RESUMO
Sea level rise (SLR) is estimated to impact 25% of the world's population along coastal areas leading to an increase in saltwater intrusion. Consequently, changes in the soil biogeochemistry of currently non-saline and/or well-drained soils due to saltwater intrusion are of major concern. Saltwater intrusion is expected to affect farmland across large broiler producer regions, where large amounts of manure containing organic arsenicals were applied over the past decades. To determine how SLR may impact the speciation and mobility of adsorbed inorganic and organic As, we used in situ real-time attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR) to determine the adsorption and desorption mechanisms of As(V) and 4-aminophenylarsonic (p-ASA, a poultry feed additive) on ferrihydrite (Fh) in the presence of sulfate at varying pH. The adsorption of As(V) and p-ASA increased at lower pH, with As(V) showing IR features consistent with the formation of inner-sphere of As-Fh surface complexes, while p-ASA also formed others structures as H-bonded As-surface complexes, likely mediated by outer-sphere complexes, based on our FTIR and batch experiments data. No observable As(V) or p-ASA desorption from the Fh surface was promoted by sulfate, however sulfate adsorption on the Fh surface was remarkably larger for p-ASA than for As(V). Complimentary, we carried out batch studies of As(V) and p-ASA desorption by Fh, using artificial seawater (ASW) at varying concentrations. The 1% ASW desorbed â¼10% of initially sorbed p-ASA, while at 100% ASW desorbed â¼40%. However, <1% of As(V) was desorbed by 1% ASW solution and only â¼7.9% were desorbed at 100% ASW. The spectroscopic data support the more extensive desorption of p-ASA compared to As(V) observed in batch experiments, suggesting that organoarsenicals may be easily desorbed and, after conversion to inorganic forms, pose a risk to water supplies.
Assuntos
Ácido Arsanílico , Arseniatos , Animais , Ácido Arsanílico/química , Adsorção , Sulfatos , Elevação do Nível do Mar , Galinhas , Compostos Férricos/química , Solo/química , Espectroscopia de Infravermelho com Transformada de Fourier , Óxidos de Enxofre , Concentração de Íons de HidrogênioRESUMO
Xichú River is a Mexican river located in an environmental preservation area called Sierra Gorda Biosphere Reserve. Around it, there are tons of abandoned mine residues that represent a serious environmental issue. Sediment samples of Xichú River, visibly contaminated by flows of an acid mine drainage, were collected to study their prokaryotic diversity. The study was based on both cultural and non-cultural approaches. The analysis of total 16S rRNA gene by MiSEQ sequencing allowed to identify 182 Operational Taxonomic Units. The community was dominated by Pseudomonadota, Bacteroidota, "Desulfobacterota" and Acidobacteriota (27, 21, 19 and 16%, respectively). Different culture conditions were used focusing on the isolation of anaerobic bacteria, including sulfate-reducing bacteria (SRB) and arsenate-reducing bacteria (ARB). Finally, 16 strains were isolated. Among them, 12 were phylogenetically identified, with two strains being SRB, belonging to the genus Solidesulfovibrio ("Desulfobacterota"), while ten are ARB belonging to the genera Azospira (Pseudomonadota), Peribacillus (Bacillota), Raineyella and Propionicimonas (Actinomycetota). The isolate representative of Raineyella genus probably corresponds to a new species, which, besides arsenate, also reduces nitrate, nitrite, and fumarate.
Assuntos
Arseniatos , Desulfovibrio , RNA Ribossômico 16S/genética , Rios/microbiologia , México , Antagonistas de Receptores de Angiotensina , Inibidores da Enzima Conversora de Angiotensina , Bactérias/genética , ÁcidosRESUMO
Arsenic-hyperaccumulator Pteris vittata is efficient in taking up arsenate (AsV) and arsenite (AsIII), however, their impacts on P. vittata growth and nutrient uptake remain unclear. The uptake of AsV and AsIII, their influences on nutrient uptake and plant biomass, and As speciation were investigated in P. vittata after exposing to 5 or 50 µM AsV or AsIII for 12 d under hydroponics. The results show that AsV uptake in P. vittata was 1.2 times more efficient than AsIII, corresponding to 1.7-2.1 fold greater biomass than the control at 50 µM As. While AsV was dominant in the roots at â¼60%, AsIII was more dominant in the fronds at â¼70% in all treatments. Macronutrients P, K, Ca, and S were increased by 118-185% at 50 µM As, with greater uptake of micronutrients Fe, Mn, Cu, and Zn at 5 µM As. Further, positive correlations between P. vittata biomass and its As contents (r = 0.97), and P. vittata biomass and its S, Mg, P, or Ca contents (r = 0.70-0.98) were observed. Our results suggest that its increased nutrient uptake probably enhanced P. vittata growth under As exposure.
Assuntos
Arsênio , Arsenitos , Pteris , Poluentes do Solo , Arsênio/análise , Arseniatos , Poluentes do Solo/análise , Raízes de Plantas/química , Nutrientes , Biodegradação AmbientalRESUMO
Microbially driven Fe(II) oxidation is vital for Fe-cycling processes. In the present study, a novel strain of nitrate-dependent Fe-oxidizing bacteria (FOB) was isolated from the riparian zone sediment of the Hanjiang River, China. It was identified as Comamonas terrigena strain HJ-2. The strain HJ-2 oxidized 2.80 mmol l-1 Fe(II) within 144 h to form Fe(III)/Fe(II) complex on the cell surface using 1.63 mmol l-1 nitrate as an electron acceptor. The formed nitrite from nitrate reduction chemically oxidized Fe(II). Surprisingly, this strain also reduced nitrilotriacetic iron to form 0.5 mmol l-1 Fe(II) in 120 h in anaerobic conditions primarily mediated by the NADH flavin oxidoreductase. Besides, the strain completely reduced 0.18 mmol l-1 nitrobenzene to aniline in 24 days and 15.6 µmol l-1 arsenate to arsenite in 7 days due to the existence of nitro and arsenate reductases. However, the Fe(II) inhibited the reduction of nitrate, nitrobenzene, and arsenate, possibly due to the impeding of transport of the solutes through the membrane or the synthesis of the related enzymes. These results provide new knowledge about the Fe(II)-cycling and the fate of some pollutants in the riparian zone. It also informed that some bacteria have universal functions on elements and contaminants transformation.
Assuntos
Comamonas , Nitratos , Nitratos/metabolismo , Arseniatos/metabolismo , Compostos Férricos/metabolismo , Compostos Ferrosos/metabolismo , Comamonas/metabolismo , Bactérias/metabolismo , OxirreduçãoRESUMO
Arsenate reducing bacteria (AsRB) enhance arsenic (As) release via reducing As(V) to As(III), and As mobility is usually controlled by As(III) re-uptake on in-situ formed secondary iron minerals. The re-uptake of As(III) under groundwater flow conditions significantly impacts the fate and transport of As. Herein, a novel As(V)-reducing bacterium Alkaliphilus IMB was isolated in an As-contaminated soil. Scanning transmission X-ray microscopy showed that dissolved As(V) was mainly bound to the cell walls whereas dissolved As(III) was homogeneously distributed around IMB, indicating that As(V) reduction occurs outside the cell membrane. To explore the effect of IMB on As mobility, IMB was incubated with As-loaded nanoscale zero-valent iron (nZVI) residues under static and flowing conditions. IMB reduced 100% dissolved As(V) to As(III) even in a short contact time (â¼1 h) during flowing incubation. The formation of As(III) did not influence As mobility under static condition as evidenced by the comparable concentrations of released As in the presence of IMB (8.5% to total As) and the abiotic control (10% to total As). Biogenic As(III) was re-adsorbed on the solids as shown by the higher ratio of solid-bound As(III) to total As in the presence of IMB (54%) than that in the abiotic control (12%). By contrast, the degree of As(III) re-adsorption was inhibited in the flowing environment, as suggested by the lower As(III) ratio in the solid (31%). This inhibition can be ascribed to the relatively slow adsorption of As(III) compared with the quick reduction of As(V) (â¼1 h). Thus, IMB significantly enhanced As release during flowing incubation as shown that 9.8% As was released in the presence of IMB while 2.1% As in the abiotic control. This study found the contrary effect of AsRB on As mobility in static and flowing environments, highlighting the importance of re-adsorption rate of As(III).
Assuntos
Arsênio , Ferro , Ferro/química , Arsênio/metabolismo , Oxirredução , Arseniatos/metabolismo , AdsorçãoRESUMO
We investigated the aqueous solubility and thermodynamic properties of two meta-autunite group uranyl arsenate solids (UAs). The measured solubility products (log Ksp) obtained in dissolution and precipitation experiments at equilibrium pH 2 and 3 for NaUAs and KUAs ranged from -23.50 to -22.96 and -23.87 to -23.38, respectively. The secondary phases (UO2)(H2AsO4)2(H2O)(s) and trögerite, (UO2)3(AsO4)2·12H2O(s), were identified by powder X-ray diffraction in the reacted solids of KUA precipitation experiments (pH 2) and NaUAs dissolution and precipitation experiments (pH 3), respectively. The identification of these secondary phases in reacted solids suggest that H3O+ co-occurring with Na or K in the interlayer region can influence the solubilities of uranyl arsenate solids. The standard-state enthalpy of formation from the elements (ΔHf-el) of NaUAs is -3025 ± 22 kJ mol-1 and for KUAs is -3000 ± 28 kJ mol-1 derived from measurements by drop solution calorimetry, consistent with values reported in other studies for uranyl phosphate solids. This work provides novel thermodynamic information for reactive transport models to interpret and predict the influence of uranyl arsenate solids on soluble concentrations of U and As in contaminated waters affected by mining legacy and other anthropogenic activities.
Assuntos
Arseniatos , Solubilidade , TermodinâmicaRESUMO
Arsenic (As) is ubiquitous in geothermal fluids, which threatens both water supply safety and local ecology. The co-occurrence of sulfur (S) and As increases the complexity of As migration and transformation in hot springs. Microorganisms play important roles in As-S transformation processes. In the present study, two Tibetan alkaline hot springs (designated Gulu [GL] and Daba [DB]) with different total As concentrations (0.88 mg/L and 12.42 mg/L, respectively) and different sulfide/As ratios (3.97 and 0.008, respectively) were selected for investigating interactions between As-S geochemistry and microbial communities along the outflow channels. The results showed that As-S transformation processes were similar, although concentrations and percentages of As and S species differed between the two hot springs. Thioarsenates were detected at the vents of the hot springs (18% and 0.32%, respectively), and were desulfurized to arsenite along the drainage channel. Arsenite was finally oxidized to arsenate (532 µg/L and 12,700 µg/L, respectively). Monothioarsenate, total As, and sulfate were the key factors shaping the changes in microbial communities with geochemical gradients. The relative abundances of sulfur reduction genes (dsrAB) and arsenate reduction genes (arsC) were higher in upstream portions of GL explaining high thiolation. Arsenite oxidation genes (aoxAB) were relatively abundant in downstream parts of GL and at the vent of DB explaining low thiolation. Sulfur oxidation genes (soxABXYZ) were abundant in GL and DB. Putative sulfate-reducing bacteria (SRB), such as Desulfuromusa and Clostridium, might be involved in forming thioarsenates by producing reduced S for chemical reactions with arsenite. Sulfur-oxidizing bacteria (SOB), such as Elioraea, Pseudoxanthomonas and Pseudomonas, and arsenite-oxidizing bacteria (AsOB) such as Thermus, Sulfurihydrogenibium and Hydrogenophaga, may be responsible for the oxidation of As-bound S, thereby desulfurizing thioarsenates, forming arsenite and, by further abiotic or microbial oxidation, arsenate. This study improves our understanding of As and S biogeochemistry in hot springs.
Assuntos
Arsênio , Arsenitos , Fontes Termais , Microbiota , Arsênio/análise , Arseniatos/análise , Arseniatos/química , Fontes Termais/química , Fontes Termais/microbiologia , Uganda , Bactérias/genética , Oxirredução , Sulfetos , Sulfatos , EnxofreRESUMO
Arsenic is abundant in the environment and takes the form of trivalent and pentavalent arsenic compounds. Arsenite has been reported to both promote and suppress erythropoietin (EPO) production and autophagy induction. EPO production is involved in hematopoiesis, and autophagy induction is involved in cytoprotection, both of which are thought to be cellular responses to arsenic stress. While there are reports that show the effects of EPO on autophagy induction, the relationship between EPO production and autophagy induction is unclear. Therefore, this study analyzed the effect of the pentavalent inorganic arsenic salt arsenate on EPO production in vitro and in vivo and EPO-induced autophagy in HepG2 cells. Exposure of HepG2 cells to low-concentration arsenate was observed to increase EPO production and induced autophagy. Moreover, a ROS scavenger suppressed the arsenate-induced increase in autophagy and EPO mRNA levels. Both EPO production and autophagy induction contributed to protection from arsenate-induced cytotoxic stress. HepG2 cells expressed the EPO receptor and production of EPO by HepG2 cells acted in an autoregulatory manner to suppress autophagy induction. In vivo administration of low-concentration arsenate to rats increased EPO mRNA levels in the liver and kidney. These results suggested that low-concentration arsenate promotes EPO production and autophagy induction in HepG2 cells, and the resultant EPO production contributes to cytoprotection of cultured cells via EPO receptor activation.
Assuntos
Arsênio , Arsenicais , Eritropoetina , Ratos , Animais , Humanos , Arseniatos/toxicidade , Arsênio/toxicidade , Células Hep G2 , AutofagiaRESUMO
In this study, a graphene oxide-based lanthanum hydroxide/chitosan foam (CSGOL foam) was synthesized for arsenate (As(V)) remediation in surface water. The synthesized CSGOL foam texture and purity was assessed using scanning electron microscopy (SEM), Brunauer-Emmett-Teller (BET) surface area, X-ray diffraction (XRD), thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FT-IR), and X-ray photoelectron spectroscopy (XPS) studies. The results proved that the foam was highly porous, stable, and had high surface functionality that facilitated adsorption for water pollutant removal. The sorption results proved that the As(V) removal was high (146.20 mg/g at pH 6 with 0.5 g/L CSGOL foam) when compared to the similar type of materials, endothermic chemisorption due to the production of monodentate and bidentate inner-sphere complexes. Furthermore, continuous column results indicated that the As(V) concentration in real surface waters was reduced to WHO standards (less than 10 µg As/L of water) of As(V) in drinking water for up to 10,000 bed volume. Further it can be used up to four cycles without loss of efficacy less than 93%. Because of its excellent removal capabilities and simple synthesis technique, CSGOL foam shows significant promise for treating As(V)-containing water. Further, the XPS analysis and batch studies results suggests that As(V) removal mechanism was involved electrostatic and surface complexation through chemical interaction predominately.
Assuntos
Arseniatos , Poluentes Químicos da Água , Espectroscopia de Infravermelho com Transformada de Fourier , Poluentes Químicos da Água/química , Água/química , Adsorção , Biopolímeros , Concentração de Íons de Hidrogênio , CinéticaRESUMO
Early-life arsenic (As) exposure is a particular health concern. However, it is unknown if As ingested early in life is more readily absorbed from the gastrointestinal (GI) tract, i.e., higher in oral bioavailability. Here, weanling (3-week) and adult (6-week-old) female mice were exposed to arsenate in the diet (10 µg g-1) over a 3-week period with As oral bioavailability estimated using As urinary excretion as the bioavailability endpoint. The As urinary excretion factor was 1.54-fold higher in weanling mice compared to adult mice (82.2 ± 7.29 versus 53.1 ± 3.73%), while weanling mice also showed 2.28-, 1.50-, 1.48-, and 1.89-fold higher As concentration in small intestine tissue, blood, liver, and kidneys, demonstrating significantly higher As oral bioavailability of early-life exposure. Compared to adult mice, weanling mice significantly differed in gut microbiota, but the difference did not lead to remarkable differences in As biotransformation in the GI tract or tissue and in overall gut metabolite composition. Although the expression of several metabolites (e.g., atrolactic acid, hydroxyphenyllactic acid, and xanthine) was up-regulated in weanling mice, they had limited ability to elevate As solubility in the intestinal tract. Compared to adult mice, the intestinal barrier function and intestinal expression of phosphate transporters responsible for arsenate absorption were similar in weanling mice. However, the small intestine of weanling mice was characterized by more defined intestinal villi with greater length and smaller width, providing a greater surface area for As to be absorbed across the GI barrier. The results highlight that early-life As exposure can be more readily absorbed, advancing the understanding of its health risk.
Assuntos
Arsênio , Microbioma Gastrointestinal , Animais , Camundongos , Feminino , Arseniatos , Mucosa Intestinal/metabolismoRESUMO
The study aimed to explicate the role of microbial co-inoculants for the mitigation of arsenic (As) toxicity in rice. Arsenate (AsV) reducer yeast Debaryomyces hansenii NBRI-Sh2.11 (Sh2.11) with bacterial strains of different biotransformation potential was attempted to develop microbial co-inoculants. An experiment to test their efficacy (yeast and bacterial strains) on plant growth and As uptake was conducted under a stressed condition of 20 mg kg-1 of arsenite (AsIII). A combination of Sh2.11 with an As(III)-oxidizer, Citrobacter sp. NBRI-B5.12 (B5.12), resulted in â¼90% decrease in grain As content as compared to Sh2.11 alone (â¼40%). Reduced As accumulation in rice roots under co-treated condition was validated with SEM-EDS analysis. Enhanced As expulsion in the selected combination under in vitro conditions was found to be correlated with higher As content in the soil during their interaction with plants. Selected co-inoculant mediated enhanced nutrient uptake in association with better production of indole acetic acid (IAA) and gibberellic acid (GA) in shoot, support microbial co-inoculant mediated better biomass under stressful condition. Boosted defense response in association with enhanced glutathione-S-transferase (GST) and glutathione reductase (GR), activities under in vitro and in vivo conditions were observed. These results indicated that the As(III) oxidizer-B5.12 accelerated the As detoxification property of the As(V) reducer-Sh2.11. Henceforth, the results confer that the coupled reduction-oxidation process of the co-inoculant reduces the accumulation of As in rice grain. These co-inoculants can be further developed for field trials to achieve higher biomass with alleviated As toxicity in rice.
Assuntos
Inoculantes Agrícolas , Arsênio , Arsenitos , Oryza , Poluentes do Solo , Arseniatos/toxicidade , Arseniatos/metabolismo , Arsênio/toxicidade , Arsênio/metabolismo , Saccharomyces cerevisiae , Oryza/metabolismo , Arsenitos/toxicidade , Arsenitos/metabolismo , Bactérias/metabolismo , Oxirredução , Inoculantes Agrícolas/metabolismo , Raízes de Plantas/metabolismo , Poluentes do Solo/análiseRESUMO
Microbes have important impacts on the mobilization of arsenic in groundwater. To study the effects of sulfide on As(V) bioreduction in sulfidic groundwater, Citrobacter sp. JH012-1 isolated from sediments in the Jianghan Plain was used in a microcosm experiment. The results showed that sulfide significantly enhanced As(V) bioreduction as an additional electron donor. The reduction rates of As(V) were 21.8%, 34.5%, 73.6% and 85.9% under 0, 15, 75 and 150 µM sulfide inputting, respectively. The main products of As(V) bioreduction were thioarsenite and orpiment and the concentration of thioarsenite reached to 5.5 and 7.1 µM in the solution with the initial 75 and 150 µM sulfide, respectively. However, under 0 and 15 µM sulfide inputting, the dominant product was arsenite with no thioarsenite accumulation. The decrease in pH enhanced the bioreduction of As(V) and promoted the formation of thioarsenite and orpiment. In addition, the percentage of thioarsenite in total arsenic decreased with the decrease in the ratio of sulfur to arsenic, indicating that the formation of thioarsenite was limited by the concentration of initial sulfide. Therefore, the presence of sulfide had a significant effect on the transformation of arsenic in groundwater. This study provides new insights into the bioreduction of As(V) and the formation of thioarsenite in sulfidic groundwater.
Assuntos
Arsênio , Água Subterrânea , Arseniatos , Arsênio/metabolismo , Sulfetos , Arsenamida , OxirreduçãoRESUMO
The microbial metabolism of arsenic plays a prominent role in governing the biogeochemical cycle of arsenic. Although diverse microbes are known to be involved in the redox transformation of inorganic arsenic, the underlying mechanisms about the arsenic redox cycle mediated by a single microbial strain remain unclear yet. Herein, we discover that Shewanella putrefaciens CN32, a well-known arsenate-respiring and dissimilatory metal-reducing bacterium, could mediate the reversible arsenic redox transformation under aerobic conditions. Genetic analysis shows that S. putrefaciens CN32 contains both ars and arr operon but lacks an As(III) oxidase encoding gene. Arsenic(V) reduction tests demonstrate that the ars operon is advantageous but not essential for As(V) respiration in S. putrefaciens CN32. The Arr complex encoded by the arr operon not only plays a crucial role in arsenate respiration under anaerobic conditions but also participates in the sequential process of As(V) reduction and As(III) oxidation under aerobic conditions. The Arr enzyme also contributes to the microbial As(III) resistance. The expression and catalysis directionality of Arr in S. putrefaciens CN32 are regulated by the carbon source types. Our results highlight the complexity of arsenic redox biotransformation in environments and provide new insights into the important contribution of Arr to the As biogeochemical cycle in nature.
Assuntos
Arsênio , Arsenicais , Shewanella putrefaciens , Arseniatos , Arsênio/metabolismo , Shewanella putrefaciens/metabolismo , OxirreduçãoRESUMO
Obtaining reliable speciation data for evaluating dietary exposure, and increasing understanding of arsenic biochemistry in algae, are hindered by the availability of suitable standards of arsenosugars, the major species in these types of samples. Moreover, chemical syntheses of such compounds have been reported to be complex and tedious. The aim of this work was to investigate the feasibility of the anionic exchange SPE cartridges (SAX and WAX) as an easy and quick alternative for the isolation and preconcentration of arsenosugars. Two commercial silica-based SPE cartridges strong anion exchange sorbent (DSC-SAX) and weak anion exchange sorbent (DSC-NH2) were compared for the SPE of three arsenosugars (PO4-Sug, SO3-Sug and SO4-Sug). The effect of pH, ionic strength, type of salt and elution solvent on the elution protocols of these arsenosugars are studied. Eluted solutions from SPE were analyzed by ICP-MS for total arsenic content and IC-ICP-MS for the study of arsenic speciation. The developed SPE procedure allows to obtain a solution containing the three arsenosugars isolated from other arsenic species with recoveries over 75% for SO3-Sug and SO4-Sug, whereas for PO4-Sug were around 45%.
Assuntos
Arsênio , Arseniatos , Monossacarídeos , Extração em Fase SólidaRESUMO
The arousal of environmental concerns due to spike in environmental degradation has necessitated proper waste management and disposal. Arsenic, a potentially toxic element in cassava wastewater, requires treatment prior to the wastewater disposal to minimize environmental pollution and associated health implications. The present study thus addressed the treatment of As5+ heavy metal in cassava wastewater using an efficient biosorbent from chemically pretreated unshelled Moringa oleifera seeds. The effect of various factors influencing the biosorption process for arsenate removal was studied including pH, contact time, biosorbent dosage, and biosorbent pretreatment concentration. The results of Fourier transform infrared spectroscopy clearly suggested that additional functional groups attributed to esters were formed in the pretreated biosorbent, which is responsible for improvement in biosorption. It was found that contact time, biosorbent dosage, and biosorbent pretreatment concentration had statistically significant effect (p values < 0.05) on arsenate removal. A maximum percentage removal of 99.9% was achieved in the synthetic solution at pH 4.0, contact time of 30 min, and dosage of 2 g for biosorbent pretreated with 1 M of chemical solution. Furthermore, through isotherm and kinetics studies, it was discovered that the biosorption process for untreated biosorbent is by ion exchange, while that for treated biosorbents indicated a multifarious adsorption mechanism. Moreover, the biosorption process was exothermic and spontaneous. Also, it is noted that the sorption capability of the biosorbent increases with pretreatment concentration. A statistical model has been developed with prediction R2 of 0.898, which incorporates the effect of treatment concentration on the percentage removal of As5+ from cassava wastewater.
Assuntos
Arsênio , Poluentes Químicos da Água , Adsorção , Arseniatos , Monitoramento Ambiental , Ésteres , Concentração de Íons de Hidrogênio , Cinética , Espectroscopia de Infravermelho com Transformada de Fourier , Termodinâmica , Poluentes Químicos da Água/análiseRESUMO
Oxidative degradation by using reactive oxygen species (ROS) is an effective method to treat pollutants. The synthesis of artificial oxidase for the degradation of dyes is a hot spot in molecular science. In this study, a nanoscale sandwich-type polyoxometalate (POM) on the basis of a tetra-nuclear cobalt cluster and trivacant B-α-Keggin-type tungstoarsenate {[Co(C8H20N4)]4}{Co4(H2O)2[HAsW9O34]2}â4H2O (abbreviated as CAW, C8H20N4 = cyclen) has been synthesized and structurally examined by infrared (IR) spectrum, ultraviolet-visible (UV-Vis) spectrum, X-ray photoelectron spectrum (XPS), single-crystal X-ray diffraction (SXRD), and bond valence sum (Σs) calculation. According to the structural analysis, the principal element of the CAW is derived from modifying sandwich-type polyanion {Co4(H2O)2 [HAsW9O34]2}8- with four [Co(Cyclen)]2+, in which 1,4,7,10-tetraazacyclododecane (cyclen) is firstly applied to modify POM. It is also demonstrated that CAW is capable of efficiently catalyzing the production of ROS by the synergistic effects of POM fragments and Co-cyclen complexes. Moreover, CAW can interfere with the morphology and proliferation of sensitive cells by producing ROS and exhibits ability in specifically eliminating methylene blue (MB) dyes from the solution system by both adsorption and catalytic oxidation.
Assuntos
Ciclamos , Poluentes Ambientais , Ânions , Arseniatos , Cobalto/química , Corantes , Azul de Metileno/química , Azul de Metileno/farmacologia , Oxirredutases , Polieletrólitos , Espécies Reativas de Oxigênio , Compostos de TungstênioRESUMO
Arsenic (As) contamination is a global public health problem. Elevated total cholesterol (TC) and low-density lipoprotein-cholesterol (LDL-C) are risk factors for cardiovascular diseases, but data on the association of urinary arsenic species' level and LDL-C are limited. We performed an association analysis based on urinary arsenic species and blood TC and LDL-C in US adults. Methods: Urinary arsenic, arsenic acid (AA), dimethylarsinic (DMA), monomethylarsonic (MMA), TC, LDL-C, and other key covariates were obtained from the available National Health and Nutrition Examination Survey (NHANES) data from 2003 to 2020. Multiple linear regression analysis and generalized linear model are used to analyze linear and nonlinear relationships, respectively. Results: In total, 6633 adults aged 20 years were enrolled into the analysis. The median total urinary arsenic level was 7.86 µg/L. A positive association of urinary arsenic concentration quartiles was observed with TC (ß: 2.42 95% CI 1.48, 3.36). The OR for TC of participants in the 80th versus 20th percentiles of urinary total arsenic was 1.34 (95% CI 1.13, 1.59). The OR for LDL-C of participants in the 80th versus 20th percentiles of urinary total arsenic was 1.36 (95% CI 1.15, 1.62). For speciated arsenics analysis, the OR for arsenic acid and TC was 1.35 (95% CI 1.02, 1.79), whereas the OR for DMA and LDL-L was 1.20 (95% CI 1.03, 1.41), and the OR for MMA and LDL-L was 1.30 (95% CI 1.11, 1.52). Conclusions: Urinary arsenic and arsenic species were positively associated with increased LDL-C concentration. Prevention of exposure to arsenic and arsenic species maybe helpful for the control of TC and LDL-C level in adults.
Assuntos
Arsênio , Adulto , Arseniatos , Arsênio/urina , Arsenicais , Ácido Cacodílico/urina , LDL-Colesterol , Exposição Ambiental/efeitos adversos , Humanos , Inquéritos NutricionaisRESUMO
Arsenic (As) biotransformation in soil affects As biogeochemical cycling and is associated with As accumulation in rice. After inoculation with 1% iron-oxidizing bacteria (FeOB) in paddy soil, As speciation, As biotransformation genes in soil, As/Fe in Fe plaques, and As accumulation in rice were characterized. Compared with the control, the available As concentrations in soils decreased while amorphous and poorly crystalline Fe-Al oxidized As and crystalline Fe-Al oxidized As fractions increased of F (FeOB) and RF (rice and FeOB) treatments. Fe concentrations increased and positively correlated with As concentrations in Fe plaques on the rice root surface (***P < 0.001). Compared with R (rice), Monomethyl As (MMA), dimethyl As (DMA), arsenate (As(V)), and arsenite (As(III)) concentrations in rice plants showed a downwards trend of RF treatment. The As concentration in grains was below the National Standard for Food Safety (GB 2762-2017). A total of 16 As biotransformation genes in rhizosphere soils of different treatments (CK, F, R and RF were quantified by high-throughput qPCR (HT-qPCR). Compared with the control, the As(V) reduction and As transport genes abundance in other treatments increased respectively by 54.54%-69.17% and 54.63%-73.71%; the As(III) oxidation and As (de) methylation genes did not change significantly; however, several As(III) oxidation genes (aoxA, aoxB, aoxS, and arsH) increased. These results revealed that FeOB could reduce, transport As, and maybe also oxidize As. In addition, As(III) oxidation gene (aoxC) in rhizosphere soil was more abundant than in non-rhizosphere soil. It indicated that radial oxygen loss (ROL) promoted As(III) oxidation in rhizosphere soils. The results provide evidence for As biotransformation by ROL and FeOB in soil-rice system. ROL affects As oxidation and immobilization, and FeOB affects As reduction, transportation and may also affect As oxidation.
Assuntos
Arsênio , Arsenitos , Ochrobactrum , Oryza , Poluentes do Solo , Arsênio/análise , Solo/química , Oryza/metabolismo , Arseniatos/metabolismo , Arsenitos/metabolismo , Ferro/química , Poluentes do Solo/análise , Raízes de Plantas/metabolismo , Biotransformação , Oxirredução , Oxigênio/análiseRESUMO
Metal(loid)s can promote the spread and enrichment of antibiotic resistance in the environmental ecosystem through a co-selection effect. Little is known about the ecological effects of entering antibiotics into the environment with long-term metal(loid)s' resistance profiles. Here, cow manure containing oxytetracycline (OTC) or sulfadiazine (SA) at four concentrations (0 (as control), 1, 10, and 100 mg/kg) was loaded to a maize cropping system in an area with high a arsenicals geological background. Results showed that exogenous antibiotics entering significantly changed the nutrient conditions, such as the concentration of nitrate nitrogen, ammonium nitrogen, and available phosphorus in the maize rhizosphere soil, while total arsenic and metals did not display any differences in antibiotic treatments compared with control. Antibiotics exposure significantly influenced nitrate and nitrite reductase activities to reflect the inhibition of denitrification rates but did not affect the soil urease and acid phosphatase activities. OTC treatment also did not change soil dehydrogenase activities, while SA treatment posed promotion effects, showing a tendency to increase with exposure concentration. Both the tested antibiotics (OTC and SA) decreased the concentration of arsenite and arsenate in rhizosphere soil, but the inhibition effects of the former were higher than that of the latter. Moreover, antibiotic treatment impacted arsenite and arsenate levels in maize root tissue, with positive effects on arsenite and negative effects on arsenate. As a result, both OTC and SA treatments significantly increased bioconcentration factors and showed a tendency to first increase and then decrease with increasing concentration. In addition, the treatments decreased translocation capacity of arsenic from roots to shoots and showed a tendency to increase translocation factors with increasing concentration. Microbial communities with arsenic-resistance profiles may also be resistant to antibiotics entering.
Assuntos
Compostos de Amônio , Arsênio , Arsenicais , Arsenitos , Oxitetraciclina , Rizosfera , Zea mays , Esterco , Antibacterianos/farmacologia , Oxitetraciclina/farmacologia , Arseniatos , Ecossistema , Nitratos , Urease , Solo , Sulfadiazina , Nitrogênio/análise , Fósforo , Fosfatase Ácida/farmacologia , Compostos de Amônio/farmacologia , Nitrito Redutases/farmacologia , OxirredutasesRESUMO
Elevated arsenic (As) is common in geothermal springs, shaping the evolution of As metabolism genes and As transforming microbes. Herein, genome-level microbial metabolisms and As cycling strategies in Tengchong geothermal springs were demonstrated for the first time based on metagenomic and metatranscriptomic analyses. Sulfur cycling was dominated by Aquificae oxidizing thiosulfate via the sox system, fueling the respiration and carbon dioxide fixation processes. Arsenate reduction via arsC [488.63 ± 271.60 transcripts per million (TPM)] and arsenite efflux via arsB (442.98 ± 284.81 TPM) were the primary detoxification pathway, with most genes and transcripts contributed by the members in phylum Aquificae. A complete arsenotrophic cycle was also transcriptionally active as evidenced by the detection of aioA transcripts and arrA transcript reads mapped onto metagenome-assembled genomes (MAGs) affiliated with Crenarchaeota. MAGs affiliated with Aquificae had great potential of reducing arsenate via arsC and fixing nitrogen and carbon dioxide via nifDHK and reductive tricarboxylic acid (rTCA) cycle, respectively. Aquificae's arsenate reduction potential via arsC was observed for the first time at the transcriptional level. This study expands the diversity of the arsC-based arsenate-reducing community and highlights the importance of Aquificae to As biogeochemistry.