Dimethylarsinic Acid Research Articles

Urinary polycyclic aromatic hydrocarbon, arsenic, and metal exposure and correlation with emphysema in smokers

PurposeEnvironmental exposure to metals and chemicals can increase the risk of acute and chronic pulmonary diseases in the human population. This study aimed to analyze seven forms of polycyclic aromatic hydrocarbons (PAHs), seven types of arsenic species, fourteen types of urinary metals including antimony, barium, cadmium, cesium, cobalt, lead, manganese, mercury, molybdenum, strontium, thallium, tin, tungsten, uranium, and the link with emphysema in the US adult cigarette smoking population. MethodsA specialized weighted complex survey design analysis using 2011–2016 National Health and Nutrition Examination Survey (NHANES) datasets was conducted. Multivariate logistic regression models were used to assess the association between urinary metals, arsenic, PAHs, and emphysema in adult smokers. R software was used to conduct the statistical analysis. ResultsAll 4th quantile concentrations of PAHs, including 1-hydroxynaphthalene, 2-hydroxynaphthalene, 3-hydroxyfluorene, 2-hydroxyfluorene, 1-hydroxypyrene, 1-hydroxyphenanthrene, and 2 & 3-hydroxyphenanthrene, were significantly associated with emphysema in smokers. The 3rd quantile of 1-hydroxypyrene were also associated with increased odds of emphysema in smokers. Among arsenic and metals, the 4th quantile of cadmium was associated with an increased odds of emphysema in smokers. The 3rd quantile of dimethylarsinic acid (DMA) and 4th quantile of mercury were found to have inverse relationships with emphysema in smokers. Several demographic factors had significant associations with emphysema in smokers. ConclusionUrinary PAHs and cadmium were associated with increased odds of emphysema in smokers. DMA and mercury had an inverse association with emphysema in smokers.

Inorganic arsenic induces MDM2, p53, and their phosphorylation and affects the MDM2/p53 complex in vitro.

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 60T-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.

Concentrations of blood and urinary arsenic species and their characteristics in general Korean population

Arsenic (As) exposure has been extensively studied by investigating As species (e.g., inorganic arsenic (iAs), monomethylarsonic acid (MMA), and dimethylarsinic acid (DMA)) in urine, yet recent research suggests that blood could be a possible biomarker of As exposure. These investigations, however, were conducted on iAs-contaminated areas, and evidence on populations exposed to low levels of iAs is limited. This study aimed to describe the levels and distributions of As species in urine and blood, as well as to estimate methylation efficiency and related factors in the Korean population. Biological samples were obtained by the Korean Ministry of Food and Drug Safety. A total of 2025 urine samples and 598 blood samples were utilized in this study. Six As species were measured using ultra-high-performance liquid chromatography with inductively coupled plasma mass spectrometry (UPLC-ICP-MS): As(V), As(III), MMA, DMA, arsenobetaine (AsB), and arsenocholine (AsC). Multiple linear regression models were used to examine the relationship between As species (concentrations and proportions) and covariates. AsB was the most prevalent species in urine and blood. The relative composition of iAs, MMA, DMA, and AsC in urine and blood differed significantly. Consumption of blue-backed fish was linked to higher levels of AsB in urine and blood. Type of drinking water and multigrain rice consumption were associated with increased iAs concentration in urine. Except for iAs, every species had correlations in urine and blood in both univariate and multivariate analyses. Adolescents and smokers presented a lower methylation efficiency (higher %MMA and lower %DMA in urine) and females presented a higher methylation efficiency (lower %iAs, %MMA, and higher %DMA in urine). In conclusion, blood iAs concentration cannot represent urinary iAs; nonetheless, different compositions of urine and blood might reflect distinct information about iAs exposure. Further investigations on exposure factors and health are needed using low-exposure groups.

Localized intensification of arsenic methylation within landfill leachate-saturated zone

Leachate-saturated zone (LSZ) of landfills is a complicated biogeochemical hotspot due to the continuous input of electron donors and acceptors from the top refuse layer with leachate migration. In this study, the methylation behavior of the arsenic (As) was investigated. The results indicate that As-methylation processes are influenced by temperature fields in LSZ. The dimethylarsinic acid biotransformation capability can be enhanced with an increase in temperature. Microbial diversity, quantification of functional gene (arsM), and co-occurrence network analysis further characterized the drivers of As methylation in LSZ. As-biogeochemical cycle pathways, as well as As-functional gene distribution among different temperature fields, were modeled on the basis of KEGG annotation. Binning analysis was further employed to assemble As-methylated metagenomes, enabling the identification of novel species for As methylation in landfills. Then, 87 high-quality draft metagenome-assembled genomes (MAGs) were reconstructed from LSZ refuse samples; nearly 15 % (13 of 87) belonged to putative As-methylates functional MAGs. Combined with the model of the As-biogeochemical cycle, nine putative functional species could complete methylation processes alone. The findings of this study highlighted the temperature influence on the As-methylation behavior in LSZ and could facilitate the management of As contamination in landfills.

Recycling banana pseudostem waste as a substrate for microalgae biofilm and their potential in arsenic removal

Arsenic (As) is the most toxic metalloid and class I carcinogen present in the drinking water affecting around 200 M people worldwide. Among various strategies microalgal biofilm based As removal is considered as most suitable option. However, sustainable technologies for As removal from water is scanty. In the present study, banana pseudostem waste was used as a substrate for growing microalgae biofilm (BSB) and its As removal capacity was compared with nylon mesh grown microalgae biofilm (NMB). Response surface methodology optimize initial As concentration as the most important parameter (p < 0.0001) for As removal as compared to substrate area and initial phosphate concentration in both BSB and NMB treatments. BSB treatment removed 97.6% of added arsenite [As(III)] and converted into less toxic forms like arsenate and dimethylarsenic acid within 5 d. The As removal efficiency of BSB treatment is 20% higher than NMB treatment due to the high As accumulation by the banana pseudostem. In both BSB and NMB treatments, As exposure led to change in microalgae community composition towards more tolerant species that produced more proteins and lipids facilitating binding of As and amelioration of induced stress, respectively. The present study signifies the use of banana pseudostem to grow tolerant microalgae for efficient removal of As from water. The study also paves way for proving the concept “waste into wealth” by utilizing the agri-wastes for the sustainable and more economical water treatment process.

Total arsenic, dimethylarsinic acid, lead, cadmium, total mercury, methylmercury and hypertension among Asian populations in the United States: NHANES 2011–2018

BackgroundNon-Hispanic Asians (NHA) in USA have been reported with higher arsenic (As), lead (Pb), cadmium (Cd), mercury (Hg) and their specific species levels, comparing with non-NHA. This study aimed to investigate the associations of these metal/metalloid levels with blood pressure levels and prevalence of hypertension among general NHA using the 2011–2018 National Health and Nutrition and Examination Survey (NHANES) data. MethodsThe study included participants aged 20 years and older with determinations of As, Dimethylarsinic acid (DMA), Pb, Cd, Hg and methyl-Hg (MeHg) in blood (n = 10, 177) and urine (n = 5, 175). These metals/metalloid levels were measured by inductively coupled plasma mass spectrometry. Systolic (SBP) and diastolic blood pressure (DBP) levels were examined through a standardized protocol. Censored normal regression model and logistic regression model were employed to explore the associations of As, DMA, Pb, Cd, Hg and MeHg levels with blood pressure levels and prevalence of hypertension respectively, and potential confounders were adjusted in these regression models. Quantile-based g-computation approach was used to analysis joint effect of metals mixture on blood pressure level and hypertension. ResultsFor NHA, urinary As and Hg levels were associated with increased DBP level; Higher blood Hg and MeHg levels were related to increased blood pressure levels and hypertension; However, negative association was observed between urinary Cd and SBP level; Blood metals mixture (including blood Pb, Cd and Hg) was associated with increased DBP level, but not for hypertension. For non-NHA, urinary As and DMA levels were associated with increased SBP level, but not DBP level and prevalence of hypertension; Urinary Pb level was associated with decreased DBP level; Nevertheless, positive associations were observed between blood Pb levels and SBP and prevalence of hypertension; Blood Hg level was associated with decreased DBP level and prevalence of hypertension; Furthermore, blood MeHg level was associated with decreased DBP level; Positive association was observed between blood metals mixture and increased SBP level among non-NHA. ConclusionsHighly exposed to Hg level among NHA was associated with increased blood pressure levels and prevalence of hypertension. Urinary As level was associated with increased DBP level among NHA. Furthermore, blood metals mixture was related to increased DBP level among NHA. Further prospective studies with larger sample size should be performed to warrant the results.

Chromatographic framework for coffee ring effect-driven separation of small molecules in surface enhanced Raman spectroscopy analysis

The applications of coffee ring effect (CRE) in analytical chemistry have been increasingly expanded from particles and macromolecules to small molecules, in particular coupled to surface-enhanced Raman spectroscopy (SERS). Despite the theory behind the formation of CRE itself from a single drop evaporation onto the dry surface is well established, the theoretical aspects of CRE-driven separation, especially the analyte-surface interactions involving small molecules, have not been conceived. Herein, we have developed a theoretical framework to describe the CRE-driven separation process of small molecules, using SERS analysis of dimethylarsinic acid (DMAV), dimethylmonothioarsinic acid (DMMTAV), and dimethyldithioarsinic acid (DMDTAV) on gold nanofilm (AuNF) as an example. By combining the CRE theory for the radial flow and the Extended Derjaguin-Landau-Verwey-Overbeek (XDLVO) theory for mass transfer between solution and AuNF surface, we adapted the conventional chromatographic theory to derive a modified van Deemter equation for the CRE-driven separation. By using this model, we predicted the travel distances of arsenicals based on the different affinity of analytes to the AuNF and evaluated the possibility of separation of unknown analytes by CRE-based SERS, demonstrating the successful adaptation of classic chromatographic theory to CRE-driven nanochromatography.

Abstract 224: Effect of Agent Orange and Agent Blue derived carcinogens on bladder cancer cell lines and a murine bladder cancer model

Abstract Agent Blue and Agent Orange were defoliants used in high quantities during Vietnam era conflicts in Southeast Asia. The US Department of Veterans Affairs has recently recognized that exposure to both Agent Blue and Agent Orange can potentially increase risk of bladder cancer (BCa) and has added BCa to the list of diseases for which Veterans can seek military benefits. Agent Blue contained significant quantities of organic arsenic and although arsenic is a recognized carcinogen, the understanding of how arsenic affects BCa is still unclear in the literature. Moreover, the effects of the Agent Orange contaminant 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) on BCa remains largely unstudied, especially in populations that were exposed during this period. We hypothesized chronic exposure to carcinogens TCDD or organic arsenic in the form of cacodylic acid (CA) would enhance cancer associated phenotypes. We treated benign urothelial cells (UROtsa and SV-HUC-1 cells) with low doses of cacodylic acid (0.05-5µM) or TCDD (0.03 - 3nM) for up to 6 months. While we found minor differences in proliferation rates there was no consistent trend across samples in either cell line nor was cellular migration affected. Because benign urothelial cells represent a transformed cell line and not true urothelial cells, we next wanted to assess how CA affected BCa formation in mice using the validated N-Butyl-N-(4-hydroxybutyl) nitrosamine (BBN) induced BCa model. TCDD was omitted from this step as its carcinogenicity in mice is understood to dramatically exceed human levels and thus is not relevant to human data. To approximate early-life exposure akin to what Vietnam Era Veterans may have experienced, we treated C57Bl/6J mice with BBN for 16 weeks or 20 weeks with or without increasing concentrations of cacodylic acid (5, 10, 50ppm) for 4 weeks during BBN treatment, starting at week 4 and ending at week 8, and evaluated outcomes associated with BCa formation and progression. While previous reports have found CA promotes BBN induced BCa, we found co-treatment with CA had no effect at 16 weeks post BBN, but reduced both bladder weights (a surrogate for tumor volume) and tumor stage after 20 weeks. RNA-sequencing was used to determine how CA affected the transcriptome of BBN induced tumors. Differential gene expression and Reactome analysis indicated the predominant changes were associated with alterations in RNA processing and translation, EGFR signaling and more. Our work thus far indicates that the ability of TCDD/CA exposure to promote BCa formation is likely context dependent. Future studies will enhance our understanding of how CA interacts with BBN acutely, and attempt to define mechanisms of how arsenic may protect against BBN induced BCa in experimental models, and whether this is clinically relevant for Vietnam Era Veterans. Citation Format: Ganeshkumar Rajendron, Erika Abbott, Jeffery Thompson, Shachi Patel, Aaron Barchowsky, Katie Dennis, Benjamin L. Woolbright, John A. Taylor. Effect of Agent Orange and Agent Blue derived carcinogens on bladder cancer cell lines and a murine bladder cancer model [abstract]. In: Proceedings of the American Association for Cancer Research Annual Meeting 2022; 2022 Apr 8-13. Philadelphia (PA): AACR; Cancer Res 2022;82(12_Suppl):Abstract nr 224.

Morpho-anatomical responses of Catharanthus roseus due to combined heavy metal stress observed under Scanning Electron Microscope

Heavy metals trigger various plant responses that basically vary with the intensity as well as duration of stress. Comprehension of the morphological and anatomical responses to such stress is essential for a holistic perception of plant resistance mechanisms to metal-excess conditions in higher plants. In the present study, the effects of heavy metals on morpho-anatomy of Catharanthus roseus based on its potential to tolerate metal stress has been studied in industrially polluted environments. The tissue samples of these plants grown in contaminated and uncontaminated soils were processed for analysis under Scanning Electron Microscope (SEM). Briefly, harvested tissues were pre-fixed using glutaraldehyde and paraformaldehyde in sodium cacodylate (CAC) buffer, followed by post fixation in osmium tetroxide. Further, the digital micrographs of critically dried samples were captured. The analysis of micrographs revealed structural changes like cell wall thickening, increased stele diameter, increased root and shoot diameter, variations in stomatal number, enlargement of trichomes and salt glands of plants grown in contaminated soil when compared to those grown in uncontaminated soil. The study also provided microscopic evidence of endophytic colonization of microorganisms within surface-disinfected plant tissues. Based on the varied morpho-anatomical responses due to heavy metal stress, several physiological and metabolic mechanisms of plants were deciphered.

Quantification of Arsenic Species in Wheat Flour Samples by Ion Chromatography Coupled to High Resolution Inductively Coupled Plasma-Mass Spectrometry (IC-HR-ICP-MS)

A method was developed for arsenic speciation of South African wheat flour by microwave-assisted extraction with ion chromatography (IC) separation and detection with high resolution inductively coupled plasma–mass spectrometry (IC-HR-ICP-MS). Method optimization included development of the extraction and elution methods for baseline separation of the As-species in the samples. The As-species were successfully extracted using deionized water and baseline separation was attained using a gradient elution method with 0.5 mM HNO3 (pH 3.4) and 50 mM HNO3 (pH 1.4). Method validation parameters, including trueness (bias), precision, linearity, limit of detection (LOD), limit of quantification (LOQ) and selectivity were evaluated to assess the quality of the results. Three certified reference materials (CRMs), NIST SRM 1568b (rice flour), NMIJ CRM 7533-a (brown rice flour), and ERM BC211 (brown rice flour) were used to evaluate the trueness of the developed method. Low limits of detection and quantification were achieved (0.3 to 2.6 pg g−1 and 1.1 to 8.6 pg g−1, respectively) for the As-species. The dominant peaks in the wheat flour were arsenite (As(III)), dimethyl arsenic acid (DMA), and arsenate (As(V)). The concentrations of the inorganic (iAs), i.e., As(III) and As(V) in the wheat flour were very low from 6.8 to 17.8 ng g−1, with a relative expanded uncertainty () of <6.9% (=2), which is below the permissible level of iAs in food and food products proposed by the World Health Organization (WHO).

Two-step micelle-to-solvent stacking of arsenic species from foods in permanently coated tubing for capillary electrophoresis

An effective and sensitive two-step stacking of arsenic species by electrokinetic injection and micelle-to-solvent stacking (MSS) using zwitterionic surfactant 3-(N,N-dimethylpalmitylammonio) propane sulfonate was successfully developed in a co-electro-osmotic flow (co-EOF) capillary zone electrophoresis (CZE). The fused silica capillaries were coated with 1% hexadimethrine bromide solution to satisfy the condition of the same EOF direction between the test anions and capillary. The background solution was 100 mM borax buffer (pH 9.2). The proposed method was performed by a CZE system equipped with a diode array detector, and the detection wavelength was monitored at 192 nm. The separation voltage was −20 kV. The group of micelles and target analytes was stacked by field-enhanced sample injection at −10 kV for 180 s. The second stacking step used 60% MeOH to serve as an organic solvent where the analytes were brought by the micelles to the MSS boundary. The enrichment factors of As(Ⅴ), As(Ⅲ), disodium methyl arsonate hexahydrate (MMA), and dimethylarsinic acid (DMA) were 1230, 840, 3820, and 1450, respectively, compared to typical injections in CZE. The limits of detection (S/N = 3) ranged from 0.382 to 0.911 ng mL−1. The intracapillary repeatabilities (%RSD, n = 3) were 0.5–1.0% for migration time and 0.3–0.7% for peak areas. The technology of two-step stacking by MSS in co-EOF CZE together with a simple extraction procedure for As(Ⅴ), As(Ⅲ), MMA and DMA were demonstrated in kelp and rice samples.

Associations of total urinary arsenic with total cholesterol and high-density lipoprotein among 12-17-year-old participants from the 2009-2016 NHANES cycles: A cross-sectional study.

Hypertension and diabetes are highly prevalent among US adults. Arsenic exposure is associated with these cardiometabolic morbidities but the relationship between arsenic exposure and cholesterol markers of cardiometabolic disease has not been elucidated, especially at younger ages, when many chronic diseases may initiate. This study examined the association of total urinary arsenic with total cholesterol (TC) and high-density lipoprotein cholesterol (HDL) and explored effect modification by weight status. The study sample consisted of 12-17-year-old participants with complete data from the 2009-2016 National Health and Nutrition Examination Survey cycles. The cross-sectional associations of creatinine-adjusted total urinary arsenic with TC and HDL were assessed using multivariable linear regression models with survey weights. Three models were built, adjusting for varying combinations of age, gender, race/ethnicity, weight status, survey cycle, family income to poverty ratio, reference person education level, arsenobetaine, and dimethylarsinic acid (DMA). Model adjustments for arsenobetaine approximated inorganic arsenic exposure, and further adjustment for DMA approximated unmethylated inorganic arsenic exposure. We also explored weight status (underweight/healthy, overweight, and obese) as a potential effect modifier of these relationships using stratified analyses and interaction tests. The final analytical sample consisted of 1,177 12-17-year-old participants. After adjusting for covariates and arsenobetaine, creatinine-adjusted arsenic was positively associated with HDL levels (β=0.063; 95% CI: 0.007, 0.119). Upon further adjustment for DMA, creatinine-adjusted arsenic was positively associated with HDL levels (β=0.079; 95% CI: 0.015, 0.143) and TC levels (β=0.258; 95% CI: 0.002, 0.515). No effect modification by weight status was observed. We found a positive association of approximated unmethylated inorganic arsenic exposure with TC, and contrary to our expectation, with HDL. There was no effect modification by weight status. Our findings should be confirmed by conducting longitudinal studies among adolescents exposed to low-level arsenic and focusing specifically on urinary inorganic arsenic concentrations.

Preclinical In Vitro Model to Assess the Changes in Permeability and Cytotoxicity of Polarized Intestinal Epithelial Cells during Exposure Mimicking Oral or Intravenous Routes: An Example of Arsenite Exposure.

The gastrointestinal tract (GIT) is exposed to xenobiotics, including drugs, through both: local (oral) and systemic routes. Despite the advances in drug discovery and in vitro pre-clinical models, there is a lack of appropriate translational models to distinguish the impact of these routes of exposure. Changes in intestinal permeability has been observed in different gastrointestinal and systemic diseases. This study utilized one such xenobiotic, arsenic, to which more than 200 million people around the globe are exposed via their food, drinking water, work environment, soil, and air. The purpose of this study was to establish an in vitro model to mimic gastrointestinal tract exposure to xenobiotics via oral or intravenous routes. To achieve this, we compared the route (mimicking oral and intravenous exposure to GIT and the dose response (using threshold approach) of trivalent and pentavalent inorganic arsenic species on the permeability of in vitro cultured polarized T84 cells, an example of intestinal epithelial cells. Arsenic treatment to polarized T84 cells via the apical and basolateral compartment of the trans-well system reflected oral or intravenous routes of exposure in vivo, respectively. Sodium arsenite, sodium arsenate, dimethyl arsenic acid sodium salt (DMAV), and disodium methyl arsonate hydrate (MMAV) were assessed for their effects on intestinal permeability by measuring the change in trans-epithelial electrical resistance (TEER) of T-84 cells. Polarized T-84 cells exposed to 12.8 µM of sodium arsenite from the basolateral side showed a marked reduction in TEER. Cytotoxicity of sodium arsenite, as measured by release of lactate dehydrogenase (LDH), was increased when cells were exposed via the basolateral side. The mRNA expression of genes related to cell junctions in T-84 cells was analyzed after exposure with sodium arsenite for 72 h. Changes in TEER correlated with mRNA expression of focal-adhesion-, tight-junction- and gap-junction-related genes (upregulation of Jam2, Itgb3 and Notch4 genes and downregulation of Cldn2, Cldn3, Gjb1, and Gjb2). Overall, exposure to sodium arsenite from the basolateral side was found to have a differential effect on monolayer permeability and on cell-junction-related genes as compared to apical exposure. Most importantly, this study established a preclinical human-relevant in vitro translational model to assess the changes in permeability and cytotoxicity during exposure, mimicking oral or intravenous routes.

Green and Simple Extraction of Arsenic Species from Rice Flour Using a Novel Ultrasound-Assisted Enzymatic Hydrolysis Method

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.

Comparison of the toxic effects of organic and inorganic arsenic in Caenorhabditis elegans using a multigenerational approach.

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 50μgL-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.

Association between environmental toxic metals, arsenic and polycyclic aromatic hydrocarbons and chronic obstructive pulmonary disease in the US adult population.

Associations between environmental metals and chemicals and adverse human health effects have emerged recently, but the links among environmental metals and respiratory diseases are less studied. The aim of this study was to assess 14 urinary metals (cadmium, barium, cobalt, molybdenum, mercury, cesium, manganese, antimony, lead, tin, strontium, tungsten, thallium, and uranium), seven species of arsenic (arsenous acid, arsenic acid, arsenobetaine, arsenocholine, dimethylarsinic acid, monomethylarsonic acid, and total arsenic) and seven polycyclic aromatic hydrocarbon (PAH) (1-hydroxynaphthalene, 2-hydroxynaphthalene, 3-hydroxyfluorene, 2-hydroxyfluorene, 1-hydroxyphenanthrene, 1-hydroxypyrene, 2 & 3-hydroxyphenanthrene) compounds' concentrations in urine and the correlation with chronic obstructive pulmonary disease (COPD) in the adult US population. A cross-sectional analysis using the 2013-2014 and 2015-2016 National Health and Nutrition Examination Survey (NHANES) dataset was conducted. Self-questionnaires related to COPD criteria were used to identify the COPD cases. The correlation between urinary metals and PAH compounds and COPD was calculated. The total study population analyzed included 2885 adults aged 20years and older. Seven types of urinary PAHs including 1-hydroxynaphthalene [odds ratio (OR): 1.832, 95% confidence interval (CI): 1.210, 2.775], 2-hydroxynaphthalene [OR: 3.361, 95% CI: 1.519, 7.440], 3-hydroxyfluorene [OR: 2.641, 95% CI: 1.381, 5.053], 2-hydroxyfluorene [OR: 3.628, 95% CI: 1.754, 7.506], 1-hydroxyphenanthrene [OR: 2.864, 95% CI: 1.307, 6.277], 1-hydroxypyrene [OR: 4.949, 95% CI: 2.540, 9.643] and 2 & 3-hydroxyphenanthrene [OR: 3.487, 95% CI: 1.382, 8.795] were positively associated with COPD. Urinary cadmium [OR: 12.382, 95% CI: 4.459, 34.383] and tin [OR: 1.743, 95% CI: 1.189, 2.555] showed positive associations with increased odds of COPD. The other types of urinary metals were not associated with COPD. The study observed that urinary PAHs, cadmium, and tin are significantly associated with COPD.

Associations between lead, cadmium, mercury, and arsenic exposure and alanine aminotransferase elevation in the general adult population: an exposure-response analysis.

Cadmium, lead, mercury, and arsenic are among the most toxic environmental contaminants. Serum alanine aminotransferase (ALT) is the most common liver biomarker. This analysis aimed to explore the associations between blood cadmium, lead, mercury, urinary total arsenic, and dimethylarsinic acid and ALT elevation in adults. Data were extracted from 5 National Health and Nutrition Examination Survey cycles (NHANES) 2007-2016. Patients with chronic viral hepatitis and excessive alcohol consumption were excluded. ALT elevation was defined according to the 2017 American College of Gastroenterology Clinical Guideline. Logistic models and restricted cubic splines were adopted to assess the exposure-response relationships. Comparing the highest to lowest quintile of exposure, the multivariable-adjusted odds ratios (95% confidence intervals) of ALT elevation were 1.38 (1.07-1.78) for blood lead (Pfor trend = 0.01), 1.37 (1.16-1.62) for blood mercury (Pfor trend < 0.01), 0.94 (0.78-1.14) for blood cadmium (Pfor trend = 0.64), 1.07 (0.79-1.45) for urinary total arsenic (Pfor trend = 0.81), and 1.25 (0.94-1.66) for urinary dimethylarsinic acid (Pfor trend = 0.18). The associations between blood lead and mercury and ALT elevation were only observed in women. In addition, the associations between urinary total arsenic [1.53 (1.02-2.29), Pfor trend = 0.02] and dimethylarsinic acid [2.17 (1.05-4.49), Pfor trend = 0.02] and ALT elevation were also observed in women. Dose-response analysis showed that there was no safe exposure threshold of blood lead and mercury's toxic effect on ALT elevation, respectively. In conclusion, lead, mercury and arsenic were associated with ALT elevation in adults, and the associations were mainly observed in women.

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.

Exposure Levels and Contributing Factors of Various Arsenic Species and Their Health Effects on Korean Adults.

Arsenic is a human carcinogen. Data on urinary arsenic species analyses of Koreans are limited. This study evaluated the arsenic exposure level, contributing factors, and health effects in Korean adults. Dietary intake information and urine samples were obtained from 2044 participants. Arsenic exposure was assessed based on urinary concentrations of arsenic species, such as inorganic arsenic, As(III) and As(V), monomethylarsonic acid (MMA), dimethylarsinic acid (DMA), and arsenobetaine (AsB), using high-performance liquid chromatography with inductively coupled plasma mass spectrometry, followed by determination of biomarkers, malondialdehyde and c-peptide. The geometric mean concentrations were 30.9 μg/L for the sum of inorganic arsenic and their metabolites, and 84.7 μg/L for the total sum of arsenic measured. Urinary concentrations of arsenic species were influenced by age, inhabitant area (inland or coastal), and seafood intake, which was positively correlated with inorganic arsenic, DMA, and AsB. Rice intake was positively correlated with inorganic arsenic and its metabolites but not with AsB. Additionally, malondialdehyde and c-peptide levels were significantly associated with urinary concentrations of various arsenic species. Seafood and rice are major sources of organic/inorganic arsenic exposure in Korean adults; however, it is necessary to evaluate whether their overconsumption could have a potentially detrimental effect on human health.

Removal of dimethylarsinic acid (DMA) in the Fe/C system: roles of Fe(II) release, DMA/Fe(II) and DMA/Fe(III) complexation

Methylated arsenic species are ubiquitous in the environment and resistant to removal by conventional treatment technologies. This study addressed this challenge based on the examination of the removal of dimethylarsinic acid (DMA) in a system that combines zerovalent iron (ZVI) and powdered activated carbon (PAC). The removal of DMA in the ZVI/PAC system was compared to that by coagulation, adsorption, electrochemical and Fenton oxidations, and other conventional methods. While only the electrochemical oxidation using a PbO2/Sb-SnO2/Ti anode allowed removing up to 60% DMA at several hours-long treatment times, the removal of DMA in the ZVI/PAC system containing 10 g/L ZVI and 2.5 g/L PAC with an initial pH of 2.0 was 95% for a 30 min reaction time. Specific roles of PAC, ZVI and its oxidation products in DMA removal were examined based on the spectroscopic data and quantum chemical modeling for the DMA/Fe(II) and DMA/Fe(III) systems. These methods demonstrated the formation of moderately strong DMA/Fe(II) and DMA/Fe(III) complexation. These results and relevant kinetic data were interpreted to indicate that the removal of DMA is governed by the rapid generation of Fe2+ ions released as a result of accelerated ZVI corrosion in the galvanic ZVI/PAC microcells and ensuing formation of DMA/ Fe2+ complexes that are readily adsorbed by PAC.