Monomethylarsenic Acid Research Articles

Study of Arsenic Contamination in the Caplina Basin, Tacna, Peru: Arsenite and Arsenate Analysis Using Inductively Coupled Plasma Mass Spectrometry and High-Performance Liquid Chromatography

This study examines arsenic contamination in the Caplina Basin, Tacna, Peru, focusing on arsenic speciation and associated risks in surface waters. Arsenic concentrations were quantified using inductively coupled plasma mass spectrometry (ICP-MS) and high-performance liquid chromatography (HPLC). Total arsenic levels ranged from 0.0304 mg/L to 0.0730 mg/L across all monitoring points, exceeding the World Health Organization (WHO) limit of 10 µg/L (0.01 mg/L) for drinking water. Arsenite (As(III)), the most toxic and mobile species, reached levels up to 0.0154 mg/L, posing a significant concern at Point 7, characterized by acidic pH (3.82) and high conductivity (1456 µS/cm). Arsenate (As(V)), less toxic but predominant under alkaline conditions, peaked at 0.0260 mg/L at Point 6 (pH 8.42). Organic species such as dimethylarsenic acid (DMA) and monomethylarsenic acid (MMA) were also detected, indicating active methylation processes and anthropogenic influences. The risk assessment revealed carcinogenic risk values ranging from 2.56 × 10⁻⁵ to 6.28 × 10⁻⁵, below the USEPA threshold (1 × 10⁻⁴), but significant for prolonged exposure. Non-carcinogenic hazard quotient (HQ) values ranged from 0.09 to 0.21. These findings highlight severe public health implications and emphasize the urgent need for comprehensive strategies, including continuous monitoring, targeted treatment technologies, and community education, in order to guarantee water quality in vulnerable areas.

The alleviation effect and its mechanism of Niuhuang Jiedu prescription on realgar-induced genotoxicity in mice

Realgar (As2S2 or As4S4) is a traditional Chinese medicine (TCM) containing arsenic. Existing studies have shown that it has genotoxicity under long-term use with large doses. Niuhuang Jiedu (NHJD) is a Chinese medicine prescription containing realgar and seven other TCMs. Whether the multiple TCMs combination in NHJD can reduce the genotoxicity induced by realgar in equivalent doses is still unknown. To research the effect of NHJD on realgar's genotoxicity and the possible mechanism involved based on the arsenic methylation metabolic pathway. Six groups (control, realgar (0.8 g/kg), NHJD (12.48g/kg), as well as Glycyrrhiza uralensis Fisch (GU), Scutellaria baicalensis Georg (SB), Rheum palmatum L (RP) plus equivalent doses of realgar, respectively) were set up. ICR mice were intragastric administered for 12 weeks. First, genotoxicology tests were conducted to evaluate the effect of NHJD, GU, SB, and RP on reducing realgar's genotoxicity. The inorganic arsenic (iAs), dimethyl arsenic acid (DMA), and monomethyl arsenic acid (MMA) were determined by HPLC-AFS, and the iAs%, MMA%, DMA%, primary methylation index (PMI), etc. Were calculated. Meanwhile, the S-adenosyl methionine (SAM) and arsenate reductase (ARR) levels, the arsenic (+3)methyltransferase (As3MT), purine-nucleoside phosphorylase (PNP), glutathione S-transfer omega1 (GSTO1) gene expression were detected, aimed to explore the possible alleviation mechanisms of NHJD. The combination of multiple TCMs in NHJD decreased the levels of MN‰, SPA%, and DNA damage caused by realgar, with similar effects observed when SB, RP, and GU were used separately with realgar. Notably, the iAs% significantly decreased, while DMA% and PMI notably increased in the NHJD and realgar+SB (or RP) groups compared to the realgar-only group (P<0.05). Increases in SAM and ARR levels were observed across various groups, but only the ARR increase in the NHJD group was statistically significant. Moreover, significant increases in As3MT mRNA and GSTO1 mRNA were noted in the NHJD group, and PNP mRNA levels significantly rose in the realgar+SB group. This study revealed that NHJD could attenuate the genotoxic effects of realgar. The botanicals SB, RP, and GU within NHJD may be key contributors to this effect. Enhancements in arsenic methylation capabilities through increased levels of SAM and ARR and elevated gene expressions of As3MT, PNP, and GSTO1 suggest potential mechanisms behind these findings.

Heavy metal concentration according to shrimp species and organ specificity: Monitoring and human risk assessment

Heavy metal concentration according to shrimp species and organ specificity: Monitoring and human risk assessment

Prenatal arsenic exposure, arsenic metabolism and neurocognitive development of 2-year-old children in low-arsenic areas

There is limited evidence on the effects of arsenic species and metabolic capacity on child neurodevelopment, particularly at low levels. Further, little is known about the critical window of exposure. To estimate the associations of arsenic exposure and arsenic metabolism in different pregnancy periods with neurodevelopment of two-year-old children. Concentrations of arsenobetaine (AsB), arsenite, arsenate, monomethyl arsenic acid (MMA), and dimethyl arsenic acid (DMA) in urine samples collected in three trimesters from 1006 mothers were measured using HPLC-ICPMS. Inorganic arsenic (iAs) was calculated as the sum of arsenite and arsenate. Total arsenic (tAs) was calculated as the sum of iAs, MMA and DMA. Child neurodevelopment was assessed with the Bayley Scales of Infant Development. The geometric mean (GM) of SG-adjusted tAs in the first, second, third trimester was 16.37, 12.94, 13.04μg/L, respectively. The mental development index (MDI) score was inversely associated with iAs and tAs. Compared to the 1st quartile, the MDI score decreased 0.43 (95%CI: -4.22, 3.36) for the 2nd, 6.50 (95%CI: -11.73, -1.27) for the 3rd, 5.42 (95%CI: -10.74, -0.10) for the 4th quartiles of iAs, and decreased 4.03 (95%CI: -7.90, -0.15) in the 4th quartile of tAs. In trimester-specific models, negative associations of DMA [-1.94 (95%CI: -3.18, -0.71)] and tAs [-1.61 (95%CI: -3.02, -0.20)] with the psychomotor development index (PDI) were only observed in 1st trimester. Our study found inverse associations between prenatal arsenic exposure, especially in early pregnancy, and neurodevelopment of children at two years old, even at low exposure levels.

Fate of 14 C-MSMA in a soil column study simulating herbicide use environments.

Monosodium methanearsonate (MSMA), a selective contact herbicide, is a sodium salt of monomethyl arsenic acid (MMA or MAA). This paper focuses on the environmental fate of MMA. Decades of research have shown that a significant portion of applied MSMA drips to soil and is sorbed quickly. The fraction available for leaching or biological uptake decreases at a biphasic rate, first rapidly and then at a slower rate. A soil column study was designed to obtain quantitative information about MMA sorption and transformation and the effects of different environmental variables on these processes, in conditions simulating the environment of MSMA use on cotton and turf. Using 14 C-MSMA, this study quantified MSMA-derived arsenic species and differentiated between added arsenic and soil background levels. Similar behavior of MSMA was observed across all test systems with respect to sorption, transformation, and mobility, despite differences in soil type and rainfall treatment. All soil columns exhibited a rapid sorption of added MMA followed by continual sorption of residues into the soil matrix. Within the first 2 days, only 20%-25% of radioactivity was extracted by water. On day 90, less than 3.1% of added MMA was in a water extractable phase. MMA sorption was most rapid in the soil with the higher clay content. Dominant extractable arsenic species were MMA, dimethylarsinic acid, and arsenate, indicating that methylation and demethylation occurred. In all MSMA-treated columns, arsenite concentrations were negligible and indiscernible from those in untreated columns.

Species composition and health risk assessment of arsenic in Agaricus blazei Murrill and Tricholoma matsutake from Yunnan Province, China

High concentrations of total arsenic (As) has been found in Agaricus blazei Murrill and Tricholoma matsutake samples. It is important to study the As species in A. blazei and T. matsutake for accurate health risk assessment. Total As was measured by inductively coupled plasma-mass spectrometry (ICP-MS). An analytical method was developed to determine As species in mushroom by using anion exchange and cation exchange chromatography coupled to ICP-MS. Total As contents ranged from 5.25 to 69.5 mg kg 1 . Arsenobetaine (AsB), inorganic arsenic (iAs), and monomethylarsenic acid (MMA) were the main form of As in A. blazei samples, which accounted for 42.7–88.8%, 1.59–26.2%, and 0.74–1.12% of the extractable As, respectively. AsB, and dimethylarsenic acid (DMA) were the main form of As in T. matsutake samples, which accounted for 88.9–97.9%, and 1.79–3.80% of the extractable As, respectively. Arsenocholine (AsC), trimethylarsine oxide (TMAO), and tetramethylarsonium cation (TMA + ) were present as well, but only at trace concentrations. The health risk index estimation results indicated that no particular risk of iAs exposure to consumers existed in T. matsutake . The iAs exposure in A. blazei can poses certain health risks. • A methodology for arsenic speciation was established. • Species arsenic in Agaricus blazei Murrill and Tricholoma matsutake was studied. • Low level of inorganic arsenic in Tricholoma matsutake has no health risk to human. • Inorganic arsenic exposure in Agaricus blazei Murrill can poses certain health risks.

Bacterial Arsenic Metabolism and Its Role in Arsenic Bioremediation.

Arsenic contaminations, often adversely influencing the living organisms, including plants, animals, and the microbial communities, are of grave apprehension. Many physical, chemical, and biological techniques are now being explored to minimize the adverse affects of arsenic toxicity. Bioremediation of arsenic species using arsenic loving bacteria has drawn much attention. Arsenate and arsenite are mostly uptaken by bacteria through aquaglycoporins and phosphate transporters. After entering arsenic inside bacterial cellarsenic get metabolized (e.g.,reduction, oxidation, methylation, etc.) into different forms. Arsenite is sequentially methylated into monomethyl arsenic acid (MMA) and dimethyl arsenic acid (DMA), followed by a transformation of less toxic, volatile trimethyl arsenic acid (TMA). Passive remediation techniques, including adsorption, biomineralization, bioaccumulation, bioleaching, and so on are exploited by bacteria. Rhizospheric bacterial association with some specific plants enhances phytoextraction process. Arsenic-resistant rhizospheric bacteria have immense role in enhancement of crop plant growth and development, but their applications are not well studied till date. Emerging techniques like phytosuction separation (PS-S) have a promising future, but still light to be focused on these techniques. Plant-associated bioremediation processes like phytoextraction and phytosuction separation (PS-S) techniques might be modified by treating with potent bacteria for furtherance.

Polymorphisms of the AS3MT gene are associated with arsenic methylation capacity and damage to the P21 gene in arsenic trioxide plant workers.

Epidemiological evidence suggests that the metabolic profiles of each individual exposed to arsenic (As) are related to the risk of cancer, coronary heart disease, and diabetes. The arsenite methyltransferase (AS3MT) gene plays a key role in As metabolism. Several single nucleotide polymorphisms in the AS3MT gene may affect both enzyme activity and gene transcription. AS3MT polymorphisms are associated with the proportions of monomethylarsenic acid (MMA) and dimethylarsenic acid (DMA) in urine as well as the incidence of cancer. P21 protein is a cyclin-dependent kinase inhibitor. Mutations of the P21 gene have been found in cancer patients. In our study, we investigate whether polymorphisms of the AS3MT gene alter As methylation capacity and adversely affect the P21 gene in arsenic trioxide plant workers. The DNA damage was examined by the quantitative polymerase chain reaction. Restriction fragment length polymorphism was used to analyze the genotype of the AS3MT gene. The results showed that DNA damage in P21 gene fragments was greater in those individuals exposed to high levels of As. There was a strong positive correlation between the DNA damage to P21 gene fragments and the percentage of MMA in urine. However, DNA damage in P21 gene fragments was negatively associated with the percentage of DMA in urine (%uDMA), primary methylation index (PMI), and secondary methylation index. We found that subjects with the rs7085104 GG or GA allele were associated with higher %uDMA and PMI and less DNA damage. The subjects with the rs11191454 GG+GA or GA allele were also associated with higher %uDMA and PMI and less DNA damage. Our results suggest that rs1191454 and rs7085104 in the AS3MT gene affect the As-induced DNA damage by altering individual metabolic efficiency.

Simultaneous quantitative speciation of selected toxic elements in water using high performance liquid chromatography coupled to inductively coupled plasma-mass spectrometry (HPLC-ICP-MS)

The aim of this study was to conduct multi-elemental speciation of As(III), dimethylarsinic acid (DMA), monomethylarsenic acid (MMA), As(V) and Cr(VI) in water samples using high performance liquid chromatography coupled to inductively coupled plasma-mass spectrometry (HPLC-ICP-MS) in a single analytical run. Chromatographic parameters, spectral interference identification, and elimination and the performance characteristics of the method were successfully optimized for quantification of As(III), DMA, MMA, As(V), Cr(VI) and Cr(III) in water samples. The percentage errors of 6.93–43.2% for identified potential interferences were eliminated by applying the inter-element mathematical correction method. The limit of detection (LOD) and limit of quantification (LOQ) of As species and Cr(VI) were varied from 0.040-0.298 μg L−1 and 0.133–2.98 μg L−1, respectively. The LOD and LOQ of total As, Cr and Pb determined using ICP-MS were ranged from 0.013-0.203 μg L−1 and 0.045–0.675 μg L−1, respectively. The accuracy of the method was confirmed by achieving the percentage recovery of 83.4% for As species, 90.2% for Cr(VI) and 110–118% for total concentrations of As, Cr and Pb using standard reference material for trace elements in water (SRM 1643f). Furthermore, the accuracy of the speciation analysis method was checked using the spiking and recovery studies and yielded percentage recoveries in the range of 78.3–95.4% for the analyte species. The quantities of species determined in water samples were in the range of 0.314–0.402 μg L−1 for As(III), 0.168–0.533 μg L−1 for DMA, 0.226–0.312 μg L−1 for MMA, 0.191–0.459 μg L−1 for As(V), 0.500–3.28 μg L−1 for Cr(VI) and 0.390–12.6 μg L−1 for Cr(III) in high-flow seasonal state of the river. In the low-flow seasonal state, concentrations varied from 0.314-0.391 μg L−1 for As(III), <0.094 μg L−1 for DMA, 0.315–26.7 μg L−1 for MMA, 0.290–0.744 μg L−1 for As(V), 0.426–5.42 μg L−1 for Cr(VI) and 0.424–96.8 μg L−1 Cr(III). Total concentrations of As, Cr and Pb in water samples of high-flow seasonal state ranged from 0.949-1.88 μg L−1, 1.08–14.9 μg L−1 and 0.190–33.8 μg L−1, respectively. In low-flow seasonal state, the total concentrations of As, Cr and Pb in water samples varied from 1.13-26.5 μg L−1, 3.28–97.5 μg L−1 and 0.455–0.610 μg L−1, respectively. The variations between analytes species and total As, Cr and Pb in seasonal states of the river were statistically insignificant (p > 0.05) at a 95% confidence level except for DMA. The nonpoint sources pollution such as atmospheric deposition of dust released from coal mining, power stations, sewage effluents discharge and agricultural activities are presumably the sources of potentially toxic elements in the Mokolo River.

Method validation for As speciation in rice using LC-ICP-MS and the inorganic arsenic limit for Brazilian rice

• A methodology for As speciation in rice using LC-ICP-MS was optimised and validated. • Arsenic species were separated and eluted in less than 8 min using 10 mM (NH 4 ) 2 HPO 4 . • Excellent sensitivity, good precision and accuracy where achieved. • Inorganic As concentration in 640 samples or rice grown in Brazil was lower than 200 ng g −1 . A methodology for As speciation in rice using liquid chromatography-inductively coupled plasma mass spectrometry (LC-ICP-MS) was optimised and validated. Chromatographic separation and elution of As(III), DMA(V) (dimethylarsenic acid), MMA(V) (monomethylarsenic acid) and As(V) were achieved in less than 8 min using 10 mmol L −1 (NH 4 ) 2 HPO 4 as the mobile phase, at pH 6 and a flow rate of 1.4 mL min −1 . The limits of detection for As(III), DMA(V), MMA(V) and As(V) in rice were 1.87, 2.89, 0.54 and 3.00 ng g -1 , respectively. The method’s accuracy was assessed through analyte recovery tests and analysis of certified reference materials, which included white and brown rice flours. The validated method was applied for As speciation in 640 rice samples, comprising polished (white) rice, parboiled rice and brown rice collected from different mesoregions in the Rio Grande do Sul State in Brazil. By comparing the total concentration of As (tAs) found in the acid digested samples with the As species sum, the average extraction efficiencies were 98 ± 13%, 93 ± 12% and 86 ± 6%, for white, parboiled, and brown rice, respectively. The average concentrations of inorganic arsenic (iAs, that is As(III) + As(V)), DMA and tAs in brown and parboiled rice were not different but differed from those in white rice; the average concentrations of tAs, iAs and DMA in brown and parboiled rice were higher than those found in white rice were. The iAs concentration in all rice samples was lower than 200 ng g −1 , which could be recommended as the maximum iAs concentration for Brazilian rice.

Ti (IV) modified vinyl phosphate magnetic nanoparticles for simultaneous preconcentration of multiple arsenic species from chicken samples followed by HPLC-ICP-MS analysis.

Ti (IV)-modified vinyl phosphate magnetic nanoparticles (Fe3 O4 @SiO2 @KH570-PO4 -Ti (IV)) was prepared for simultaneous extraction of multiple arsenic species, followed by high performance liquid chromatography (HPLC)- inductively coupled plasma mass spectrometry (ICP-MS) analysis. Inorganic arsenic (iAs), dimethyl arsenic acid (DMA), monomethyl arsenic acid (MMA), p-amino phenyl arsenic acid (p-ASA), 4-hdroxyphenylarsenic acid (4-OH), phenyl arsenic acid (PAA), and 3-nitro-4-hydroxyphenylarsenic acid (ROX) were investigated as interest analytes. It was found that they were quantitatively adsorbed on Fe3 O4 @SiO2 @KH570-PO4 -Ti (IV) at pH 5, and desorbed completely with 0.1mol/L sodium hydroxide solution. Enrichment factor of 100-fold was obtained by consuming 100mL sample solution. Under the optimal conditions, the method combining MSPE with HPLC-ICP-MS presented a linear range of 1-5000ng/L for seven arsenic species. The limits of detection were 0.39, 0.60, 0.23, 1.85, 0.54, 0.48, and 0.84ng/L for DMA, MMA, p-ASA, iAs, 4-OH, PAA, ROX, with the relative standard deviations (c = 10ng/L, n = 7) of 3.6, 3.9, 5.5, 12.4, 6.1, 5.8, 5.0, respectively. The accuracy of the method was validated by analyzing BCR 627 Tuna fish. The application potential of the method was further evaluated by chicken muscle and liver samples. No target arsenic species were detected in these samples, and good recoveries (80.6-123%) were obtained for the spiked samples at low, medium, and high concentration levels.

Occurrence, speciation analysis and health risk assessment of arsenic in Chinese mitten crabs (Eriocheir sinensis) collected from China

Abstract Arsenic (As) is a major hazardous element in natural environments, and arsenic pollution is becoming an issue of concern worldwide. The more toxic inorganic arsenic, such as trivalent arsenite As(Ⅲ) and pentavalent arsenate As(Ⅴ), which normally can transform to organic arsenic compounds, such as arsenobetaine (AsB), arsenocholine (AsC), monomethyl arsenic acid (MMA), dimethyl arsenic acid (DMA), trimethyl arsenic acid (TMA), arsenosugars and arsenolipids. In this study, a total of 2130 individuals of Chinese mitten crabs were collected from seven locations and mixed to 71 samples. Total arsenic and six major species (AsC, AsB, DMA, MMA, As (Ⅲ), and As (Ⅴ)) were determined by inductively coupled plasma mass spectrometry (ICP-MS) and high-performance liquid chromatography-inductively coupled plasma mass spectrometry (HPLC-ICP-MS), respectively. The target hazard quotient (THQ) was utilized to evaluate the human health risk. The total arsenic concentration and totals for the six arsenic forms are 0.25–1.66 mg/kg and 0.05–1.19 mg/kg wet mass, respectively. Except for HH and LH, the six arsenic species concentrations accounted for more than 50.0 % of the total arsenic. The less toxic AsB is the most predominant in crabs, comprising 50.0 %–90.0 % of the sum of six types of arsenic. The more toxic inorganic arsenic only range from 0.01 to 0.21 mg/kg wet mass, much less than the limit content of 0.50 mg/kg inorganic As in crustacea. The THQ values of inorganic arsenic through the consumption of Chinese mitten crabs are estimated, and the values are all less than 1, indicating that intaking Chinese mitten crabs collected from China will not cause an appreciable hazard risk to human health.

Arsenic exposure increased expression of HOTAIR and LincRNA-p21 in vivo and vitro.

Arsenic is an environmental contaminant, its multiple effects on human tend to increase the rate of disease, cancer and other health problems. Some of long non-coding RNAs (lncRNAs) can be induced in major cellular processes such as necrosis, proliferation, and mutation. While the toxicity of arsenic is well established, the association between arsenic exposure and long non-coding RNAs has not been studied enough. This study investigated the association between arsenic and the expression of HOTAIR and LincRNA-p21 in vivo and vitro. In epidemiological studies, the expression of HOTAIR and LincRNA-p21 was increased after long-term arsenic exposure. HOTAIR and LincRNA-p21 expression were positively linked to monomethylarsenic acid (MMA), dimethylarsenic acid (DMA), inorganic arsenic (iAs), total arsenic (tAs), and MMA% and negatively linked to secondary methylation index (SMI). In A549 cells, arsenic exposure resulted in enhanced HOTAIR and LincRNA-p21 expression dose-dependently. The expression of HOTAIR was considerably high in the presence of NaAsO2 and MMA but showed no difference in DMA compared with control group. And LincRNA-p21 expression was increased in the presence of NaAsO2, MMA, and DMA. The expression of HOTAIR and LincRNA-p21 induced by iAs was much higher than that induced by MMA and DMA. Compared with the control group, treatment of A549 cells with NaAsO2/S-adenosylmethionine (SAM) and NaAsO2/glutathione (GSH) combination increased HOTAIR and LincRNA-p21 expression. The expression of LincRNA-p21 in combination of NaAsO2/GSH was significantly decreased compared with NaAsO2 alone. Besides, in the presence of arsenic, both of HOTAIR and LincRNA-p21 were upregulated significantly when P53 was knocked down. We revealed that inorganic arsenic, its methylated metabolites, and arsenic metabolism efficiency affect the expression of HOTAIR and LincRNA-p21.

Abundance and diversity of microbial arsenic biotransformation genes in the sludge of full-scale anaerobic digesters from a municipal wastewater treatment plant

Arsenic (As) is a potential contaminant in sewage sludge that may affect waste treatment and limit the use of these waste materials as soil amendments. Anaerobic digestion (AD) is an important and effective process for the treatment of sewage sludge and the chemical speciation of As is particularly important in sludge AD. However, the biotransformation genes of As in sludge during AD has not been fully explored. In this study, the influent and effluent sludge of anaerobic digester in a wastewater treatment plant (WWTP) was collected to investigate the species transformations of As, the abundance and diversity of As biotransformation genes was explored by real-time PCR (qPCR) and metagenomic sequencing, separately. The results showed that arsenite [As(III)] and arsenate [As(V)] were predominant in the influent sludge, whereas the relative abundance of monomethylarsenic acid (MMA) increased by 25.7% after digestion. As biotransformation genes were highly abundant, and the As(III) S-adenosylmethionine methyltransferase (arsM) gene was the predominant which significantly increased after AD by qPCR analysis. Metagenomic analysis indicated that the diversity of the arsM-like sequences also increased significantly after AD. Most of the arsM-like sequences in all the influent and effluent sludge samples were related to Bacteroidetes and Alphaproteobacteria. Furthermore, co-occurrence network analysis indicated a strong correlation between the microbial communities and As. This study provides a direct and reliable reference on As biotransformation genes and microbial community in the AD of sludge.

Changes in urinary arsenic species and methylation capacity in original arsenic exposure cohort after water quality improvement.

Water quality improvement is the most efficient way to prevent arsenic exposure. After the cessation of arsenic ingestion, arsenic methylation capacity of the exposed population can change significantly. The factors associated with these changes remain poorly understood. Therefore, arsenic methylation capacity in a study cohort was estimated before and after water quality improvement in the present study. Results indicated that urinary content of the arsenic species in the study cohort significantly decreased after water quality improvement. In addition, the proportions of inorganic arsenic (%iAs) and monomethyl arsenic acid (%MMA) were significantly decreased, while proportions of dimethyl arsenic (%DMA) increased. The primary methylation index (PMI) and secondary methylation index (SMI) increased from 0.85 to 0.92 and 0.82 to 0.84, respectively. Arsenic species urinary content and arsenic methylation index varied slightly between the study cohort after water quality improvement and the control cohort. The rate of increase in PMI was higher than that in SMI. The study group aged 31-50years had the highest increase in PMI. Logistic regression revealed that %DMA before water quality improvement was negatively associated with the increase in PMI, while %iAs were positively related, and %MMA were positively associated with the increase in SMI. It is concluded that urinary arsenic species content and arsenic methylation capacity increased to the levels of the control cohort after water quality improvement. An increase in primary arsenic methylation capacity may be a burden on the secondary arsenic methylation capacity. The main role of arsenic methylation capacity recovery may be the cessation of arsenic exposure.

A method for rapid determination of arsenic species in vegetables using microwave-assisted extraction followed by detection with HPLC hyphenated to inductively coupled plasma-mass spectrometry.

Driven by the significant need for characterization of the chemical speciation of arsenic in food, this work developed a method for rapid determination of four common arsenic species, namely, arsenite, arsenate, monomethyl arsenic acid, and dimethyl arsenic acid, in vegetables using microwave-assisted extraction, followed by detection with high-performance liquid chromatography hyphenated to inductively coupled plasma-mass spectrometry. Initial screening results showed that microwave-assisted extraction using 1% HNO3 exhibited the highest overall efficiencies for all arsenic species without causing significant degradation of the organic ones. With the aid of response surface methodology, the optimum conditions established for extraction of arsenic species from vegetables were: 500mg of freeze-dried vegetable sample, extracted by closed vessel microwave-assisted extraction using 10mL of 2% v/v HNO3 at 90°C for 17min. Application of the method in the analysis of 24 market vegetable samples indicates that the extraction efficiencies for total arsenic species were in the range of 91.4-106%. Arsenite and arsenate were found to be the predominant arsenic species in the vegetables, which suggests that vegetable consumption could be an important route of inorganic arsenic exposure for the population with a heavy vegetable diet in arsenic polluted regions.

The use of HPLC-NAA and HPLC-ICP-MS for the speciation of As in infant food

Arsenic and its inorganic species: As (III), As (V), dimethylarsenic acid (DMA) and monomethylarsenic acid (MMA) were determined in hypoallergenic formulas and grain porridges commercially available on Polish market, dedicated for infant 0-8 months. After quantitative extraction with 0.5% HNO3, separation of individual species was performed by high performance liquid chromatography (HPLC), and their determination by neutron activation analysis (NAA) and inductively coupled plasma mass spectrometry (ICP-MS). Due to relatively low content of As in the analysed samples, it was only possible to determine DMA using the HPLC-ICP-MS mode. HPLC separation coupled with off-line determination by NAA enabled the determination of more extracted As species (especially inorganic) with good accuracy. Certified reference material (CRM) Rice Flour SRM 1568b (NIST) was used for the validation of both procedures.

Total Arsenic and Arsenic Species Determination in Freshwater Fish by ICP-DRC-MS and HPLC/ICP-DRC-MS Techniques.

Analytical methods for the determination of total arsenic (TAs) and arsenic species (arsenite—As(III), arsenate—As(V), monomethylarsenic acid—MMA, dimethylarsenic acid—DMA and arsenobetaine—AsB) in freshwater fish samples were developed. Inductively coupled plasma mass spectrometry with dynamic reaction cell (ICP-DRC-MS) and high-performance liquid chromatography hyphenated to ICP-DRC-MS were used for TAs and arsenic species determination, respectively. The DRC with oxygen as a reaction gas was used. Sample preparation, digestion, and extraction were optimized. Microwave assisted digestion and extraction provided good recovery and extraction efficiency. Arsenic species were fully separated in 8 min using 10 mmol L−1 of ammonium dihydrogen phosphate and 10 mmol L−1 of ammonium nitrate. Overlapping of AsB and As(III) of arsenic species in the presence of a high concentration of AsB and trace amounts of As(III) were studied. Detailed validation of analytical procedures proved the reliability of analytical measurements. Both procedures were characterized by short-term and long-term precision: 2.2% (TAs) up to 4.2% (AsB), and 3.6% (TAs) up to 7.2% (DMA), respectively. Limits of detection (LD) were in the range from 0.056 µg L−1 for TAs to 0.15 µg L−1 for As(V). Obtained recoveries were in the range of 85%–116%. Developed methods were applied to freshwater fish samples analysis.

Application of the adverse outcome pathway (AOP) approach to inform mode of action (MOA): A case study with inorganic arsenic

ABSTRACTThe aim of this study was to establish a process for deriving a chemical-specific mode of action (MOA) from chemical-agnostic adverse outcome pathway (AOPs), using inorganic arsenic (iAs) as a case study. The AOP developed for this case study are related to disruption of cellular signaling by chemicals that strongly bind to vicinal dithiols in cellular proteins, leading to disruption of inflammatory and oxidative stress signaling along with inhibition of the DNA damage responses. The proposed MOA for iAs incorporates this AOP, overlaid on a background of increasing oxidative stress and/or co-exposure to mutagenic chemicals or radiation. The most challenging aspect of developing a MOA from AOP is the incorporation of metabolism and dose-response, neither of which may be considered in the development of an AOP. The cellular responses to relatively low concentrations (below 100 parts per billion) of iAs in drinking water appear to be secondary to binding of trivalent arsenite and its trivalent metabolite, monomethyl arsenous acid to key cellular vicinal dithiols in target tissues, resulting in a co-carcinogenic MOA. The proposed AOP may also be applied to non-cancer endpoints, enabling an integrated approach to conducting a risk assessment for iAs.

Role of AQP9 in transport of monomethyselenic acid and selenite.

AQP9 is an aquaglyceroporin with a very broad substrate spectrum. In addition to its orthodox nutrient substrates, AQP9 also transports multiple neutral and ionic arsenic species including arsenic trioxide, monomethylarsenous acid (MAsIII) and dimethylarsenic acid (DMAV). Here we discovered a new group of AQP9 substrates which includes two clinical relevant selenium species. We showed that AQP9 efficiently transports monomethylselenic acid (MSeA) with a preference for acidic pH, which has been demonstrated in Xenopus laevis oocyte following the overexpression of human AQP9. Specific inhibitors that dissipate transmembrane proton potential or change the transmembrane pH gradient, such as FCCP, valinomycinand nigericin did not significantly inhibit MSeA uptake, suggesting MSeA transport is not proton coupled. AQP9 was also found to transport ionic selenite and lactate, with much less efficiency compared with MSeA uptake. Selenite and lactate uptake via AQP9 is pH dependent and inhibited by FCCP and nigericin, but not valinomycin. The selenite and lactate uptake via AQP9 can be inhibited by different lactate analogs, indicating that their translocation share similar mechanisms. AQP9 transport of MSeA, selenite and lactate is all inhibited by a previously identified AQP9 inhibitor, phloretin, and the AQP9 substrate arsenite (AsIII). These newly identified AQP9 selenium substrates imply that AQP9 play a significant role in MSeA uptake and possibly selenite uptake involved in cancer therapy under specific microenvironments.