Extent of As(III) versus As(V) adsorption on iron (oxyhydr) oxides depends on the presence of vacancy cluster-like micropore sites: Insights into a seesaw effect.

Iron (oxyhydr)oxides are ubiquitous in terrestrial environments and play a crucial role in controling the fate of arsenic in sediments and groundwater. Although there is evidence that different iron (oxyhydr)oxides have different affinities towards As(III) and As(V), it is still unclear why As(V) adsorption on some iron (oxyhydr)oxides is larger than As(III) adsorption, while it is opposite for other ones. In this study, six typical iron (oxyhydr)oxides are selected to evaluate their adsorption capacities for As(III) and As(V). The characteristics of these iron minerals such as morphology, arsenic adsorption species, and pore size distribution are carefully examined using transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDS), positron annihilation lifetime (PAL) spectroscopy, and X-ray absorption spectroscopy (XAS). We confirm a seesaw effect occurred in different iron minerals for As(III) and As(V) immobilization, i.e., at pH 6.0, adsorption of As(V) on hematite (0.73 µmol m-2) and magnetite (0.33 µmol m-2) is higher than for As(III) (0.61 µmol m-2 and 0.27 µmol m-2, respectively), for goethite and lepidocrocite it is almost equal, while As(III) sorption on ferrihydrite (5.77 µmol m-2) and schwertmannite (28.41 µmol m-2) showed higher sorption than As(V) (1.53 µmol m-2 and 12.99 µmol m-2, respectively). PAL analysis demonstrates that ferrihydrite and schwertmannite have a large concentration of vacancy cluster-like micropores, significantly more than goethite and lepidocrocite, followed by hematite and magnetite. The difference of adsorption of As(III) and As(V) to different iron (oxyhydr)oxides is due to differences in the abundance of vacancy cluster-like micropore sites, which are conducive for smaller size As(III) immobilization but not for larger size of As(V). The findings of this study provide novel insights into a seesaw effect for As(III) and As(V) immobilization on naturally occurring iron mineral.

Phosphorous accumulation associated with mitochondrial PHT3-mediated enhanced arsenate tolerance in Chlamydomonas reinhardtii.

Arsenate is a highly toxic element and excessive accumulation of arsenic in the aquatic environment easily triggers a problem threatening the ecological health. Phytoremediation has been widely explored as a method to alleviate As contamination. Here, the green algae, Chlamydomonas reinhardtii was investigated by profiling the accumulation of arsenate and phosphorus, which share the same uptake pathway, in response to arsenic stress. Both C. reinhardtii wild type C30 and the Crpht3 mutant were cultured under arsenic stress, and demonstrated a similar growth phenotype under limited phosphate supply. Sufficient phosphate obviously increased the uptake of polyphosphate and intercellular phosphate in the Crpht3 mutant, which increased the arsenic tolerance of the Crpht3 mutant under stress from 500 µmol L-1 As(V). Upregulation of the PHT3 gene in the Crpht3 mutant increased accumulation of phosphate in the cytoplasm under arsenate stress, which triggered a regulatory role for the differentially expressed genes that mediated improvement of the glutathione redox cycle, antioxidant activity and detoxification. While the wild type C30 showed weak arsenate tolerance because of little phosphate accumulation. These results suggest that the enhanced arsenic tolerance of the Crpht3 mutant is regulated by the PHT3 gene mediation. This study provides insight onto the responsive mechanisms of the PHT3 gene-mediated in alleviating arsenic toxicity in plants.

Some remarks on "Efficient removal of total arsenic (As3+/5+) from contaminated water by novel strategies mediated iron and plant extract activated waste flowers of marigold".

We explain here that the authors of the article cited in the title have misrepresented the species of As(III) and As(V) in solutions and, in particular, have neglected their speciation as a function of pH. Their discussion of (ad)sorption mechanisms is therefore unsatisfactory, especially since organic matter (flower waste) and the presence of iron oxyhydroxides should be taken into account. Furthermore, the modeling of (ad)sorption kinetics and isotherms was based on linearized equations, whereas the corresponding nonlinear equations should have been used. Therefore, we believe that the authors of the original article should make corrections and additions to it. This Letter to the Editor is motivated by a concern to avoid the dissemination of approximate or even incorrect concepts in the scientific literature, which could mislead novice researchers.

24-Epibrassinolide mitigates arsenate stress in seedlings of Oryza sativa (IR-20) via the induction of phenylpropanoid pathway.

The introduction of arsenic, a hazardous metalloid, into the soil system due to heavy industrialization has negatively affected agricultural productivity, resulting in limited crop yields. A recent breakthrough in stress-responsive hormones, specifically brassinosteroids, has extensively covered the role of antioxidant enzyme defense systems in heavy metal stress mitigation. Considering the antioxidant properties and metal complex formation abilities of polyphenols, our study focuses on examining their role in arsenate toxicity amelioration by 24-epibrassinolide. We demonstrate enhanced growth parameters of sodium arsenate-stressed seedlings upon application of 24-epibrassinolide, with increased root and shoot polyphenol levels analyzed by high-performance liquid chromatography. Specifically, the concentration of catechin, sinapic acid, 4-hydroxy benzoic acid, protocatechuic acid, 4-coumaric acid, and myricetin were elevated, indicating induction of phenylpropanoid signaling pathway. Further, we also report a decrease in the generation of superoxide anions and hydrogen peroxide validated the antioxidant effects of these metabolites through the nitrobluetetrazolium and diaminobenzidine staining method. In addition, evaluation of transcript level of genes encoding for specific enzymes of the phenylpropanoid pathway in shoot and root showed a significant upregulation in mRNA expression of phenylalanine ammonia-lyase-1, cinnamate-4-hydroxylase, and caffeic acid o-methyltransferase-1 upon exogenous application of 24-epibrassinolide in arsenate stressed Oryza sativa.

Adsorption of Bichromate and Arsenate Anions by a Sorbent Based on Bentonite Clay Modified with Polyhydroxocations of Iron and Aluminum by the "Co-Precipitation" Method.

The physicochemical properties of natural bentonite and its sorbents were studied. It has been established the modification of natural bentonites using polyhydroxoxides of iron (III) (mod.1_Fe_5-c) and aluminum (III) (mod.1_Al_5-c) by the "co-precipitation" method led to changes in their chemical composition, structure, and sorption properties. It was shown that modified sorbents based on natural bentonite are finely porous (nanostructured) objects with a predominance of pores of 1.5-8.0 nm in size. The modification of bentonite with iron (III) and aluminum compounds by the "co-precipitation" method also leads to an increase in the sorption capacity of the obtained sorbents with respect to bichromate and arsenate anions. A kinetic analysis showed that, at the initial stage, the sorption process was controlled by an external diffusion factor, that is, the diffusion of the sorbent from the solution to the liquid film on the surface of the sorbent. The sorption process then began to proceed in a mixed diffusion mode when it limited both the external diffusion factor and the intra-diffusion factor (diffusion of the sorbent to the active centers through the system of pores and capillaries). To clarify the contribution of the chemical stage to the rate of adsorption of bichromate and arsenate anions by the sorbents under study, kinetic curves were processed using equations of chemical kinetics (pseudo-first-order, pseudo-second-order, and Elovich models). It was found that the adsorption of the studied anions by the modified sorbents based on natural bentonite was best described by a pseudo-second-order kinetic model. The high value of the correlation coefficient for the Elovich model (R2 > 0.9) allows us to conclude that there are structural disorders in the porous system of the studied sorbents, and their surfaces can be considered heterogeneous. Considering that heterogeneous processes occur on the surface of the sorbent, it is natural that all surface properties (structure, chemical composition of the surface layer, etc.) play an important role in anion adsorption.

Meta-omics analysis reveals the marine arsenic cycle driven by bacteria.

Arsenic is a toxic element widely distributed in the Earth's crust and ranked as a class I human carcinogen. Microbial metabolism makes significant contributions to arsenic detoxification, migration and transformation. Nowadays, research on arsenic is primarily in areas affected by arsenic pollution associated with human health activities. However, the biogeochemical traits of arsenic in the global marine ecosystem remain to be explicated. In this study, we revealed that seawater environments were primarily governed by the process of arsenate reduction to arsenite, while arsenite methylation was predominant in marine sediments which may serve as significant sources of arsenic emission into the atmosphere. Significant disparities existed in the distribution patterns of the arsenic cycle between surface and deep seawaters at middle and low latitudes, whereas these situations tend to be similar in the Arctic and Antarctic oceans. Significant variations were also observed in the taxonomic diversity and core microbial community of arsenic cycling across different marine environments. Specifically, γ-proteobacteria played a pivotal role in the arsenic cycle in the whole marine environment. Temperature, dissolved oxygen and phosphate were the crucial factors that related to these differentiations in seawater environments. Overall, our study contributes to a deeper understanding of the marine arsenic cycle.

Foliar-selenium enhances plant growth and arsenic accumulation in As-hyperaccumulator Pteris vittata: Critical roles of GSH-GSSG cycle and arsenite antiporters PvACR3.

It is known that selenium (Se) enhances plant growth and arsenic (As) accumulation in As-hyperaccumulator Pteris vittata, but the associated mechanisms are unclear. In this study, P. vittata was exposed to 50 µM arsenate (AsV) under hydroponics plus 25 or 50 µM foliar selenate. After 3-weeks of growth, the plant biomass, As and Se contents, As speciation, malondialdehyde (MDA) and glutathione (GSH and GSSG) levels, and important genes related to As-metabolism in P. vittata were determined. Foliar-Se increased plant biomass by 17 - 30 %, possibly due to 9.1 - 19 % reduction in MDA content compared to the As control. Further, foliar-Se enhanced the As contents by 1.9-3.5 folds and increased arsenite (AsIII) contents by 64 - 136 % in the fronds. The increased AsV reduction to AsIII was attributed to 60 - 131 % increase in glutathione peroxidase activity, which mediates GSH oxidation to GSSG (8.8 -29 % increase) in the fronds. Further, foliar-Se increased the expression of AsIII antiporters PvACR3;1-3;3 by 1.6 - 2.1 folds but had no impact on phosphate transporters PvPht1 or arsenate reductases PvHAC1/2. Our results indicate that foliar-Se effectively enhances plant growth and arsenic accumulation by promoting the GSH-GSSG cycle and upregulating gene expression of AsIII antiporters, which are responsible for AsIII translocation from the roots to fronds and AsIII sequestration into the fronds. The data indicate that foliar-Se can effectively improve phytoremediation efficiency of P. vittata in As-contaminated soils.

Arsenate reductase of Rufibacter tibetensis is a metallophosphoesterase evolved to catalyze redox reactions.

An arsenate reductase (Car1) from the Bacteroidetes species Rufibacter tibetensis 1351T was isolated from the Tibetan Plateau. The strain exhibits resistance to arsenite [As(III)] and arsenate [As(V)] and reduces As(V) to As(III). Here we shed light on the mechanism of enzymatic reduction by Car1. AlphaFold2 structure prediction, active site energy minimization, and steady-state kinetics of wild-type and mutant enzymes give insight into the catalytic mechanism. Car1 is structurally related to calcineurin-like metallophosphoesterases (MPPs). It functions as a binuclear metal hydrolase with limited phosphatase activity, particularly relying on the divalent metal Ni2+. As an As(V) reductase, it displays metal promiscuity and is coupled to the thioredoxin redox cycle, requiring the participation of two cysteine residues, Cys74 and Cys76. These findings suggest that Car1 evolved from a common ancestor of extant phosphatases by incorporating a redox function into an existing MPP catalytic site. Its proposed mechanism of arsenate reduction involves Cys74 initiating a nucleophilic attack on arsenate, leading to the formation of a covalent intermediate. Next, a nucleophilic attack of Cys76 leads to the release of As(III) and the formation of a surface-exposed Cys74-Cys76 disulfide, ready for reduction by thioredoxin.

Effect of long-term inorganic arsenic exposure on erythropoietin production in vitro.

Arsenic is widely present in the environment in trivalent and pentavalent forms; long-term arsenic exposure due to environmental pollution has become a problem. Previous reports have shown that 24-h exposure to arsenate (as pentavalent arsenic) potentiates erythropoietin (EPO) production via reactive oxygen species (ROS) in EPO-producing HepG2 cells. However, the effects of long-term arsenate exposure on EPO production remain unclear. In HepG2 cells subcultured for 3 weeks in the presence of arsenate, EPO mRNA levels were lower than those in untreated cells. Levels of ARSENITE METHYLTRANSFERASE mRNA, as well as those of Nuclear factor erythroid 2-related factor 2, glutathione, and superoxide dismutase proteins, were increased compared to untreated cells, but levels of malondialdehyde were not significantly altered. Thus, long-term exposure to arsenate enhances ROS scavenging, suggesting that the ROS-induced accumulation of EPO mRNA is attenuated by arsenate exposure. The induction of EPO accumulation by hypoxia also was attenuated by long-term arsenate exposure, suggesting an impairment in responsivity of EPO production. Furthermore, mRNA levels of SIRTUIN-1, which affects EPO transcription, were potentiated by long-term arsenate exposure. These results suggest that long-term arsenate exposure has multiple, distinct effects on EPO production in vitro.

Construction of Tetrahymena strains with highly active arsenic methyltransferase genes for arsenic detoxification in aquatic environments.

Biomethylation is an effective means of arsenic detoxification by organisms living in aquatic environments. Ciliated protozoa (including Tetrahymena species) play an important role in the biochemical cycles of aquatic ecosystems and have a potential application in arsenic biotransformation. This study compared arsenic tolerance, accumulation, methylation, and efflux in 11 Tetrahymena species. Nineteen arsenite (As(III)) S-adenosylmethionine (SAM) methyltransferase (arsM) genes, of which 12 are new discoveries, were identified, and protein sequences were studied. We then constructed recombinant cell lines based on the Tetrahymena thermophila (T. thermophila) wild-type SB210 strain and expressed each of the 19 arsM genes under the control of the metal-responsive the MTT1 promoter. In the presence of Cd2+ and As(V), expression of the arsM genes in the recombinant cell lines was much higher than in the donor species. Evaluation of the recombinant cell line identified one with ultra-high arsenic methylation enzyme activity, significantly higher arsenic methylation capacity and much faster methylation rate than other reported arsenic methylated organisms, which methylated 89% of arsenic within 6.5 h. It also had an excellent capacity for the arsenic detoxification of lake water containing As(V), 56% of arsenic was methylated at 250 µg/L As(V) in 48 h. This study has made a significant contribution to our knowledge on arsenic metabolism in protozoa and demonstrates the great potential to use Tetrahymena species in the arsenic biotransformation of aquatic environments.

Photochemical transformation and immobilization of thallium in the presence of iron and arsenic: Mechanistic insights from the coupled formation of arsenate complexes.

Despite the occurrence of thallium (Tl) in the acidic mining-affected areas being highly positively correlated with iron (Fe) and arsenic (As), the effects of the two accompanying elements on Tl redox transformation and immobilization remain largely unknown. Here, we investigated the photochemical redox kinetics and immobilization efficiency of Tl for a wide range of As/Fe and As/Tl ratios under acidic conditions. We provided the first experimental confirmation of the complexation of Tl(III) with As(V) by the spectrophotometric method and revealed the role of Tl(III)-As(V) complexes in decreasing the photoreduction rate of Tl(III) under sunlight. Additionally, the negative impact of colloidal Fe(III)-As(V) and Fe(III)-As(III) complexes formation on decreasing photoactive Fe(III) speciation and thus the apparent quantum yield of •OH was highlighted, which consequently hindered the oxidative conversion of Tl(I) to Tl(III). We rationalize the kinetics results by developing the model which quantitatively describes the photochemistry of Tl. Furthermore, we demonstrated the colloid-facilitated immobilization of Tl(III) through the formation of Tl(III)-As(V) clusters and surface adsorption onto the complexes. This study broadens the mechanistic understanding of redox transformation and immobilization potential of Tl and aids in assessing Tl speciation as well as its coupled transformation with Fe and As species in the sunlit water environment.

Iron minerals: A frontline barrier against combined toxicity of microplastics and arsenic.

The coexistence of microplastics (MPs) and arsenic (As) in terrestrial ecosystems presents challenges to controlling soil pollution and performing environmental risk assessments. In this study, the interactions among As, polystyrene MPs, and goethite in porous media were investigated and the individual and combined toxicities of MPs and As on wheat germination were evaluated. An additional experiment was conducted to assess the mitigating effect of goethite on the toxicity of the two contaminants. The results showed that the presence of MPs reduced As accumulation in wheat and decreased the acute lethal toxicity of As pollutants (the half-lethal concentration of As during wheat germination increased by 68.21%). However, MPs exhibited inhibitory effects on wheat germination and served as carriers to promote the migration of As within the plant body. The addition of goethite mitigated both individual and combined toxicities and further increased the half-lethal concentration for the combined pollution of As and MPs by 39.48%. This was primarily attributed to the adsorption and immobilization of arsenate and MPs on the medium and root surfaces. In our study, goethite reduced soluble As by 48.29% under the combined pollution scenarios and formed iron plaques on wheat roots, effectively obstructing pollutant entry. Thus, iron minerals serve as pioneering barriers to combined toxicity. Our findings contribute to the understanding of the combined toxicity of MPs and As in crops and offer potential strategies for managing combined pollution.

Phenomic profiling to reveal tolerance mechanisms and regulation of ascorbate-glutathione cycle in wheat varieties (Triticum aestivum L.) under arsenic stress.

The potential of arsenic (As) tolerant and sensitive varieties of wheat (Triticum aestivum L.) has yet to be explored despite of alarming situation of arsenic toxicity. To fill this gap, the study aimed to explore the role of antioxidants, phytochelatins, and ascorbate-glutathione for As tolerance in wheat. A total of eight varieties were exposed to different arsenate treatments (0, 1, 5, 10, 50, 100, 200, 500, 1000, 2000, and 10,000 µM) initially to screen effective treatment as well as contrasting varieties via Weibull distribution frequency for further analysis. The Weibull analysis found 200 µM as the most effective treatment in the present study. Selected varieties were analyzed for accumulation of total As and As speciation, oxidative stress (malondialdehyde, hydrogen peroxide), antioxidants (superoxide dismutase, catalase, peroxidase), phytochelatins, and ascorbate-glutathione cycle (glutathione-S-transferase, glutathione reductase, glutathione peroxidase, ascorbate peroxidase). Tolerant varieties showed less accumulation and translocation of total As, arsenate, and arsenite to the shoots compared with sensitive varieties under 200 µM treatment. Low concentration in tolerant varieties correlated with better growth and development response. Tolerant varieties showed higher induction of metabolites (glutathione, phytochelatins) compared to sensitive ones. Furthermore, tolerant varieties showed better performance of antioxidant and ascorbate-glutathione cycle enzymes in response to As exposure. The findings of the present study provided great insight into the wheat tolerance mechanism upon As exposure between contrasting varieties.

Mechanisms and health implications of toxicity increment from arsenate-containing iron minerals through in vitro gastrointestinal digestion.

Inadvertent oral ingestion is an important exposure pathway of arsenic (As) containing soil and dust. Previous researches evidenced health risk of bioaccessible As from soil and dust, but it is unclear about As mobilization mechanisms in health implications from As exposure. In this study, we investigated As release behaviors and the solid-liquid interface reactions toward As(V)-containing iron minerals in simulated gastrointestinal bio-fluids. The maximum As release amount was 0.57 mg/L from As-containing goethite and 0.82 mg/L from As-containing hematite at 9 h, and the As bioaccessibility was 10.8% and 21.6%, respectively. The higher exposure risk from hematite-sorbed As in gastrointestinal fluid was found even though goethite initially contained more arsenate than hematite. Mechanism analysis revealed that As release was mainly coupled with acid dissolution and reductive dissolution of iron minerals. Proteases enhanced As mobilization and thus increased As bioaccessibility. The As(V) released and simultaneously transformed to high toxic As(III) by gastric pepsin, while As(V) reduction in intestine was triggered by pancreatin and freshly formed Fe(II) in gastric digests. CaCl2 reduced As bioaccessibility, indicating that calcium-rich food or drugs may be effective dietary strategies to reduce As toxicity. The results deepened our understanding of the As release mechanisms associated with iron minerals in the simulated gastrointestinal tract and supplied a dietary strategy to alleviate the health risk of incidental As intake.

Effect of Arsenate and p-Phenylenediamine on the Expression of Aquaporins in Cultured Human Urothelial Cells.

BACKGROUND: Exposure to arsenic (As) or p­phenylenediamine (PPD) can lead to dysfunction, or even cancer, in various types of organs, including the urinary bladder, yet the underlying mechanisms remain unclear. Aquaporins (AQPs) are widely expressed small water channel proteins that provide the major route for the transport of water and other small molecules across plasma membranes in diverse cell types. Altered expression of AQPs has been associated with pathologies in all major organs, including the urinary bladder. OBJECTIVE: The present in vitro study was performed as a first step towards exploring the possible involvement of AQPs in As- and PPD­induced bladder diseases. METHODS: An immortalized normal human urothelial cell line was employed. Cells were exposed to different concentrations of sodium arsenate (0­20 µM) or PPD (0­200 µM) for 48 h. Cell viability was subsequently assessed. The mRNA and protein expression levels of AQPs (specifically, AQP3, 4, 7, 9, and 11) were analyzed using reverse transcription­quantitative polymerase chain reaction and Western blot analyses, respectively. RESULTS: The viability of the cells was decreased in a concentration-dependent manner upon exposure to arsenate. The mRNA and protein expression levels of AQP3, 4, 7, and 9 were substantially reduced, whereas the expression of AQP11 was largely unchanged. As for the experiments with PPD, treatment with increasing concentrations of PPD induced a gradual decrease in cell viability. The mRNA and protein expression levels of AQP3, 4, and 11 were generally unaltered; however, a marked reduction in the expression levels of AQP7 was observed, contrasting with a gradual concentration-dependent decrease in the expression of AQP9. CONCLUSION: The importance of the differential expression profiles of the AQPs induced by arsenate and PPD requires further investigation; nevertheless, the findings of the present study suggest that AQPs have a role in As­ and PPD­induced bladder diseases.

Unraveling the multifaceted resilience of arsenic resistant bacterium Deinococcus indicus.

Arsenic (As) is a toxic heavy metal widely found in the environment that severely undermines the integrity of water resources. Bioremediation of toxic compounds is an appellative sustainable technology with a balanced cost-effective setup. To pave the way for the potential use of Deinococcus indicus, an arsenic resistant bacterium, as a platform for arsenic bioremediation, an extensive characterization of its resistance to cellular insults is paramount. A comparative analysis of D. indicus cells grown in two rich nutrient media conditions (M53 and TGY) revealed distinct resistance patterns when cells are subjected to stress via UV-C and methyl viologen (MV). Cells grown in M53 demonstrated higher resistance to both UV-C and MV. Moreover, cells grow to higher density upon exposure to 25 mM As(V) in M53 in comparison with TGY. This analysis is pivotal for the culture of microbial species in batch culture bioreactors for bioremediation purposes. We also demonstrate for the first time the presence of polyphosphate granules in D. indicus which are also found in a few Deinococcus species. To extend our analysis, we also characterized DiArsC2 (arsenate reductase) involved in arsenic detoxification and structurally determined different states, revealing the structural evidence for a catalytic cysteine triple redox system. These results contribute for our understanding into the D. indicus resistance mechanism against stress conditions.

The Development of Fe3O4-Monolithic Resorcinol-Formaldehyde Carbon Xerogels Using Ultrasonic-Assisted Synthesis for Arsenic Removal of Drinking Water.

Inorganic arsenic in drinking water from groundwater sources is one of the potential causes of arsenic-contaminated environments, and it is highly toxic to human health even at low concentrations. The purpose of this study was to develop a magnetic adsorbent capable of removing arsenic from water. Fe3O4-monolithic resorcinol-formaldehyde carbon xerogels are a type of porous material that forms when resorcinol and formaldehyde (RF) react to form a polymer network, which is then cross-linked with magnetite. Sonication-assisted direct and indirect methods were investigated for loading Fe3O4 and achieving optimal mixing and dispersion of Fe3O4 in the RF solution. Variations of the molar ratios of the catalyst (R/C = 50, 100, 150, and 200), water (R/W = 0.04 and 0.05), and Fe3O4 (M/R = 0.01, 0.03, 0.05, 0.1, 0.15, and 0.2), and thermal treatment were applied to evaluate their textural properties and adsorption capacities. Magnetic carbon xerogel monoliths (MXRF600) using indirect sonication were pyrolyzed at 600 °C for 6 h with a nitrogen gas flow in the tube furnace. Nanoporous carbon xerogels with a high surface area (292 m2/g) and magnetic properties were obtained. The maximum monolayer adsorption capacity of As(III) and As(V) was 694.3 µg/g and 1720.3 µg/g, respectively. The incorporation of magnetite in the xerogel structure was physical, without participation in the polycondensation reaction, as confirmed by XRD, FTIR, and SEM analysis. Therefore, Fe3O4-monolithic resorcinol-formaldehyde carbon xerogels were developed as a potential adsorbent for the effective removal of arsenic with low and high ranges of As(III) and As(V) concentrations from groundwater.

Mechanistic Study of Arsenate Adsorption onto Different Amorphous Grades of Titanium (Hydr)Oxides Impregnated into a Point-of-Use Activated Carbon Block.

Millions of households still rely on drinking water from private wells or municipal systems with arsenic levels approaching or exceeding regulatory limits. Arsenic is a potent carcinogen, and there is no safe level of it in drinking water. Point-of-use (POU) treatment systems are a promising option to mitigate arsenic exposure. However, the most commonly used POU technology, an activated carbon block filter, is ineffective at removing arsenic. Our study aimed to explore the potential of impregnating carbon blocks with amorphous titanium (hydr)oxide (THO) to improve arsenic removal without introducing titanium (Ti) into the treated water. Four synthesis methods achieved 8-16 wt.% Ti loading within the carbon block with 58-97% amorphous THO content. The THO-modified carbon block could adsorb both oxidation states of arsenic (arsenate and arsenite) in batch or column tests. Modified carbon block with higher Ti and amorphous content always led to better arsenate removal, achieving arsenic loadings up to 31 mg As/mg Ti after 70,000 bed volumes in continuous flow tests. Impregnating carbon block with amorphous THO consistently outperformed impregnation using crystalline TiO2. The best-performing system (TTIP-EtOH carbon block) was an amorphous THO derived using titanium isopropoxide, ethanol, and acetic acid via sol-gel technique, aged at 80° for 18 hours and dried overnight at 60°. Comparable pore size distribution and surface area of the impregnated carbon blocks suggested that chemical properties play a more crucial role than physical and textural properties in removing arsenate via amorphous Ti-impregnated carbon block. Freundlich isotherms indicated energetically favorable adsorption for amorphous chemically synthesized adsorbents. The mass transport coefficients for the amorphous TTIP-EtOH carbon block were fitted using a pore surface diffusion model, resulting in Dsurface = 3.1×10-12 cm2/s and Dpore = 3.2×10-6 cm2/s. Impregnating the carbon block with THO enabled effective arsenic removal from water without adversely affecting the pressure drop across the unit or the carbon block's ability to remove polar organic chemical pollutants efficiently.

Tyrosol and Olive Oil Ameliorate Sodium Arsenate-Induced Nephrotoxicity by Modulating of Oxidative Stress and Histological Changes in Mice.

Background: Sodium arsenate (Na 3As0 4, Sodium As) is an important toxic substance that leads to nephrotoxicity. Due to having bioactive molecules, such as polyphenols and tyrosol, olive oil plays a significant role in scavenging free radicals. This study aimed to investigate the effects of olive oil and tyrosol on As-induced nephrotoxicity. Methods: In our study, 42 adult male BALB/c mice were randomly divided into six groups: control (normal saline), olive oil (0.4 ml/d, gavage), tyrosol (5 mg/kg/d), Sodium As (15 mg/kg), olive oil + Sodium As, and tyrosol + Sodium As (olive oil and tyrosol received one hour before Sodium As). Drugs were administreted once daily for 30 consecutive days. On the 31st day of the study, oxidative stress parameters in kidney tissue, FRAP in plasma, renal function parameters in serum, and histopathological assays were performed. Results: Sodium As-induced renal damage as characterized by a significant increase of creatinine and BUN (P < 0.001) and histopathological changes. Also, Sodium As markedly altered oxidative stress biomarkers such as a significant increase in MDA (P < 0.001) and significantly decreased in FRAP and GSH (P < 0.01). Olive oil and tyrosol administration significantly improved the renal antioxidant defense system and decreased MDA concentration, markedly preserving the tissue structure and functional markers of kidney. However, these effects were more effective for tyrosol than olive oil. Conclusions: Our results suggest that olive oil and tyrosol can be used as a protective agent in preventing Sodium As-induced nephrotoxicity due to antioxidant property.

Oral administration of Nigella sativa oil attenuates arsenic-induced redox imbalance, DNA damage, metabolic distress, and histopathological alterations in rat intestine.

BACKGROUND: Exposure to arsenic, a widespread environmental toxin, produces multiple organ toxicity, including gastrointestinal toxicity. Nigella sativa (NS) has long been revered for its numerous health benefits under normal and pathological states. In view of this, the present study attempts to evaluate the protective efficacy of orally administered Nigella sativa oil (NSO) against arsenic-induced cytotoxic and genotoxic alterations in rat intestine and elucidate the underlying mechanism of its action. METHODS: Rats were categorized into the control, NaAs, NSO, and NaAs+NSO groups. After pre-treatment of rats in the NaAs+NSO and NSO groups daily with NSO (2 ml/kg bwt, orally) for 14 days, NSO treatment was further continued for 30 days, with and without NaAs treatment (5 mg/kg bwt, orally), respectively. Various biochemical parameters, such as enzymatic and non-enzymatic antioxidants, carbohydrate metabolic and brush border membrane marker enzyme activities were evaluated in the mucosal homogenates of all the groups. Intestinal brush border membrane vesicles (BBMV) were isolated, and the activities of membrane marker enzyme viz. ALP, GGTase, LAP, and sucrase were determined. Further, the effect on kinetic parameters viz KM (Michaelis-Menten constant) and Vmax of these enzymes was assessed. Integrity of enterocyte DNA was examined using the comet assay. Histopathology of the intestines was performed to evaluate the histoarchitectural alterations induced by chronic arsenic exposure and/or NSO supplementation. Arsenic accumulation in the intestine was studied by inductively coupled plasma-mass spectroscopy (ICP-MS). RESULTS: NaAs treatment caused substantial changes in the activities of brush border membrane (BBM), carbohydrate metabolism, and antioxidant defense enzymes in the intestinal mucosal homogenates. The isolated BBM vesicles (BBMV) also showed marked suppression in the marker enzyme activities. Severe DNA damage and mucosal arsenic accumulation were observed in rats treated with NaAs alone. In contrast, oral NSO supplementation significantly alleviated all the adverse alterations induced by NaAs treatment. Histopathological examination supported the biochemical findings. CONCLUSION: NSO, by improving the antioxidant status and energy metabolism, could significantly alter the ability of the intestine to protect against free radical-mediated arsenic toxicity in intestine. Thus, NSO may have an excellent scope in managing gastrointestinal distress in arsenic intoxication.