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Wolverines are facultative scavengers that feed near the top of terrestrial food chains. We characterized concentrations of mercury and other trace elements in tissues of wolverine from a broad geographic area, representing much of their contemporary distribution in northwestern North America. We obtained tissues from 504 wolverines, from which mercury was measured on muscle (n = 448), kidney (n = 222), liver (n = 148), hair (n = 130), and brain (n = 52). In addition, methylmercury, seven trace elements (arsenic, cadmium, chromium, cobalt, lead, nickel, selenium), and arsenic compounds were measured on a subset of samples. Concentrations of mercury and other trace elements varied between tissues and were generally highest in kidney compared to brain, liver and muscle. Mercury was predominately as methylmercury in brain and muscle, but largely as inorganic mercury in liver and kidney. Mercury concentrations of hair were moderately correlated with those of internal tissues (Pearson r = 0.51–0.75, p ≤ 0.004), making hair a good non-lethal indicator of broad spatial or temporal differences in mercury exposure to wolverine. Arsenobetaine was the dominant arsenic compound identified in tissues, and arsenite, arsenocholine and dimethylarsinic acid were also detected. A preliminary risk assessment suggested the cadmium, lead, mercury, and selenium concentrations in our sample of wolverines were not likely to pose a risk of overt toxicological effects. This study generated a comprehensive dataset on mercury and other trace elements in wolverine, which will support future contaminants study of this northern terrestrial carnivore. [ABSTRACT FROM AUTHOR]

The European Commission asked EFSA for a risk assessment on small organoarsenic species in food. For monomethylarsonic acid MMA(V), decreased body weight resulting from diarrhoea in rats was identified as the critical endpoint and a BMDL10 of 18.2 mg MMA(V)/kg body weight (bw) per day (equivalent to 9.7 mg As/kg bw per day) was calculated as a reference point (RP). For dimethylarsinic acid DMA(V), increased incidence in urinary bladder tumours in rats was identified as the critical endpoint. A BMDL10 of 1.1 mg DMA(V)/kg bw per day (equivalent to 0.6 mg As/kg bw per day) was calculated as an RP. For other small organoarsenic species, the toxicological data are insufficient to identify critical effects and RPs, and they could not be included in the risk assessment. For both MMA(V) and DMA(V), the toxicological database is incomplete and a margin of exposure (MOE) approach was applied for risk characterisation. The highest chronic dietary exposure to DMA(V) was estimated in 'Toddlers', with rice and fish meat as the main contributors across population groups. For MMA(V), the highest chronic dietary exposures were estimated for high consumers of fish meat and processed/preserved fish in 'Infants' and 'Elderly' age class, respectively. For MMA(V), an MOE of ≥ 500 was identified not to raise a health concern. For MMA(V), all MOEs were well above 500 for average and high consumers and thus do not raise a health concern. For DMA(V), an MOE of 10,000 was identified as of low health concern as it is genotoxic and carcinogenic, although the mechanisms of genotoxicity and its role in carcinogenicity of DMA(V) are not fully elucidated. For DMA(V), MOEs were below 10,000 in many cases across dietary surveys and age groups, in particular for some 95th percentile exposures. The Panel considers that this would raise a health concern. [ABSTRACT FROM AUTHOR]

Photocatalytic oxidation–adsorption synergistic treatment of organic arsenic pollutants is a promising wastewater treatment technology, which not only degrades organic arsenic pollutants by photocatalytic degradation but also removes the generated inorganic arsenic by adsorption. This paper compares the results of photocatalytic oxidation–adsorption co‐treatment of organic arsenic pollutants such as monomethylarsonic acid, dimethylarsinic acid, phenylarsonic acid, p‐arsanilic acid, and 3‐nitro‐4‐hydroxyphenylarsonic acid on titanium dioxide, goethite, zinc oxide, and copper oxide. It examines the influence of the morphology of organic arsenic molecules, pH, coexisting ions, and the role of natural organic matter. The photocatalytic oxidation–adsorption co‐treatment mechanism is investigated, comparing the hydroxyl radical oxidation mechanism, the hydroxyl radical and superoxide anion radical cooxidation mechanism, and the hydroxyl radical and hole cooxidation mechanism. Finally, the future prospects of metal oxide photocatalytic materials and the development of robust and efficient technologies for removing organic arsenic are envisioned. [ABSTRACT FROM AUTHOR]

Elevated concentrations of arsenic, lithium and boron in drinking water have already been reported in Bolivia. Arsenic is known to cause genotoxicity but that caused by lithium and boron is less well known. The aim of the present cross‐sectional study was to evaluate potential genotoxic effects of exposure to arsenic, while considering exposure to lithium and boron and genetic susceptibility. Women (n = 230) were recruited in villages located around Lake Poopó. Exposure to arsenic was determined as the sum of concentrations of arsenic metabolites inorganic arsenic, monomethylarsonic acid (MMA), and dimethylarsinic acid (DMA) in urine. Exposure to lithium and boron was determined based on their concentrations in urine. Genetic susceptibility was determined by GSTM1 (glutathione S‐transferase‐mu‐1) and GSTT1 (glutathione S‐transferase‐theta‐1) null genotypes and AS3MT (Arsenite Methyltransferase) rs3740393. Genotoxicity was measured in peripheral blood leukocytes using the comet assay. The geometric means of arsenic, lithium, and boron concentrations were 68, 897, and 3972 μg/L, respectively. GSTM1 and GSTT1 null carriers had more DNA strand breaks than gene carriers (p =.008, p =.005). We found no correlation between urinary arsenic and DNA strand breaks (rS =.03, p =.64), and only a weak non‐significant positive association in the adjusted multivariate analysis (β =.09 [−.03;.22], p =.14). Surprisingly, increasing concentrations of lithium in urine were negatively correlated with DNA strand breaks (rS = −.24, p =.0006), and the association persisted in multivariate analysis after adjusting for arsenic (β = −.22 [−.36; −.08], p =.003). We found no association between boron and DNA strand breaks. The apparent protective effect of lithium merits further investigation. [ABSTRACT FROM AUTHOR]

Limited studies have demonstrated that inorganic arsenic exposure is positively associated with serum vitamin D levels, although the correlation between urinary arsenic species and serum vitamin D has not been investigated in areas of water-borne arsenicosis. A cross-sectional study of 762 participants was conducted in Wenshui Country, Shanxi Province, a water-borne arsenicosis area. The results showed a positive relationship between urinary arsenic species (inorganic arsenic (iAs), methylarsonic acid (MMAV), dimethylarsinic acid (DMAV) and serum 25(OH)D. Log-binomial regression analysis indicated a 0.4% increase in the risk of vitamin D excess for every 1-unit increment in the Box–Cox transformed urinary DMAV after adjustment for covariates. After stratifying populations by inorganic arsenic methylation metabolic capacity, serum 25(OH)D levels in the populations with iAs% above the median and primary methylation index (PMI) below the median increased by 0.064 ng/mL (95% CI: 0.032 to 0.096) for every one-unit increase in the Box–Cox transformed total arsenic (tAs) levels. Serum 25(OH)D levels increased by 0.592 ng/mL (95% CI: 0.041 to 1.143) for every one-unit rise in the Box–Cox transformed iAs levels in people with skin hyperkeratosis. Overall, our findings support a positive relationship between urinary arsenic species and serum 25(OH)D. It was recommended that those residing in regions with water-borne arsenicosis should take moderate vitamin D supplements to avoid vitamin D poisoning. [ABSTRACT FROM AUTHOR]

We have adapted a semiautomated method for tracking Caenorhabditis elegans spontaneous locomotor activity into a quantifiable assay by developing a sophisticated method for analyzing the time course of measured activity. The 16‐h worm Adult Activity Test (wAAT) can be used to measure C. elegans activity levels for efficient screening for pharmacological and toxicity‐induced effects. As with any apical endpoint assay, the wAAT is mode of action agnostic, allowing for detection of effects from a broad spectrum of response pathways. With caffeine as a model mild stimulant, the wAAT showed transient hyperactivity followed by reversion to baseline. Mercury chloride (HgCl2) produced an early dose–response hyperactivity phase followed by pronounced hypoactivity, a behavior pattern we have termed a toxicant "escape response." Methylmercury chloride (meHgCl) produced a similar pattern to HgCl2, but at much lower concentrations, a weaker hyperactivity response, and more pronounced hypoactivity. Sodium arsenite (NaAsO2) and dimethylarsinic acid (DMA) induced hypoactivity at high concentrations. Acute toxicity, as measured by hypoactivity in C. elegans adults, was ranked: meHgCl > HgCl2 > NaAsO2 = DMA. Caffeine was not toxic with the wAAT at tested concentrations. Methods for conducting the wAAT are described, along with instructions for preparing C. elegans Habitation Medium, a liquid nutrient medium that allows for developmental timing equivalent to that found with C. elegans grown on agar with OP50 Escherichia coli feeder cultures. A de novo mathematical parametric model for adult C. elegans activity and the application of this model in ranking exposure toxicity are presented. We introduce the 16‐h worm Adult Activity Test (wAAT), which can be used to measure C. elegans spontaneous locomotor activity levels for efficient screening of pharmacological and toxicity induced effects. Acute toxicity, as measured by hypoactivity in C. elegans adults, was ranked: meHgCl > HgCl2 > NaAsO2 = DMA. Caffeine induced only transient mild hyperactivity. Detailed methods including a de novo mathematical parametric model for adult C. elegans activity and the application of this model in ranking exposure effects are presented. [ABSTRACT FROM AUTHOR]

Background: Edible insects may contain arsenic. Analysis of arsenic species is necessary in order to accurately assess arsenic exposure. Objective: An analytical method was validated and used to determine and quantitate arsenic species in edible insects. Methods: Arsenic species were extracted from edible insects by heating at 100°C in 0.3 mol/L nitric acid. The concentration of arsenic species was then determined by LC-inductively coupled plasma-mass spectrometry (LC-ICP-MS) using an octadecylsilane (ODS) column with a mobile phase containing an ion-pair reagent. Results: The LOD (0.007-0.012 mg/kg), LOQ (0.021-0.038 mg/kg), repeatability (1.2-3.2%), intermediate precision (2.8-4.5%), and trueness (recoveries 97-102% based on spiked samples) of the proposed method were satisfactory for inorganic arsenic, dimethylarsinic acid (DMA), and arsenobetaine (AB) in edible insects. Total arsenic was detected in all samples obtained in Japan (Asian forest scorpion, diving beetles, giant water bug, grasshoppers, June beetles, mole crickets, male rhino beetle, female rhino beetle, sago worms, and silkworm pupae) and consisted of mostly inorganic arsenic. Beetles in particular showed relatively high levels. Conclusion: Arsenic content varies among edible insect species. Feed control is important, as arsenic concentrations in edible insects may be feed dependent. Highlights: Arsenic species in edible insects were analyzed by LC-ICP-MS using an ODS column with a mobile phase containing an ion-pair reagent. Inorganic arsenic was detected in most samples, with concentrations ranging from <0.04 to 29.3 mg/kg. [ABSTRACT FROM AUTHOR]

The possibility of regulating the structure and morphology of precipitates forming in the CaO–P2O5–H2O system in the low concentration region during neutralization of acidic solutions with lime milk is studied. The effect of the main technological parameters (temperature and pH) on the crystallization of calcium phosphates from dilute CaO–P2O5–H2O solutions, other conditions being equal, is determined. The formation of dicalcium phosphate under neutralization of the model acidic solutions in the range of pH 4.5–6.5 is reported; at higher pH values, the formation of tricalcium phosphate crystalline hydrate is observed. The formation of hydroxyapatite crystals is not established. It is demonstrated by the physicochemical analysis of the forming precipitates that an increase in the neutralization temperature facilitates an increase in the tricalcium phosphate crystallization rate at lower pH values. [ABSTRACT FROM AUTHOR]

In this report, a new method involving glassy carbon electrodes modified with chitosan (Cs) was tested for the detection of carminic acid (CA) in the presence of allure red by square wave voltammetry. The modified electrode (Cs/GCE) presented activity toward the oxidation of CA at potential values less than 0.3 V The signal is generated from the oxidation of carboxylic acid in the chemical structure of CA. Compared to that of the unmodified electrode, the anodic peak current of the Cs/CGE electrode increased by more than 500 %, and the oxidation potential shifted to a lower potential. This result indicates that the sensitivity increases and the energy to oxidize CA decreases with the Cs/GCE. The optimal parameters were pH 3.0 and PBS buffer, the square wave voltammetry with accumulation time was tACC 30 s, the accumulation potential was EACC 0.0 V, the oxidation signal was proportional to the concentration of CA between 0.99 and 10.90 μmol/L, and the detection limit was 0.20 μmol/L. The relative standard deviation (R.S. D) was 5.0 % using five different electrodes. The Cs/GCE was used for food samples spiked with CA with consistent results [ABSTRACT FROM AUTHOR]

In the current study, we assessed the impact of DMA (dimethylarsinic acid) and MPs (microplastics) interactions in C. elegans over the course of five generations. We found that the redox state of the organisms changed over generations as a result of exposure to both pollutants. From the third generation onward, exposure to MPs reduced GST activity, indicating reduced detoxifying abilities of these organisms. Additionally, dimethylarsinic exposure decreased the growth of organisms in the second, fourth, and fifth generations. In comparison to isolated pollutants, the cumulative effects of co-exposure to DMA and MPs seem to have been more harmful to the organisms, as demonstrated by correlation analysis. These findings demonstrate that DMA, despite being considered less hazardous than its inorganic equivalents, can still have toxic effects on species at low concentrations and the presence of MPs, can worsen these effects. [ABSTRACT FROM AUTHOR]

Dimethylarsinic acid (DMA) is a major metabolite in the urine of humans and rats exposed to inorganic arsenicals, and is reported to induce rat bladder carcinogenesis. In the present study, we focused on early pathways of carcinogenesis triggered by DMA that were also active in tumors. RNA expression in the bladder urothelium of rats treated with 0 and 200 ppm DMA in the drinking water for 4 weeks and in bladder tumors of rats treated with 200 ppm DMA for 2 years was initially examined using microarray analysis and Ingenuity Pathway Analysis (IPA). Expression of 160 genes was altered in both the urothelium of rats treated for 4 weeks with DMA and in DMA-induced tumors. IPA associated 36 of these genes with liver tumor diseases. IPA identified the amphiregulin (Areg)-regulated pathway as a Top Regulator Effects Network. Therefore, we focused on Areg and 6 of its target genes: cyclin A2, centromere protein F, marker of proliferation Ki-67, protein regulator of cytokinesis 1, ribonucleotide reductase M2, and topoisomerase II alpha. We confirmed high mRNA expression of Areg and its 6 target genes in both the urothelium of rats treated for 4 weeks with DMA and in DMA-induced tumors. RNA interference of human amphiregulin (AREG) expression in human urinary bladder cell lines T24 and UMUC3 decreased expression of AREG and its 6 target genes and decreased cell proliferation. These data suggest that Areg has an important role in DMA-induced rat bladder carcinogenesis. • Areg expression was up-regulated in DMA-exposed urothelium and DMA-induced tumors. • Areg regulates proliferation and cell cycle linked genes in rat bladder urothelium. • AREG regulates proliferation and cell cycle linked genes in bladder cancer cells. [ABSTRACT FROM AUTHOR]

Crystalline admixture (CA) can be incorporated into concrete to achieve self-healing of concrete cracks. In this study, both CA and superabsorbent polymer (SAP) were used as self-healing agents to investigate the effects of CA on the self-healing performance and mechanical properties of mortar with internally added SAP at different self-healing ages. The healing effect of cracks in mortar is assessed by crack observation and impermeability. The structure and composition of the filler in the cracks were analyzed by microscopic experiment. The experimental results indicate that CA enhances the healing of cracks in mortar specimens. The chemical reactions of CA primarily contribute to significantly improving the early-age crack-healing ability of the specimens, and the water absorption and expansion ability as well as the internal curing effect of SAP also facilitate the crack-healing process. Increasing the CA content leads to an increase in the Ca/Si ratio of C-S-H, causing a transition from a layered structure to a more compact needle-like structure. When 4% CA was added to the mortar, it resulted in an adequate formation of needle-like C-S-H structures, which eventually penetrate and fill the pits formed by SAP, compensating for the strength loss caused by SAP. [ABSTRACT FROM AUTHOR]

Titanium dioxide (TiO2) and zinc oxide (ZnO) have attracted wide attention due to their photocatalytic properties despite other usages such as pigments in foodstuffs, paint, and cosmetics. They have a high demand due to their broad functionality, long-term stability, and non-toxicity. Although TiO2 and ZnO are good photocatalysts for the degradation of various environmental pollutants, their small adsorption coefficient limits this ability. This work deals with encapsulating TiO2 and ZnO with hollow silica (HS); TiO2-HS and ZnO-HS to increase the surface area adsorption and to control the photocatalytic activity of both catalysts. Sol-gel method through a wet precipitation process following that of the Stober Method was applied to prepare the desired TiO2-HS and ZnO-HS which gave distinct outcomes in the characterization by Brunauer-Emmett-Teller (BET) where TiO2-HS has a reduced surface area compared to the naked TiO2 while ZnO-HS has an increased surface area compared to the naked ZnO. This was proven by further characterizations using FTIR, XRD, and EDX. The physical appearance and morphology of TiO2-HS and ZnO-HS were shown by the FESEM and TEM images. The catalytic activity of TiO2-HS and ZnO-HS was tested in the degradation of dimethylarsinic acid. Results show a lower percentage of degradation by TiO2-HS compared to TiO2 while ZnO-HS gave a higher degradation percentage as compared to ZnO. Thus, the silica doping has been proven to reduce the photocatalytic properties of TiO2 but enhance the photocatalytic activity of ZnO. [ABSTRACT FROM AUTHOR]

Fifty-one rice samples, i.e. 25 rice varieties, 8 rice products, and 18 rice containing baby foods from the Austrian market were surveyed for arsenic, cadmium, and lead. Inorganic arsenic (iAs) is most toxic to human health, and its mean concentrations in rice were 120 µg kg−1, 191 µg kg−1 in rice products, and 77 µg kg−1 in baby foods. The average dimethylarsinic acid and methylarsonic acid concentrations were 56 µg kg−1 and 2 µg kg−1, respectively. The highest iAs concentration was found in rice flakes (237 ± 15 µg kg−1), close to the Maximum Level (ML) set by the EU regulation for husked rice (250 µg kg−1). The levels of cadmium (12 to 182 µg kg−1) and lead (6 to 30 µg kg−1) in the majority of rice samples were below the European ML. Upland grown rice from Austria showed both, low inorganic arsenic (<19 µg kg−1) and cadmium (<38 µg kg−1) concentrations. [ABSTRACT FROM AUTHOR]

Exposures to arsenic and mercury are known to pose significant threats to human health; however, the effects specific to organic vs. inorganic forms are not fully understood. Caenorhabditis elegans' (C. elegans) transparent cuticle, along with the conservation of key genetic pathways regulating developmental and reproductive toxicology (DART)-related processes such as germ stem cell renewal and differentiation, meiosis, and embryonic tissue differentiation and growth, support this model's potential to address the need for quicker and more dependable testing methods for DART hazard identification. Organic and inorganic forms of mercury and arsenic had different effects on reproductive-related endpoints in C. elegans, with methylmercury (meHgCl) having effects at lower concentrations than mercury chloride (HgCl2), and sodium arsenite (NaAsO2) having effects at lower concentrations than dimethylarsinic acid (DMA). Progeny to adult ratio changes and germline apoptosis were seen at concentrations that also affected gravid adult gross morphology. For both forms of arsenic tested, germline histone regulation was altered at concentrations below those that affected progeny/adult ratios, while concentrations for these two endpoints were similar for the mercury compounds. These C. elegans findings are consistent with corresponding mammalian data, where available, suggesting that small animal model test systems may help to fill critical data gaps by contributing to weight of evidence assessments. [ABSTRACT FROM AUTHOR]

A series of electrospun polyvinyl alcohol (PVA) fiber membranes were crosslinked with citric acid (CA) at concentrations of 10, 20, and 30 wt.% (designated as CA10, CA20, and CA30). The effects of CA on the chemical structure, mechanical strength, swelling resistance, and cytotoxicity of the crosslinked PVA fibrous membranes were investigated. Infrared spectroscopy indicated the enhanced esterification of carboxyl and hydroxyl groups between CA and PVA. The modulus and strength of the electrospun PVA membrane increased due to the crosslinking between CA and PVA. The crosslinking of the PVA fiber matrix with CA increased the PVA binding point, thereby increasing the swelling resistance and modulus; however, the concentration of CA used was limited. Results showed that the water absorption of the PVA membranes decreased from 6.58 ± 0.04 g/g for CA10 to 3.56 ± 3.33 g/g for CA20 and 2.85 ± 0.40 g/g for CA30 with increasing CA. The water absorption remained unchanged after the membrane was soaked for a period of time, so no significant difference was found in the water absorption capacity of the same group after immersion from 1 h to 3 d. The tensile strength increased from 20.52 MPa of CA10 to 22.09 MPa of CA20. With an increased amount of CA used for crosslinking, the tensile strength and modulus of CA30 decreased to 11.48 and 13.94 MPa, respectively. Our study also showed that CA was not toxic to L929 cell viability when used for fiber crosslinking at less than 20 wt.% PVA, meaning it may be a good candidate as a support layer for guided tissue engineering. [ABSTRACT FROM AUTHOR]

To assess the association of environmental chemical factors with osteopenia and/or bone fractures. All data were extracted from the National Health and Nutrition Survey (NHANES) 2017–2018 of American adults aged 20–59 years old; invalid data were excluded based on dual-energy X-ray absorptiometry. For the ultimate valid data set, multivariate logistic regression models were applied to evaluate the association of environmental chemical factors with osteopenia and bone fractures. The valid dataset was obtained from 2640 individuals, who completed a questionnaire of demographic characteristics. Urinary manganese and monomethylarsonic acid were positively associated with osteopenia in American adults, but not bone fracture. However, several environmental factors (e.g., arsenous acid, arsenocholine, dimethylarsinic acid, and 2-thioxothiazolidine-4-carboxylic acid) did not affect bone mineral density, but were significantly associated with bone fracture. Multiple environmental chemical factors significantly affect bone mass or fracture risk. However, the risk of environmental chemical factors on fractures is independent of osteopenia in US Adults. The influence of environmental chemical factors on bone quality should be considered and monitored. [ABSTRACT FROM AUTHOR]

The effect of Ca content on chemical stability and electrical properties of Ba 1− x Ca x Ce 0.8 Gd 0.2 O 3−δ (BCCG, 0 ≤ x ≤ 0.06) proton conducting electrolyte is investigated in this work. The BCCG pellets were fabricated via a solid-state reaction method and high-temperature sintering at 1600 °C for 10 h in air. In XRD patterns, BCCG exhibited an orthorhombic phase, and the diffraction peaks of calcium-modified BaCe 0.8 Gd 0.2 O 3−δ (BCG)-based samples shifted toward the high-angle side compared to BCG, indicating that Ca2+ occupies the A site. The chemical stability showed that adding a small amount of Ca2+ improves the stability against water while it deteriorates the stability in CO 2 -containing atmosphere. The highest conductivity was obtained for 1% Ca substitution (x = 0.01, BCCG1), where it increased from 1.1 × 10−3 to 2.8 × 10−3 S cm−1 at 400 °C and from 1.7 × 10−2 to 3.1 × 10−2 S cm−1 at 800 °C compared to that of x = 0. The partial conductivities were greater for BCCG1 compared with BCG material. Proton conductivity was dominant for BCCG1 sample at 600 °C. [Display omitted] • The introduced Ca2+ ions were located in the same positions as the original Ba2+ ions in BaCe 0.8 Gd 0.2 O 3−δ (BCG). • Ba 0.99 Ca 0.01 Ce 0.8 Gd 0.2 O 3−δ showed the highest conductivity in all samples. • Transference numbers of BaCe 0.8 Gd 0.2 O 3−δ and Ba 0.99 Ca 0.01 Ce 0.8 Gd 0.2 O 3−δ were compared. [ABSTRACT FROM AUTHOR]

Arsenic contamination in soil and water is a major problem worldwide. Inorganic arsenic is widely present as arsenate and arsenite. Arsenic is transferred to crops through the soil and irrigation water. It is reported to reduce crop production in plants and can cause a wide array of diseases in humans, including different types of cancers, premature delivery, stillbirth, and spontaneous abortion. Arsenic methyltransferase (AS3MT) in the human body converts inorganic arsenic into monomethylarsonic acid and dimethylarsinic acid, which are later excreted from the body. Arsenic transfer from the soil to grains of rice involves different transporters such as Lsi1, Lsi2, and Lsi6. These transporters are also required for the transfer of silicate, which makes them important for the plant. Different mitigation strategies have been used to mitigate arsenic from crops, such as plant growth-promoting bacteria, fungi, and nanoparticles, as well as using different plant genotypes and plant extracts. Different factors such as nitric oxide, Fe, and jasmonate also affect the response of a plant to the oxidative stress caused by arsenic. This review highlights the various effects of arsenic on plants with respect to their biochemical, molecular, and physiological aspects and the employment of classical and innovative methods for their mitigation. The current review is expected to initiate further research to improve As remediation to mitigate the effect of heavy metal pollution on the environment. [ABSTRACT FROM AUTHOR]

Environmental context: The arsenic content and its speciation in harvested rice are dependent on the genetics of the rice variety, the agricultural practise as well as the speciation of arsenic in the soil. The geochemical conditions and therefore the microbiological regime in the paddy fields can influence the biomethylation of the arsenic in the porewater and therefore can influence the extent of arsenic uptake and its speciation in rice plants. Rationale: Rice is routinely monitored throughout the world for compliance with regulatory limits of inorganic arsenic. Rice grains are well known for their relatively high arsenic concentration in the form of dimethylarsinic acid, methylarsonic acid and inorganic arsenic with other arsenic containing compounds rarely occurring. During a routine survey by the US FDA, an unexpected arsenic compound was noted. Methodology: The compound was eventually identified using a combination of liquid chromatography with elemental (HPLC–ICPMS) and molecular mass spectrometry (HPLC–ESMS) as well as chemical derivatisation. Results: Here we report the identification of the previously unknown arsenical in rice grain, dimethylarsonyldimethylarsinic acid; its origin is unknown. Environmental context. The arsenic content and its speciation in harvested rice are dependent on the genetics of the rice variety, the agricultural practise as well as the speciation of arsenic in the soil. The geochemical conditions and therefore the microbiological regime in the paddy fields can influence the biomethylation of the arsenic in the porewater and therefore can influence the extent of arsenic uptake and its speciation in rice plants. [ABSTRACT FROM AUTHOR]

Arsenic is a known carcinogen and is naturally available in earth's crust. Inorganic arsenic is an environmental pollutant with immunosuppressive properties. Human papillomavirus (HPV) is considered one of the most common sexually transmitted diseases in the United States. HPV is linked to several types of cancers in males, including oral, anal, and penile cancer. However, limited information is available on the effect of arsenic on HPV in males. The purpose of this study was to examine the association of urinary arsenic species (speciated and total) and the prevalence of HPV infection in the male population. HPV prevalence in males was analyzed using the 2013–2014 and 2015–2016 National Health and Nutrition Examination Survey (NHANES) dataset. Logistic regression analysis was used to examine associations of seven types of urinary arsenic species (arsenous acid, arsenic acid, arsenobetaine, arsenocholine, dimethylarsinic acid (DMA), monomethylarsonic acid (MMA), total arsenic acid) with HPV risk for male participants aged 18–59 years (N = 1516). Demographic characteristics were included in the logistic regression model for each arsenic variable. All statistical analyses were conducted by using the software R (version 4.2.0). Increasing DMA was positively associated with the prevalence of low-risk HPV (odds ratio (OR): 1.075, 95% confidence interval (CI): 1.025, 1.128) in addition to the sum of total toxic arsenic species (TUA1) including arsenous acid, arsenic acid, DMA, and MMA (OR: 1.068, 95% CI: 1.022, 1.116). High-risk HPV strains were found to be positively associated with arsenic acid (OR: 1.806, 95% CI: 1.134, 2.876) and total arsenic minus the sum of the two organic arsenic species arsenobetaine and arsenocholine (TUA2) at quartile 3 (Q3) level (OR: 1.523, 95% CI: 1.102, 2.103). The logistic regression models also showed that race and marital status were significant factors related to high-risk HPV. Our study reported that DMA and TUA1 are associated with low-risk HPV and arsenic acid is associated with high-risk HPV infections in males. Future research is required to confirm or refute this finding. [ABSTRACT FROM AUTHOR]

Arsenic, as a human carcinogen, has posed a certain threat to environmental health globally. However, the underlying mechanism of the arsenic carcinogenic effect remains largely undetermined. The up-regulation of MDM2 seems to play a crucial part in tumors in especial carcinomas of the diffuse type. The interaction of MDM2 and p53 is closely relevant to the pathogenesis of tumors. In this study, we aimed to investigate the effect on MDM2, p53, and their phosphorylation after As(III). In the epidemiological study, we investigated that MDM2 expression was up-regulation and was positively linked to methylated metabolites (monomethylarsonic acid (MMA) and dimethylarsinic acid (DMA)) after As(III)-exposure. In vitro studies employing A549 and 16HBE cells confirmed the epidemiological data. Studies on MDM2 phosphorylation sites consisting of Ser166, Ser260, and Ser394 in response to arsenic exposure, which have not been studied presently, indicated that As(III) could induce the expression of MDM2 phosphorylation. Moreover, we studied the alterations of p53 and its N-terminus phosphorylation sites of Ser9, Ser15, and Ser33, which demonstrated that p53 and its phosphorylation were highly expressed after As(III) exposure. Subsequently, Co-immunoprecipitation assays validated our hypothesis that the bonding of MDM2 and p53 was altered by arsenic exposure. What's more, outcomes coming from different cell types of A549, 16HBE, and 60 T-16HBE revealed that MDM2 and its phosphorylation expression existed a significant difference. The study provides evidence that As(III) and its methylated metabolites modulate the expression of MDM2, p53, and their phosphorylation and then affect the interaction between MDM2 and p53. [ABSTRACT FROM AUTHOR]

The effect of calcium (Ca)–cadmium (Cd) interactions on the plant Cd bioaccumulation process may be closely related to the ecological Ca/Cd stoichiometry in the substrate. However, owing to the complexity of plant absorption, accumulation mechanisms and influencing factors, the mechanism of Ca-mediated Cd bioaccumulation and Cd tolerance in Capsicum is still unclear. In this study, the bioaccumulation, subcellular distribution and chemical forms of Cd in Capsicum were analysed via pot experiments to reveal the Ca-mediated Cd bioaccumulation process and its detoxification mechanism under different Ca/Cd stoichiometric ratios. The results revealed that an increase in the substrate Ca/Cd ratio promoted the accumulation of Cd in the roots; restricted the transport of Cd to the stems, leaves and peppers; and promoted the accumulation of Cd in the aboveground leaves but decreased its accumulation in edible parts. Cd was enriched mainly in the cell wall and cell-soluble fraction in each tissue and was enriched in only 1 %–13 % of the organelles. The accumulation of Cd in the cell wall and cell-soluble fractions of roots treated with different Ca concentrations increased by 56.57 %–236.98 % and 64.41 %–442.14 %, respectively. The carboxyl, hydroxyl and amino groups on the root cell wall play important roles in binding and fixing Cd2+. Moreover, the increase in the Ca content also increased the proportion of pectin and protein-bound Cd (F- NaCl), insoluble phosphate-bound Cd (F- C) and insoluble oxalate-bound Cd (F- HCl) in the roots, stems and leaves and reduced the proportion of highly active chemical forms such as inorganic acid salt-bound Cd (F- E) and water-soluble phosphate-bound Cd (F- W). Our study revealed that the bioaccumulation of Cd in Capsicum was influenced by the Ca/Cd ratio and that Ca could alleviate Cd stress by regulating the subcellular distribution and chemical form ratio of Cd in different tissues where the cell wall plays an important role in Cd tolerance and detoxification. [Display omitted] • Ca promoted the accumulation of Cd in roots and reduced its transfer ability. • The subcellular distribution and chemical form were important to reduce Cd toxicity. • Ca adjusted the chemical form of Cd and decreased the activity of Cd. • Ca promoted the immobilization of Cd by cell wall and soluble components of cells. • Cd in cell wall was mainly held by pectin and cellulose, and regulated by Ca. [ABSTRACT FROM AUTHOR]

Investigating natural processes in arsenic (As) polluted areas and plants that have naturally chosen to grow there pose practical restoration recommendations. This study aimed to assess long-term changes in natural As dendroremediation dynamics for Quercus robur L. and Tilia cordata Mill., tree species capable of growing in areas polluted by mining activities. We examined total As and its forms, as well as B, Ca, K, Mg, Na and P, in soil and trees over 5 years. We also characterized pH and EC of soil, examined proline content in tree organs, and calculated Bioconcentration Factor (BCF) and Translocation Factor (TF) for As. Initial As concentrations in soil were 37.0 mg kg⁻1 under Q. robur and 34.7 mg kg⁻1 under T. cordata , significantly decreasing after 5 years to 10.5 mg kg⁻1 and 9.51 mg kg⁻1, respectively. This corresponds to pollution reduction of up to 71.8%. A notable decrease in As(III) and dimethylarsinic acid, along with increase in other organic As forms in soil, was observed. Additionally, concentrations of essential elements in soil, as well as its pH and EC, decreased over time. Both tree species accumulated substantial amounts of As in their organs, but the dynamics of this process were species-specific. During first 4 years, T. cordata accumulated more As and exhibited higher BCF, but in the 5th year, it was clearly surpassed by Q. robur. The highest TF was calculated for Q. robur in year 3, and for T. cordata in years 2 and 3. Generally, limited aboveground movement of As was indicated: BCF >1 were calculated for years 2 and 3, while TF were consistently <1. Proline content increased significantly in all organs, correlating with As, especially in Q. robur. In contrast, Q. robur leaves mapping revealed stable macroelement distributions, but clear variations were observed for T. cordata., which may suggest specific reaction to stress. These findings suggest that both species can effectively restore As-polluted areas, though with different dynamics. The selection of species for dendrorestoration should be based on whether the goal is faster remediation with lesser overall reduction (e.g. T. cordata) or slower remediation with ultimately greater pollution reduction (e.g. Q. robur). [Display omitted] • Forest tree species are able to natural restoration arsenic-polluted post-mining areas. • Arsenic in the soil was reduced from 35.9 ± 3.9 to 10.0 ± 3.0 mg kg−1 in 5 years. • Increasing time-dependent dynamics of the formation of organic arsenic in the soil. • BCF higher for T. cordata during the first 4 years, for Q. robur in the year 5. • TF highest for Q. robur in year 3 and T. cordata in years 2 and 3. [ABSTRACT FROM AUTHOR]

The arsenic (As) content of seaweed has been extensively studied due to its toxicological concerns. As a primary producer, seaweed plays a vital role in the biochemical cycling of As in marine environments. Several studies have focused on the growth and behavior of seaweed under a salinity gradient; however, information related to the impact of salinity on As uptake, biotransformation mechanism, and time-dependent speciation patterns of these plants is limited. This study aimed to investigate the temporal effects of salinity on these factors in seaweed. Three seaweed species, Sargassum fusiforme , Sargassum thunbergii, and Sargassum horneri , were maintained in a 1% Provasoli-enriched seawater medium for 14 d under 5‰, 15‰, 25‰, and 34‰ salinities. The results revealed that the high salinity media promoted a rapid uptake of As by all three species. Arsenic accumulation inside the cell approached 100% within seven days of culture for S. thunbergii, irrespective of the salinity content of the media. In addition, As(V) biotransformation and release by S. fusiforme and S. thunbergii were time-dependent, while S. horneri released dimethylarsinic acid (DMAA) from day 3 of the culture. All seaweed species showed methylation of As(V) to DMAA during the culture period. Furthermore, S. thunbergii released DMAA when As(V) was completely depleted from the culture media, whereas the release by S. fusiforme and S. horneri was relatively earlier than that of S. thunbergii. S. horneri showed minimal tolerance to low salinity, as the cells revealed significant damage. Based on the results of this study, a conceptual model was developed that demonstrated the effects of salinity on As uptake and the biotransformation mechanism of seaweed. [Display omitted] • As(V) uptake by seaweed increased with greater salinity of the medium. • As(V) uptake was faster in Sargassum thunbergii than in S. fusiforme and S. horneri. • Speciation and release of two species depended on time and not As(V) and salinity. • Hyposalinity promoted DMAA(V) release over As(V) uptake. • Sargassum horneri was the least saline-tolerant of the three species. [ABSTRACT FROM AUTHOR]

BACKGROUND: High arsenic exposure has been related to diabetes, but at low-moderate levels the evidence is mixed. Arsenic metabolism, which is partly genetically controlled and may rely on certain B vitamins, plays a role in arsenic toxicity. OBJECTIVE: We evaluated the prospective association of arsenic exposure and metabolism with type 2 diabetes and insulin resistance. METHODS: We included 1,838 American Indian men and women free of diabetes (median age, 36 y). Arsenic exposure was assessed as the sum of inorganic arsenic (iAs), monomethylarsonate (MMA), and dimethylarsinate (DMA) urine concentrations (ΣAs). Arsenic metabolism was evaluated by the proportions of iAs, MMA, and DMA over their sum (iAs%, MMA%, and DMA%). Homeostasis model assessment for insulin resistance (HOMA2-IR) was measured at baseline and follow-up visits. Incident diabetes was evaluated at follow-up. RESULTS: Median ΣAs, iAs%, MMA%, and DMA% was 4.4 μg/g creatinine, 9.5%, 14.4%, and 75.6%, respectively. Over 10,327 person-years of follow-up, 252 participants developed diabetes. Median HOMA2-IR at baseline was 1.5. The fully adjusted hazard ratio [95% confidence interval (CI)] for incident diabetes per an interquartile range increase in ΣAs was 1.57 (95% CI: 1.18, 2.08) in participants without prediabetes at baseline. Arsenic metabolism was not associated with incident diabetes. ΣAs was positively associated with HOMA2-IR at baseline but negatively with HOMA2-IR at follow-up. Increased MMA% was associated with lower HOMA2-IR when either iAs% or DMA% decreased. The association of arsenic metabolism with HOMA2-IR differed by B-vitamin intake and AS3MT genetics variants. CONCLUSIONS: Among participants without baseline prediabetes, arsenic exposure was associated with incident diabetes. Low MMA% was cross-sectional and prospectively associated with higher HOMA2-IR. Research is needed to confirm possible interactions of arsenic metabolism with B vitamins and AS3MT variants on diabetes risk. https://doi.org/10.1289/EHP2566.

In Southeast Asian nations, cultured hybrid groupers are facing serious infestation by the marine parasitic leech Zeylanicobdella arugamensis (Annelida, Hirudinea). They attach to the hybrid groupers by sucking and biting on the surface of the skin, paving the way for secondary infection upon the fish. The objective of the study is to utilize the locally available seaweed to control the infestation of parasitic leeches. The methanol extracts of the brown alga Sargassum polycystum C. Agardh, 1824 (Phaeophyceae) from Sabah were prepared and investigated for antiparasitic efficacy against Z. arugamensis through in vitro bioassay. A total of 126 adult leeches from the host hybrid groupers were obtained from the fish hatchery. The parasitic leeches were treated with the methanol extracts of S. polycystum for 180 min by preparing five different dosages at concentrations of 100, 50, 25, 12.5, and 6.25 mg/mL. The brown alga was found to have high antiparasitic efficacy, resulting in 100% leech mortality over a short period of time. It showed the highest antiparasitic efficacy (total mortality of leeches) in a short time limit of 0.96 ± 0.44 min, for 100 mg/mL of the extract. Observations on leech behavior in the positive control and the seaweed extract treatments showed vigorous swimming before mortality. LC-MS/MS analysis was used to reveal the phytochemical composition of the extract to understand the nature of the main components responsible for its antiparasitic activities. A total of 29 metabolites were identified via Q Exactive HF Orbitrap mass spectrometry, including two flavonoids (ephedrannin A and hinokiflavone), two organoarsenics (1-dimethylarsinoyl-heptadecane and cacodylic acid), four heterocyclic compounds, and two chlorophyll breakdown products. The presence of bioactive compounds could increase the mortality rate of parasitic leeches. Thus, this study concludes that the brown alga showed high efficacy in its antiparasitic activities and can be effectively applied for treatment in grouper aquaculture farms for sustainable aquaculture. [ABSTRACT FROM AUTHOR]

Ingested inorganic arsenic (iAs) is a human carcinogen that is also linked to other adverse health effects, such as respiratory outcomes. Yet, among populations consuming low-arsenic drinking water, the impact of iAs exposure on childhood respiratory health is still uncertain. For a Spanish child study cohort (INfancia y Medio Ambiente—INMA), low-arsenic drinking water is usually available and ingestion of iAs from food is considered the major source of exposure. Here, we explored the association between iAs exposure and children's respiratory outcomes assessed at 4 and 7 years of age (n = 400). The summation of 4-year-old children's urinary iAs, monomethylarsonic acid (MMA), and dimethylarsinic acid (DMA) was used as a biomarker of iAs exposure (∑As) (median of 4.92 μg/L). Children's occurrence of asthma, eczema, sneeze, wheeze, and medication for asthma and wheeze at each assessment time point (i.e., 4- and 7-year) was assessed with maternal interviewer-led questionnaires. Crude and adjusted Poisson regression models using Generalized Estimating Equation (GEE) were performed to account for the association between natural logarithm transformed (ln) urinary ∑As in μg/L at 4 years and repeated assessments of respiratory symptoms at 4 and 7 years of age. The covariates included in the models were child sex, maternal smoking status, maternal level of education, sub-cohort, and children's consumption of vegetables, fruits, and fish/seafood. The GEE—splines function using Poisson regression showed an increased trend of the overall expected counts of respiratory symptoms with high urinary ∑As. The adjusted expected counts (95% confidence intervals) at ln-transformed urinary ∑As 1.57 (average concentration) and 4.00 (99th percentile concentration) were 0.63 (0.36, 1.10) and 1.33 (0.61, 2.89), respectively. These exploratory findings suggest that even relatively low-iAs exposure levels, relevant to the Spanish and other populations, may relate to an increased number of respiratory symptoms during childhood. [ABSTRACT FROM AUTHOR]

Chemical diffusion of Ca has been characterized in natural enstatite under buffered conditions (IW, NNO) and in air. Experiments were conducted using synthesized powder sources, with Ca diffusion profiles measured with Rutherford Backscattering Spectrometry. A variety of sources of diffusant were used to investigate the effects of silica activity and Ca concentration on diffusion. Calcium diffusion appears relatively insensitive to crystallographic orientation and oxygen fugacity under the range of investigated conditions, and also appears little influenced by differences in silica activity and Ca concentration in the diffusant source. For Ca diffusion in a natural enstatite, we obtain the following Arrhenius relation for diffusion over the temperature range 750–1150 °C, D = 1.17 × 10−10exp(−240 ± 10 kJ mol−1/RT) m2sec−1. Calcium diffusion is slower than Mg, Cr and Fe in enstatite, but faster than larger divalent cations Pb and Eu that also are likely to preferentially occupy the M2 site. Calcium diffusion is also faster than that for trivalent REE and tetravalent Ti in enstatite. Calcium diffusivities in enstatite are intermediate between Ca diffusivities in clinopyroxene and olivine, with Ca diffusion in enstatite about 2 orders of magnitude faster than Ca self-diffusion in diopside and 2 orders of magnitude slower than Ca diffusion in olivine. Diffusion parameters obtained from this study were used to develop a simple model for closure temperature of the Ca-in-opx thermometer of Brey and Köhler (1990). By coupling closure temperature and the Ca-in-opx thermometer, it is possible to constrain cooling rates of peridotites and pyroxenites. Applications to peridotites from the Lanzo Massif and the Oman ophiolite are presented. [ABSTRACT FROM AUTHOR]

Seaweeds consumption is one of main internal exposure sources of arsenic for human. However, the absence of representative bio-availabilities of arsenic species makes the accurate assessment of arsenic health risk originating from seaweeds consumption impossible. Herein, the arsenic species in various seaweeds collected from Fujian of China were investigated, and the bio-accessibilities/bio-availabilities of arsenic species existing in seaweeds were evaluated in vitro and in vivo. Results revealed that in vitro bio-availabilities of arsenic species presenting in seaweeds, which obtained with Caco-2 cells, were lower than those of pure arsenic standards, and varied with order of inorganic arsenic (iAs) > dimethylarsinic acid (DMA) ≈ arsenobetaine (AsB) > arsenosugars. During gastrointestinal digestion of mice, As 5+ was partly methylated into monomethylarsonic acid (MMA) and DMA, which makes the in vivo bioavailability of iAs (⁓31.8 %) obtained with mouse metabolic experiment is much higher than its in vitro bio-availability (⁓10.3 %). The in vivo bio-availabilities of DMA and total arsenic (tAs) are similar to their in vitro bio-availabilities. As the dominant arsenic species in most seaweeds, arsenosugars have an ⁓0.0 % of in vivo bioavailability and only a ⁓3.7 % of in vitro bioavailability. The simulated calculation of target hazard quotient (THQ) and target cancer risk (TR) revealed that the arsenic risk originating from seaweeds was greatly degraded by taking into consideration of arsenic species and bio-availabilities, and all seaweeds collected from Fujian are safety for consumption. The simulated calculation also revealed that arsenic risk of seaweeds can be also more accurately assessed based on tAs together with bioavailability, which provides a simple but accurate and protective method for the risk assessment of arsenic originating from seaweeds. Our work provides the possible representative bio-availabilities of arsenic species presenting in seaweeds for accurately assessing arsenic risk of seaweeds, and novel insights into the bio-availabilities of arsenic in animal., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

The limitation of using a standardized method for the determination of total arsenic in water samples containing various organoarsenic compounds by the hydride generation technique in combination with atomic absorption spectrometry is presented in the publication. The study was carried for aqueous solutions of the organoarsenic compounds with significantly different molecular structures such as: dimethylarsinic acid, phenylarsonic acid and p-arsanilic acid and mixtures thereof. It was found that, the percentage arsenic concentration determination by hydride generation atomic absorption spectrometry in relation to the total content of the element in the samples depends on the structure of organoarsenic compound. The determination of As by hydride generation in water samples solutions containing various inorganic and organic forms of arsenic species is challenging. [ABSTRACT FROM AUTHOR]

This work focuses on providing fast and reliable separations of arsenobetaine (AsB), trimethylarsine oxide (TMAO), dimethylarsinic acid (DMA), monomethylarsonic acid (MMA), arsenocholine (AsC), arsenite (As(III)), and arsenate (As(V)). Two different methods are presented: (1) a one-column method for the determination of AsB, DMA, MMA, AsC, As(III), and As(V) with a separation time of ∼2 minutes and (2) a two-column method for the determination of AsB, TMAO, DMA, MMA, AsC, As(III), and As(V) with a separation time of ∼4.5 minutes. Recovery of the two methods falls between 94 and 107%. Methods were evaluated for accuracy by analyzing proficiency samples from Centre de Toxicologie du Québec (CTQ) and New York Department of Health (NYDOH). Correlation between the measured values and reference values was very good, with a <4.5% difference in results. Limits of detection in a urine matrix ranged from 2.8–6.0 ng L−1 As and 4.1–9.1 ng L−1 As for the one- and two-column methods, respectively. [ABSTRACT FROM AUTHOR]

Although arsenic (As) is a persistent contaminant in the environment, few studies have assessed its effects over generations, as it requires an animal model with a short lifespan and rapid development, such as the nematode Caenorhabditis elegans. Furthermore, few studies have evaluated the effects of As metabolites such as dimethylarsinic acid (DMAV), and several authors have considered DMA as a moderately toxic intermediate of As, although recent studies have shown that this chemical form can be more toxic than inorganic arsenic (iAs) even at low concentrations. In the present study, we compared the toxic effects of arsenate (AsV) and DMAV in C. elegans over 5 subsequent generations. We evaluated biochemical parameters such as reactive oxygen species (ROS) concentration, the activity of antioxidant defense system (ADS) enzymes such as catalase (CAT) and glutathione-S-transferase (GST), and nonenzymatic components of ADS such as reduced glutathione (GSH) and protein-sulfhydryl groups (P-SH). Exposure to 50 μg L−1 of AsV led to an increase in ROS generation and GSH levels together with a decrease in GST activity, while exposure to DMAV led to an increase in ROS levels, with an increase in lipid peroxidation, CAT activity, and a decrease in GSH levels. In addition, both treatments reduced animal growth from the third generation onward and caused disturbances in their reproduction throughout all 5 generations. This study shows that the accumulated effects of DMA need to be considered; it highlights the importance of this type of multigenerational approach for evaluating the effects of organic contaminants considered low or nontoxic. [ABSTRACT FROM AUTHOR]

It is well established that arsenic (As) has many toxic compounds, and in particular, inorganic As (iAs) has been classified as a type-1 carcinogen. The measuring of As species in rice flour is of great importance since rice is a staple of the diet in many countries and a major contributor to As intake in the Asian diet. In this study, several solvents and techniques for the extraction of As species from rice flour samples prior to their analysis by HPLC-ICP-MS were investigated. The extraction methods were examined for their efficiency in extracting various arsenicals from a rice flour certified reference material, NMIJ-7532a, produced by the National Metrology Institute of Japan. Results show that ultrasound-assisted extraction at 60 °C for 1 h and then heating at 100 °C for 2.5 h in the oven using a thermostable α-amylase aqueous solution was highly effective in liberating the arsenic species. The recoveries of iAs and dimethylarsinic acid (DMA) in NMIJ-7532a were 99.7% ± 1.6% (n = 3) and 98.1% ± 2.3% (n = 3), respectively, in comparison with the certificated values. Thus, the proposed extraction method is a green procedure that does not use any acidic, basic, or organic solvents. Moreover, this extraction method could effectively maintain the integrity of the native arsenic species of As(III), As(V), monomethylarsonate (MMA), DMA, arsenobetaine (AsB) and arsenocholine (AsC). Under the optimum extraction, chromatography and ICP-MS conditions, the limits of detection (LOD) obtained were 0.47 ng g−1, 1.67 ng g−1 and 0.80 ng g−1 for As(III), As(V) and DMA, respectively, while the limits of quantification (LOQ) achieved were 1.51 ng g−1, 5.34 ng g−1 and 2.57 ng g−1 for As(III), As(V) and DMA, respectively. Subsequently, the proposed method was successfully applied to As speciation analysis for several rice flour samples collected from contaminated areas in China. [ABSTRACT FROM AUTHOR]

The unprecedented use of high-resolution continuum source molecular absorption spectrometry (HR-CS MAS) for the fractionation of organic and inorganic sulfur (S) species through monitoring the CS molecule is presented here. Two separate methods for determining organic (CS org) and inorganic (CS ino) sulfur were developed to work sequentially. The optimized temperature program for both methodologies has two pyrolysis steps and one vaporization step (1st T pyr : 1800 and 2ndT pyr : 800 °C, and T vap : 2500 °C). The fractionation was achieved by implementing hydrophobic Pd NPs and Ca as chemical modifiers for the CS org and CS ino methods. Method development was performed by applying different statistical models, allowing the definition of optimal conditions for the chemical modifier mass, and minimizing the S species interconversion, i.e., Doehlert design, and central composite design. The limits of detection (LoD) for CS org and CS ino were 2.4 and 2.1 mg L−1, respectively. Recovery tests evaluated the method's specificity and accuracy; over 92 % recovery was found for both CS org and CS ino. Thus, the proposed methods offer a reliable alternative for fractionating organic and inorganic S by using HR-CS MAS. [Display omitted] • HR-CS MAS was used for the fractionation of inorganic and organic sulfur compounds. • Ionic Ca and Pd NPs were employed as chemical modifiers to promote fractionation. • The quantification of inorganic and organic sulfur species in coal was possible. [ABSTRACT FROM AUTHOR]

• The error of the CA method caused by grid anisotropy are analyzed. • Five methods to avoid the grid anisotropy are compared. • The application scope of each method are summarized. • B-Z reaction and crystal process are selected for case study. Cellular Automata (CA) is a qualitative simulation method widely used in complex systems. However, the anisotropy of the bottom grid is influenced by the sharp boundary, which leads to the problem of grid-induced anisotropy. It not only makes the CA show the anisotropy in the simulation of isotropic propagation, but also produces errors in the simulation of anisotropic propagation. Through a simple binary CA simulation, this paper discusses reasons and processes of grid anisotropy from three aspects: cellular space, neighbor rules and evolution rules, and the error between CA simulation and standard circle propagation is evaluated. Afterwards, five methods for reducing grid anisotropy are introduced and compared in isotropic and anisotropy propagation simulation. For illustration purpose, these methods are considered in the actual system of isotropic and anisotropic propagation, and then the CA model is successfully applied to the classical isotropic propagation, i.e. the chemical wave in B-Z reaction-diffusion system, and classical anisotropic propagation, i.e. the dendritic growth in crystallization system. The results show that the composition shape of neighboring cells affects the isotropic propagation process of CA simulation, and the square grid is one of potential upgrading methods. The weight of neighbors algorithm is more suitable for simulating diffusion processes, and the limited circular neighbourhood algorithm is more suitable for crystal growth process. These results can be a reference for quantitative application of CA in fields of chemical wave propagation and dendrite growth. [ABSTRACT FROM AUTHOR]

Arsenic (As) remediation is challenging due to the complex nature and the persistence of these metalloid compounds. While it may seem that differences between As forms influence have been extensively described, new findings challenge the previously accepted knowledge, particularly for woody plants. Therefore, this study focused on 2-year-old Tilia cordata Mill. seedlings early (0, 2, 4, 12, 24 h) and late (3, 7, 12, 18, 25, 33 days) responses during growth under: As(III), As(V) or dimethylarsinic acid (DMA) (0.3 mM). Time-dependent transformations of As forms, distribution in plants, and microbiological characteristics (actinobacteria, bacteria, fungi, enzyme activity) were investigated. The highest increase in total As content was observed in plants exposed to As(V) and As(III). Dynamic metalloid form changes in the solution and tree organs were indicated. The most phytotoxic was DMA. This form was the main factor limiting the growth and effective accumulation of As. Despite experimenting in hydroponics, microorganisms played an important role in As form transformations, suggesting the potential for microbial-assisted dendroremediation strategies. The study confirmed that trees can convert more toxic forms into less toxic ones (e.g. As(III) to phytochelatins - As(III)-(PC 3)), whose presence in roots seedlings exposed to As(III) and As(V) has been identified. The formation of hydrophobic forms (e.g. dimethylarsinoyl lipid) in the roots of seedlings grown under As(V) was confirmed. It is the first discovery for trees, previously observed only in bacteria and algae. The dynamics of metalloid form changes indicated that T. cordata transforms As forms according to their needs, which may give tree species an advantage in phytoremediation techniques. It holds great promise for the potential of dendroremediation. [Display omitted] • Biotransformation of As forms began at the first hours of tree seedlings growth. • Phytotoxicity for T. cordata seedlings decreased as follows: DMA > As(III) > As(V). • Low concentrations of As(V) in solution stimulated seedlings' biomass increase. • T. cordata seedlings have ability to convert more toxic into less toxic As forms. • First discovery hydrophobic As forms (e.g. dimethylarsinoyl lipid) in tree roots. [ABSTRACT FROM AUTHOR]

The arsenic (As) methylation capacity is an important determinant of susceptibility to As-related diseases. Total As (TAs) or inorganic As (iAs) was reported to associated with As methylation capacity. We measured urinary concentrations of iAs, monomethylarsonic acid (MMA), and dimethylarsinic acid (DMA) by using HPLC-HG-AFS and calculated the primary methylation capacity index (PMI) and secondary methylation capacity index (SMI) in 209 university students in Hefei, China, a non-As endemic area. Volunteers were given a standardized questionnaire asking about their sociodemographic characteristics. Bayesian kernel machine regression (BKMR) analysis was used to estimate the association of lnTAs and lniAs levels with methylation indices (ln%MMA, ln%DMA, lnPMI, lnSMI). The median concentrations of iAs, MMA, and DMA were 1.22, 0.92, and 12.17 μg/L, respectively; the proportions of iAs, MMA, and DMA were 8.76%, 6.13%, and 84.84%, respectively. Females had higher %DMA and lower %MMA than males. The combined levels of lnTAs and lniAs showed a decrease in the changes in ln%DMA and lnSMI. With regard to the single exposure level, the lnTAs showed positive correlations with ln%DMA, lnPMI, and lnSMI when lniAs was set at a specific level, while lniAs showed negative correlations with ln%DMA, lnPMI, and lnSMI when lnTAs was set at a specific level; all the dose-response relationships were nonlinear. Our results suggested that combined levels of TAs and iAs play an important role in reducing As methylation capacity, especially iAs, and the reduction only occurs when TAs and iAs are present up to a certain combined level. [ABSTRACT FROM AUTHOR]

Caffeic acid (CA) is found abundantly in fruits, vegetables, tea, coffee, oils, and more. CA and its derivatives have been used for many centuries due to their natural healing and medicinal properties. CA possesses various biological and pharmacological activities, including antioxidant, anti-inflammatory, anticancer, and neuroprotective effects. The potential therapeutic effects of CA are mediated via repression and inhibition of transcription and growth factors. CA possesses potential anticancer and neuroprotective effects in human cell cultures and animal models. However, the biomolecular interactions and pathways of CA have been described highlighting the target binding proteins and signaling molecules. The current review focuses on CA's chemical, physical, and pharmacological properties, including antioxidant, anti-inflammatory, anticancer, and neuroprotective effects. We further described CA's characteristics and therapeutic potential and its future directions. [ABSTRACT FROM AUTHOR]

Dimethylmonothioarsinic acid (DMMTA(V)) and dimethyldithioarsinic acid (DMDTA(V)), which are commonly found in landfill leachate and pore water of rice paddy soil, have attracted considerable attention for their high toxicity. This study aims to evaluate the behavior and potential risks of DMMTA(V) and DMDTA(V) in the environment by conducting an equilibrium sorption test using 2-line ferrihydrite and acute toxicity (immobilization) test using Daphnia magna. The overall maximum sorption capacity (qm) derived by the Langmuir isotherm model showed an increase in the order of inorganic arsenate (As(V)) > dimethylarsinic acid (DMA(V)) > DMMTA(V) > DMDTA(V), which was likely due to steric hindrance due to the presence of methyl and thiol groups. Moreover, DMMTA(V) and DMDTA(V) showed no or negligible change in qm with pH change, while qm decreased rapidly with increasing pH in As(V) and DMA(V). The 50% inhibition concentrations (IC50) for As(V), DMA(V), DMMTA(V), and DMDTA(V), which were measured after 48 h exposure to D. magna, were 9.5, > 30, 1.7, and 6.5 mg/L, respectively. Overall, the results demonstrated that DMMTA(V) and DMDTA(V) have high mobility and eco-toxicity in the environment and that methylated thioarsenicals should be accurately monitored and controlled. [ABSTRACT FROM AUTHOR]

Arsenic is a known carcinogen and neurotoxin and is found in the natural earth crust. Arsenic exposure can develop depression, memory dysfunction, and neurodegenerative disorder. The mechanism of arsenic toxicity on the nervous system is not known. There is a lack of research on the association between arsenic exposure and sleep disturbance in humans. This study aims to investigate the relationship between six types of urinary speciated arsenic exposure and sleep disturbance in adults from the general population using the National Health and Nutrition Examination Survey (NHANES) 2015–2016 dataset. Sleep disturbance was measured using self-reported questionnaires, asking participants if they had ever told a doctor they had trouble sleeping. We utilized multivariate logistic regression analysis using complex survey procedures to examine the association between six types of urinary arsenic concentration and trouble sleeping. The total sample included 1,611 adults who were 20 years and older. Of the study participants, 30.0% had trouble sleeping. Compared to individuals with urinary arsenous acid below the lower level of detection (LLOD), those with urinary arsenous acid at or above the detection limit had lower odds of trouble sleeping [odds ratio: 0.72 (95% confidence interval 0.51–1.00, p-value: 0.05)]. The other five types of urinary speciated arsenic studied (arsenic acid, arsenobetaine, arsenocholine, dimethylarsinic acid, monomethylarsonic acid) were not associated with a sleep disorder. More studies are required to confirm or refute these findings. [ABSTRACT FROM AUTHOR]

• Method to analyze arsenic species in human RBCs was provided and validated. • Arsenic profile of plasma and RBCs from APL patients treated with ATO was confirmed. • MMA was the predominant methylated arsenic in RBCs of APL patients treated with ATO. • Binding ability of As species in human RBCs was evaluated in vivo for the first time. • High affinity with human Hb was responsible for the accumulation of arsenic in RBCs. Arsenic trioxide (ATO) has been successfully applied in the treatment of acute promyelocytic leukemia (APL). Arsenic metabolites including inorganic arsenic and methylated arsenic could lead to different toxicity and curative effect. This study aims to establish a method to determine arsenic species in red blood cells (RBCs), clarify the distribution characteristics of arsenic species in RBCs. Steady state blood samples were collected from 97 APL patients. H 2 O 2 and HClO 4 were used to release the hemoglobin bounding arsenic and precipitate protein. Arsenite (iAsIII), arsenate (iAsV), monomethylarsonic acid (MMAV) and dimethylarsinic acid (DMAV) in plasma and RBCs were detected by HPLC-HG-AFS. Free and bound arsenic species in RBCs were separated by 30 kDa molecular mass cutoff filters and determined to evaluate hemoglobin binding capacity of different arsenic species. The method was validated with accuracy ranged from 84.75% to 104.13%. Arsenic species in RBCs followed the trend iAs > MMA > DMA (p < 0.01), while the concentration of DMA was significantly higher than iAs and MMA in plasma (p < 0.01). The correlation between iAs concentration in plasma and corresponding RBCs arsenic level was weak. And the concentrations of DMA and MMA in plasma were moderately positive correlated with those in RBCs. Hemoglobin-binding ratios of iAs, MMA and DMA were all over 70 %. In this study, we provided a reliable method to determine arsenic species in RBCs of APL patients treated with ATO by HPLC-HG-AFS. It was confirmed that the concentration of DMA is the highest in plasma, while MMA is the most predominant methylated arsenic in RBCs. High affinity of MMA with human Hb was responsible for the accumulation of arsenic in RBCs of APL patients. [ABSTRACT FROM AUTHOR]

Synchrotron powder diffraction data is presented for the monoclinic polymorph of dimethylarsinic acid, (CH3)2AsO(OH) (DMAV). Rietveld refinement with GSASII yielded lattice parameters of a = 15.9264(15) Å, b = 6.53999(8) Å, c = 11.3401(9) Å, and β = 125.8546(17)° (Z = 8, space group C2/c). The Rietveld-refined structure was compared with both a density functional theory (DFT)-optimized structure and the published, low-temperature single-crystal structure, and all three structures exhibited excellent agreement. The triclinic polymorph of DMAV was also DFT optimized with CRYSTAL17 to determine the positions of the hydrogen atoms. Monoclinic DMAV forms zigzag chains parallel to the b-axis with adjacent DMAV molecules connected by an O–H⋯O bond, whereas triclinic DMAV forms dimers connected by two O–H⋯O bonds. [ABSTRACT FROM AUTHOR]

GaAs growth by hydride vapor phase epitaxy (HVPE) has regained interest as a potential route to low cost, high efficiency thin film photovoltaics. In order to attain the highest efficiencies, deep level defect incorporation in these materials must be understood and controlled. The arsenic anti-site defect, AsGa or EL2, is the predominant deep level defect in HVPE-grown GaAs. In the present study, the relationships between HVPE growth conditions and incorporation of EL2 in GaAs epilayers were determined. Epitaxial n-GaAs layers were grown under a wide range of deposition temperatures (TD) and gallium chloride partial pressures (PGaCl), and the EL2 concentration, [EL2], was determined by deep level transient spectroscopy. [EL2] agreed with equilibrium thermodynamic predictions in layers grown under conditions in which the growth rate, RG, was controlled by conditions near thermodynamic equilibrium. [EL2] fell below equilibrium levels when RG was controlled by surface kinetic processes, with the disparity increasing as RG decreased. The surface chemical composition during growth was determined to have a strong influence on EL2 incorporation. Under thermodynamically limited growth conditions, e.g., high TD and/or low PGaCl, the surface vacancy concentration was high and the bulk crystal was close to equilibrium with the vapor phase. Under kinetically limited growth conditions, e.g., low TD and/or high PGaCl, the surface attained a high GaCl coverage, blocking As adsorption. This competitive adsorption process reduced the growth rate and also limited the amount of arsenic that incorporated as AsGa. A defect incorporation model which accounted for the surface concentration of arsenic as a function of the growth conditions, was developed. This model was used to identify optimal growth parameters for the growth of thin films for photovoltaics, conditions in which a high growth rate and low [EL2] could be attained. [ABSTRACT FROM AUTHOR]

Yellowknife, Northwest Territories, Canada, is located near two closed gold mines. Elevated arsenic concentrations reported in fish are a public health concern. We collected 180 samples of three species of commonly consumed fish in 2013–2018 and analyzed arsenic species, including inorganic arsenic (As(III) and As(V)), monomethylarsonate (MMA), dimethylarsinic acid (DMA), and arsenobetaine. The average total arsenic concentration in fish muscle tissue was 2.30 ± 1.72 µg/g dry weight, and that in burbot liver tissue was 3.16 ± 2.49 µg/g dry weight. Nontoxic arsenobetaine was the main arsenic species in fish muscle (mean = 58.6 ± 34.5%), whereas DMA was the predominant species in burbot liver (mean = 76.6 ± 21.6%). On average, inorganic arsenic species accounted for less than 20% of the arsenic detected in fish. Data on the consumption of locally caught fish were collected from 1611 residents in Yellowknife in 2017 and 2018, including 1417 general residents and 194 members of the Yellowknives Dene First Nation. We evaluated the health risks from inorganic arsenic exposure using Monte Carlo simulations. Our results indicated that there were negligible non-cancer health risks, and the cancer risk was below the baseline cancer risk level of arsenic exposure among the Canadian general population. [ABSTRACT FROM AUTHOR]

The present study used various amounts of P-arsanilic acid (AsA) in pot experiments to evaluate the effects of AsA on arsenic (As) accumulation, speciation and meanwhile using the in vitro digestion/Caco-2 cell model to evaluate the bioavailability of As in rice. The results indicated a linear relationship between As in rice and As in soil, and at 75 mg AsA/kg of soil, As content in rice exceeded the statutory permissible limit of 0.2 mg As/kg dry weight in China. Speciation studies indicated that inorganic As (Asi), dimethylarsinic acid (DMA), and monomethylarsonic acid (MMA) were the main As species in rice. Bioavailability of As experiment indicated that As uptake and transport amount by Caco-2 cells increased with increasing As accumulation in rice. In general, the content of AsA in soil reached or exceeded 75 mg/kg, which is not suitable for growing rice. [ABSTRACT FROM AUTHOR]

Dietary patterns provide a comprehensive assessment of food consumption, including essential nutrients and potential exposure to environmental contaminants. While pro-vegetarian (PVG) dietary patterns have shown health benefits in adults, their effects on children are less well studied. This study aims to explore the association between children's adherence to the most common PVG dietary patterns and their exposure to metals, assessed through urine concentration. In our study, we included a population of 723 children aged 4-5-years from the INfancia y Medio Ambiente (INMA) cohort in Spain. We calculated three predefined PVG dietary patterns, namely general (gPVG), healthful (hPVG), and unhealthful (uPVG), using dietary information collected through a validated Food Frequency Questionnaire. Urinary concentrations of various essential and heavy metals (Co, Cu, Zn, Se, Mo, Pb, and Cd) were measured using mass spectrometry. Additionally, urinary arsenic speciation, including arsenobetaine (AsB), dimethylarsinic acid (DMA), monomethylarsonic acid (MMA), and inorganic arsenic (iAs), was measured. The sum of urinary MMA and iAs was used to assess iAs exposure. We estimated primary (PMI) and secondary iAs methylation (SMI) indices. To explore the association between PVG dietary patterns in quintiles and metal exposure, we utilized multiple-adjusted linear regression models and the quantile g-computation approach. Compared with the lowest quintile, participants in the highest quintile of gPVG showed a 22.7% lower urinary Co (95% confidence interval (CI): −38.7; −1.98) and a 12.6% lower Se (95%CI: −22.9; −1.00) concentrations. Second quintile of adherence to hPVG was associated with a 51.7% lower urinary iAs + MMA concentrations (95%CI: −74.3; −8.61). Second quintile of adherence to an uPVG was associated with a 13.6% lower Se levels (95%CI: −22.9; −2.95) while the third quintile to this pattern was associated with 17.5% lower Mo concentrations (95%CI: −29.5; −2.95). The fourth quintile of adherence to gPVG was associated with a 68.5% higher PMI and a 53.7% lower SMI. Our study showed that adherence to a gPVG dietary pattern in childhood may modestly reduce the intakes of some essential metals such as Co and Se. Further investigations are warranted to explore any potential health implications. [ABSTRACT FROM AUTHOR]

Arsenic species patterns in urine are associated with risk for cancer and cardiovascular diseases. The organic anion transporter coded by the gene SLCO1B1 may transport arsenic species, but its association with arsenic metabolites in human urine has not yet been studied. The objective of this study is to evaluate associations of urine arsenic metabolites with variants in the candidate gene SLCO1B1 in adults from the Strong Heart Family Study. We estimated associations between % arsenic species biomarker traits and 5 single-nucleotide polymorphisms (SNPs) in the SLCO1B1 gene in 157 participants, assuming additive genetics. Linear regression models for each SNP accounted for kinships and were adjusted for sex, body mass index, and study center. The minor allele of rs1564370 was associated with lower %MMA (p = .0003) and higher %DMA (p = .0002), accounting for 8% of the variance for %MMA and 9% for %DMA. The rs1564370 minor allele homozygote frequency was 17% and the heterozygote frequency was 43%. The minor allele of rs2291075 was associated with lower %MMA (p = .0006) and higher %DMA (p = .0014), accounting for 7% of the variance for %MMA and 5% for %DMA. The frequency of rs2291075 minor allele homozygotes was 1% and of heterozygotes was 15%. Common variants in SLCO1B1 were associated with differences in arsenic metabolites in a preliminary candidate gene study. Replication of this finding in other populations and analyses with respect to disease outcomes are needed to determine whether this novel candidate gene is important for arsenic-associated disease risks.