34S and Δ33S' values of medium-sized pyrite grains ranging from 100 to 300 µm and the average δ34S and Δ33S' values of CAS. Model calculations revealed that the influence of sulfur disproportionation on the δ34S values of these medium-sized pyrite grains was insignificant. In contrast, within the dolostone layers of the middle part of Member 3, isotope fractionation was determined to be 34ε = 47.5. The 34ε value in the middle part of Member 3 was calculated from the average δ34S values of the rim of medium-sized pyrite grains and the average δ34S values of CAS. This observation revealed an increase in microbial sulfur isotope fractionation during the Shuram excursion at the drill core site. Furthermore, our investigation revealed correlations between δ34SCRS values and CRS concentrations and between CRS and TOC concentrations, implying that organic matter load to sediments controlled the δ34SCRS values rather than oceanic sulfate concentrations. However, these CRS and TOC concentrations are local parameters that can change only at the kilometer scale with local redox conditions and the intensity of primary production. Therefore, the decreasing δ34SCRS values likely resulted from local redox conditions and not from a global increase in the oceanic sulfate concentration.
Assuntos
Sedimentos Geológicos , Isótopos de Enxofre , Enxofre , Sedimentos Geológicos/química , Sedimentos Geológicos/microbiologia , China , Isótopos de Enxofre/análise , Enxofre/análise , Enxofre/metabolismo , Água do Mar/química , Água do Mar/microbiologia , Sulfetos/análise , Sulfetos/metabolismo , Sulfatos/análise , Sulfatos/metabolismo , Oceanos e Mares , FerroRESUMO
This paper presents findings on groundwater physiochemical composition and radioactivity levels in households in Bac Lieu province, Vietnam. Through discriminant analysis, it was observed that groundwater quality exhibits spatial variations corresponding to saline intrusion zones. The paired-samples T-tests revealed significantly different ratios of Ra-224, Ra-226, and Ra-228 isotopes between Na-Cl and Ca-Na-HCO3 water types. All three water types had a ratio of Ra-226/Ra-228 of approximately one, indicating the presence of groundwater aquifers beneath the crust and fluvial marine sediment. Furthermore, strong associations between sulfate and calcium suggest that CO2 enrichment in groundwater aquifers indicates anoxic aquatic environments. Twenty-five of the thirty-three evaluated samples exceeded the national technical regulations for domestic water quality with parameters such as chloride, sulfate, sodium, gross alpha, or total dissolved solids. Fifteen samples exceeded gross alpha's allowable contamination threshold of 0.1 Bq/L. The combination of Ra-226 and Ra-228 did not surpass the U.S. Environmental Protection Agency's recommended limit of 0.185 Bq/L. However, nineteen samples exhibited annual committed effective doses of radium isotopes for infants that exceeded the WHO recommendation of 0.1 mSv/year.
Assuntos
Água Subterrânea , Rádio (Elemento) , Poluentes Radioativos da Água , Vietnã , Água Subterrânea/química , Poluentes Radioativos da Água/análise , Humanos , Rádio (Elemento)/análise , Monitoramento de Radiação/métodos , Características da Família , Sulfatos/análiseRESUMO
Soil contamination with heavy metals from industrial and mining activities poses significant environmental and public health risks, necessitating effective remediation strategies. This review examines the utilization of sulfate-reducing bacteria (SRB) for bioremediation of heavy metal-contaminated soils. Specifically, it focuses on SRB metabolic pathways for heavy metal immobilization, interactions with other microorganisms, and integration with complementary remediation techniques such as soil amendments and phytoremediation. We explore the mechanisms of SRB action, their synergistic relationships within soil ecosystems, and the effectiveness of combined remediation approaches. Our findings indicate that SRB can effectively immobilize heavy metals by converting sulfate to sulfide, forming stable metal sulfides, thereby reducing the bioavailability and toxicity of heavy metals. Nevertheless, challenges persist, including the need to optimize environmental conditions for SRB activity, address their sensitivity to acidic conditions and high heavy metal concentrations, and mitigate the risk of secondary pollution from excessive carbon sources. This study underscores the necessity for innovative and sustainable SRB-based bioremediation strategies that integrate multiple techniques to address the complex issue of heavy metal soil contamination. Such advancements are crucial for promoting green mining practices and environmental restoration.
Assuntos
Biodegradação Ambiental , Metais Pesados , Microbiologia do Solo , Poluentes do Solo , Sulfatos , Metais Pesados/metabolismo , Poluentes do Solo/metabolismo , Sulfatos/metabolismo , Bactérias Redutoras de Enxofre/metabolismo , Bactérias/metabolismo , Mineração , Solo/químicaRESUMO
Glycosaminoglycans (GAGs) are negatively charged polysaccharides found on cell surfaces, where they regulate transport pathways of foreign molecules toward the cell. The structural and functional diversity of GAGs is largely attributed to varied sulfation patterns along the polymer chains, which makes understanding their molecular recognition mechanisms crucial. Molecular dynamics (MD) simulations, thanks to their unmatched microscopic resolution, have the potential to be a reference tool for exploring the patterns responsible for biologically relevant interactions. However, the capability of molecular dynamics force fields used in biosimulations to accurately capture sulfation-specific interactions is not well established, partly due to the intrinsic properties of GAGs that pose challenges for most experimental techniques. In this work, we evaluate the performance of molecular dynamics force fields for sulfated GAGs by studying ion pairing of Ca2+ to sulfated moietiesâN-methylsulfamate and methylsulfateâthat resemble N- and O-sulfation found in GAGs, respectively. We tested available nonpolarizable (CHARMM36 and GLYCAM06) and explicitly polarizable (Drude and AMOEBA) force fields, and derived new implicitly polarizable models through charge scaling (prosECCo75 and GLYCAM-ECC75) that are consistent with our developed "charge-scaling" framework. The calcium-sulfamate/sulfate interaction free energy profiles obtained with the tested force fields were compared against reference ab initio molecular dynamics (AIMD) simulations, which serve as a robust alternative to experiments. AIMD simulations indicate that the preferential Ca2+ binding mode to sulfated GAG groups is solvent-shared pairing. Only our scaled-charge models agree satisfactorily with the AIMD data, while all other force fields exhibit poorer agreement, sometimes even qualitatively. Surprisingly, even explicitly polarizable force fields display a notable disagreement with the AIMD data, likely attributed to difficulties in their optimization and possible inherent limitations in depicting high-charge-density ion interactions accurately. Finally, the underperforming force fields lead to unrealistic aggregation of sulfated saccharides, which qualitatively disagrees with our understanding of the soft glycocalyx environment. Our results highlight the importance of accurately treating electronic polarization in MD simulations of sulfated GAGs and caution against over-reliance on currently available models without thorough validation and optimization.
Assuntos
Glicosaminoglicanos , Simulação de Dinâmica Molecular , Eletricidade Estática , Sulfatos , Glicosaminoglicanos/química , Sulfatos/química , Ácidos Sulfônicos/química , Benchmarking , Cálcio/químicaRESUMO
Sodium diclofenac (DCF) widely exists in actual water matrices, which can negatively impact ecosystems and aquatic environments even at low-strength. Herein, the adsorption-concentration-mineralization process was innovatively constructed for low-strength DCF elimination by freeze-dried biocarbon and oven-dried biocarbon coupled with cobalt oxide composites derived from the same waste biomass. Surprisingly, low-strength DCF of 0.5 mg/L was adsorbed rapidly and enriched to high-strength DCF under light with a concentration efficiency of 99.67 % by freeze-dried biocarbon. Subsequently, the concentrated DCF was economically mineralized by bifunctional oven-dried biocarbon coupled with cobalt oxide composites for peroxydisulfate (PDS) activation with full PDS activation and 76.11 % mineralization efficiency. Compared with direct low-strength DCF oxidation, adsorption-concentration-mineralization consumed less energy and none PDS residues. Mechanisms confirmed that DCF was adsorbed by freeze-dried biocarbon through hydrogen bonds and π-π stacking interactions, which were switched on due to electron-induced effect by light in DCF desorption-concentration. Furthermore, nonradical pathway (electron transfer) and radical pathway (SO4â¢-) were involved in efficient PDS activation by oven-dried biocarbon coupled with cobalt oxide composites for concentrated DCF mineralization, and the former was more prominent, in which graphitic carbon, cobalt redox cycle and carboxy groups were the main active sites. Overall, an energy-efficient strategy was proposed for elimination of low-strength DCF in real water matrices.