Intake of Inorganic Arsenic in the North American Diet

Dietary intake of inorganic arsenic, previously assumed to be an insignificant source of arsenic exposure in humans, was estimated for Canadian and United States populations. Input data included arsenic contents of various food groups, a limited historical database from the Ontario Ministry of the Environment measuring the percent inorganic arsenic in food groups, and food consumption data. Estimated daily dietary intake of inorganic arsenic ranges from 8.3 to 14?µg/day in the United States and from 4.8 to 12.7?µg/day in Canada for various age groups. These data suggest that between 21% to 40% of total dietary arsenic occurs in inorganic forms. Uncertainties regarding total arsenic in dairy products in the data set applied here may account for observed differences between United States and Canadian estimates. While estimates provided here are preliminary because of limitations in data on the proportion of inorganic arsenic in foods, this analysis suggests that dietary intake of inorganic arsenic is higher than is currently assumed. Additional research is needed to more fully characterize inorganic arsenic concentrations in foods. Future study is also needed on the variability of total and inorganic arsenic in foods and the bioavailability of dietary inorganic arsenic.     

Study on the effects of arsenic pollution on the communities of macro-invertebrate in Xieshui River

In 2006 and 2007, five sampling stations were set up in Xieshui River and its tributaries to study the macro-invertebrate communities, and measure physicochemical parameters and contents of different forms of arsenic. A comparative analysis and multivariate statistical methods were used to explore the effects of arsenic pollution on the macro-invertebrate communities. In this study, sixty species were identified, including 39 aquatic insects, 10 mollusks, 5 oligochaetes, 1 crustacean, and 5 others. Results of the comparative analysis indicated that the macro-invertebrate communities at the station with serious arsenic pollution tended to be simple and showed a significant decreasing in density, biomass, and biodiversity in comparison with the other stations. Arsenic pollution also had a major effect on the dominant species and groups. For instance, EPT taxa disappeared at the station with serious arsenic pollution, and chironomids that belong to the genus Cardiocladius were very tolerant to high concentrations of arsenic. Results of the functional feeding groups (FFGs) analysis indicated that the predators were more tolerant to arsenic pollution, while the scrapers, filterers, and collectors were relatively sensitive to arsenic pollution. Results of a non-metric multidimensional scaling (nMDS) analysis showed that when the concentration of inorganic arsenic decreased to the range between the criteria continuous concentration (CCC) and the criteria maximum concentration (CMC), the effects of inorganic arsenic on the macro-invertebrate communities seemed to be insignificant. Results of a BVSTEP (Bio-Env Step-Wise Procedure) analysis showed that water temperature, rotifer density, trivalent arsenic, pentavalent arsenic, and total inorganic arsenic greatly influenced species appearance, while rotifer density and various forms of arsenic had a considerable impact on the species composition.     

Comparative Molecular Docking Studies with ABCC1 and Aquaporin 9 in the Arsenite Complex Efflux

Arsenic is the most toxic metalloid present in the natural environment in both organic and inorganic arsenic forms. Inorganic arsenic is often more hazardous than the organic form. Arsenite and arsenate compounds are the major inorganic forms which are toxic causing severe human health dysfunction including cancer. Excretion of arsenic from the system is found elusive. Therefore, it is of interest to screen channel proteins with the arsenic complex in the different combination of arsenic, GSH (glutathione) and arsenic, selenium using docking methods. The mode of arsenic removal. The complex structure revealed the mode of arsenic binding efficiency with the receptor aquaporine 9 and ABCC1 channel protein. This provides insights to understand the mechanism of arsenic efflux. These inferences find application in the design, identification and development of novel nutracetucal or any other formulation useful in the balance of arsenic efflux.     

Importance of Arsenic Speciation in Populations Exposed to Arsenic in Drinking Water

Total arsenic in urine is often the principal means for assessing chronic exposure to arsenic-contaminated drinking water. This approach ignores many components of the human diet, especially fish and seafood that contain arsenic at significant concentrations. The toxicity differences between the inorganic forms and the dietary forms suggest both should be evaluated when attempting to assess risk from arsenic exposure. Urine biomonitoring for 53 participants was used to confirm reduction in arsenic exposure resulting from well water remediation removing inorganic arsenic from drinking water. Initially, only total arsenic urine assays were performed, but spikes in total arsenic urine concentrations were determined to be diet related and demonstrated the need for analytical methods that differentiate the arsenic species. A secondary analysis was added that quantified inorganic-related arsenic in urine and the dietary forms related to fish and seafood by subtraction from total arsenic. Significant differences were found between the inorganic arsenic component and the total arsenic measured in their urine. On average, approximately 76% of total arsenic in urine was attributed to fish and other organo-arsenic dietary sources, implying a potential significant overestimate of exposure, and demonstrating the need for differentiation of the inorganic-related arsenic from dietary arsenic.     

Arsenic and cadmium in the marine macroalgae (Porphyra yezoensis and Laminaria Japonica) — forms and concentrations

Abstract

Total arsenic, inorganic arsenic (iAs), total cadmium concentrations and chemical forms of cadmium were analysed in Porphyra yezoensis collected monthly from January to April in 2011 and in Laminaria Japonica collected monthly from March to July in 2010. Results showed that total As concentrations in P. yezoensis were much lower than those in L. Japonica. The iAs concentrations in both macroalgae were all below the maximum limit according to the legislation in China, while total Cd concentrations in all samples of P. yezoensis exceeded the maximum limit. The percentage of iAs to total As decreased in both macroalgae with the time. The results provide important information showing that both macroalgae are able to metabolise inorganic arsenic to organic forms. Thus both macroalgae have evolved arsenic resistance which is linked to the capability of metabolising toxic inorganic arsenic. In addition, the results suggest that the transformation rate of arsenate to organic arsenic in both algae increases with the growth and metabolic rate that increase with elevated environmental temperature. Temperatures rise from January to April in Jiangsu province and from March to July in Liaoning Province. Most Cd was associated with pectates and protein (extractable by 1 M NaCl) in both algae, and only a small percentage of the Cd was inorganic (extractable by 80% ethanol). The Cd chemical forms have no obvious relationship with the time in both algae.     

Biological Responses to Arsenic Compounds

Arsenic is a metalloid that generates various biological effects on cells and tissues. Depending on the specific tissue exposed and the time and degree of exposure, diverse responses can be observed. In humans, prolonged and/or high dose exposure to arsenic can have a variety of outcomes, including the development of malignancies, severe gastrointestinal toxicities, diabetes, cardiac arrhythmias, and death. On the other hand, one arsenic derivative, arsenic trioxide (As₂O₃), has important antitumor properties. This agent is a potent inducer of antileukemic responses, and it is now approved by the Food and Drug Administration for the treatment of acute promyelocytic leukemia in humans. The promise and therapeutic potential of arsenic and its various derivatives have been exploited for hundreds of years. Remarkably, research focused on the potential use of arsenic compounds in the treatment of human diseases remains highly promising, and it is an area of active investigation. An emerging approach of interest and therapeutic potential involves efforts to target and block cellular pathways activated in a negative feedback manner during treatment of cells with As₂O₃. Such an approach may ultimately provide the means to selectively enhance the suppressive effects of this agent on malignant cells and render normally resistant tumors sensitive to its antineoplastic properties.Arsenic forms complexes with other elements, and it exists in inorganic and organic forms (1–3). The three major inorganic forms of arsenic are arsenic trisulfide (As₂S₃, yellow arsenic), arsenic disulfide (As₂S₂, red arsenic), and arsenic trioxide (As₂O₃, white arsenic) (1–3). There are two different oxidative states of arsenic that correlate with its cytotoxic potential, As(III) and As(V). Among them, As(III) is the most potent form and primarily accounts for its pro-apoptotic and inhibitory effects on target cells and tissues (3). The various forms of arsenic exist in nature primarily in a complex with pyrite (4, 5), although under certain circumstances, arsenic can dissociate from soil and enter natural waters (6), providing a contamination source for humans or animals who ingest such waters. In fact, most associations between long term exposure to arsenic and development of malignancies or other health disorders result from drinking contaminated water, especially in developing countries. Interestingly, pollution of the air with arsenic can also occur under certain circumstances, such as in the case of emissions from coal burning in China (7), providing an additional source of human exposure.The metabolism of arsenic in humans includes reduction to the trivalent state and oxidative methylation to the pentavalent state (reviewed in Ref. 2). There is also reduction of arsenic acid to the arsenous form and subsequent methylation (2). The generation of inorganic or organic trivalent arsenic forms has important implications with regard to the toxicity of this agent, as such compounds are more toxic to the cells and exhibit more carcinogenic properties (2, 3). Thus, many of the consequences of exposure to arsenic as discussed below are the result of the activities and toxicities of the various metabolic products of arsenic compounds. It should be also noted that arsenic has the ability to bind to reduced thiols, including sulfhydryl groups in some proteins (2). Depending on the cellular context, such protein targeting may explain some of its cellular effects and generation of its toxicities and/or therapeutic effects.     

Microbial responses to environmental arsenic

Microorganisms have evolved dynamic mechanisms for facing the toxicity of arsenic in the environment. In this sense, arsenic speciation and mobility is also affected by the microbial metabolism that participates in the biogeochemical cycle of the element. The ars operon constitutes the most ubiquitous and important scheme of arsenic tolerance in bacteria. This system mediates the extrusion of arsenite out of the cells. There are also other microbial activities that alter the chemical characteristics of arsenic: some strains are able to oxidize arsenite or reduce arsenate as part of their respiratory processes. These type of microorganisms require membrane associated proteins that transfer electrons from or to arsenic (AoxAB and ArrAB, respectively). Other enzymatic transformations, such as methylation-demethylation reactions, exchange inorganic arsenic into organic forms contributing to its complex environmental turnover. This short review highlights recent studies in ecology, biochemistry and molecular biology of these processes in bacteria, and also provides some examples of genetic engineering for enhanced arsenic accumulation based on phytochelatins or metallothionein-like proteins.     

Arsenic (+3 oxidation state) methyltransferase and the methylation of arsenicals

Metabolic conversion of inorganic arsenic into methylated products is a multistep process that yields mono-, di-, and trimethylated arsenicals. In recent years, it has become apparent that formation of methylated metabolites of inorganic arsenic is not necessarily a detoxification process. Intermediates and products formed in this pathway may be more reactive and toxic than inorganic arsenic. Like all metabolic pathways, understanding the pathway for arsenic methylation involves identification of each individual step in the process and the characterization of the molecules which participate in each step. Among several arsenic methyltransferases that have been identified, arsenic (+3 oxidation state) methyltransferase is the one best characterized at the genetic and functional levels. This review focuses on phylogenetic relationships in the deuterostomal lineage for this enzyme and on the relation between genotype for arsenic (+3 oxidation state) methyltransferase and phenotype for conversion of inorganic arsenic to methylated metabolites. Two conceptual models for function of arsenic (+3 oxidation state) methyltransferase which posit different roles for cellular reductants in the conversion of inorganic arsenic to methylated metabolites are compared. Although each model accurately represents some aspects of enzyme's role in the pathway for arsenic methylation, neither model is a fully satisfactory representation of all the steps in this metabolic pathway. Additional information on the structure and function of the enzyme will be needed to develop a more comprehensive model for this pathway.     

Arsenicals affect base excision repair by several mechanisms

Inorganic arsenic is a strong, widespread human carcinogen. How exactly inorganic arsenic exerts carcinogenicity in humans is as yet unclear, but it is thought to be closely related to its metabolism. At exposure-relevant concentrations arsenic is neither directly DNA reactive nor mutagenic. Thus, more likely epigenetic and indirect genotoxic effects, among others a modulation of the cellular DNA damage response and DNA repair, are important molecular mechanisms contributing to its carcinogenicity. In the present study, we investigated the impact of arsenic on several base excision repair (BER) key players in cultured human lung cells. For the first time gene expression, protein level and in case of human 8-oxoguanine DNA glycosylase 1 (hOGG1) protein function was examined in one study, comparing inorganic arsenite and its trivalent and pentavalent mono- and dimethylated metabolites, also taking into account their cellular bioavailability. Our data clearly show that arsenite and its metabolites can affect several cellular endpoints related to DNA repair. Thus, cellular OGG activity was most sensitively affected by dimethylarsinic acid (DMA(V)), DNA ligase IIIα (LIGIIIα) protein level by arsenite and X-ray cross complementing protein 1 (XRCC1 protein) content by monomethylarsonic acid (MMA(V)), with significant effects starting at ≥3.2μM cellular arsenic. With respect to MMA(V), to our knowledge these effects are the most sensitive endpoints, related to DNA damage response, that have been identified so far. In contrast to earlier nucleotide excision repair related studies, the trivalent methylated metabolites exerted strong effects on the investigated BER key players only at cytotoxic concentrations. In summary, our data point out that after mixed arsenic species exposure, a realistic scenario after oral inorganic arsenic intake in humans, DNA repair might be affected by different mechanisms and therefore very effectively, which might facilitate the carcinogenic process of inorganic arsenic.     

Dietary Arsenic Intake in Taiwanese Districts with Elevated Arsenic in Drinking Water

Inorganic arsenic in dietary staples (i.e., yams and rice) may have substantially contributed to exposure and adverse health effects observed in an endemic Taiwanese population historically exposed to arsenic in drinking water. Observations of this population were used by the U.S. Environmental Protection Agency to derive toxicity values that form the basis for arsenic risk assessment and various regulations in the United States. However, data were previously insufficient to accurately estimate dietary intake. Rice and yam samples collected in 1993 and 1995 from Taiwanese districts with endemic arsenic were analyzed for total arsenic and for inorganic and organic mono and dimethylarsenic. The acid digestion techniques used in the analyses are among the best to preserve organic arsenic in the test sample. Furthermore, concurrent analyses of the proportion of inorganic arsenic in split samples of rice and yams collected in the 1995 investigation were in good agreement, despite using a different digestion method. These data support a likely mean dietary intake of 50?µg/day with a range of 15 to 211?µg/day. Consideration of dietary intake may result in a downward revision of the assumed potency of ingested arsenic as reflected in EPA's toxicity values.     

Chemical speciation of arsenic in urine of patients with blackfoot disease

Blackfoot disease is a peripheral vascular disease resulting in gangrene of the lower extremities. Although extensive epidemiological study has implicated high arsenic content in artesian well water of the endemic area bears some important connection with the disease, the etiology of the disease is still not clarified. In this study, attention is paid to chemical speciation of arsenic in order to find out whether the concentrations of arsenic species in urine of Blackfoot disease patients are different from those of controls. Experimental results indicate that the total arsenic, inorganic arsenic, monomethylarsonic acid, and other forms of arsenic in the urine of patients are significantly higher than those of the contols. The possible connection of those arsenic species with the etiology of the disease is discussed.     

抗砷性微生物及其抗砷分子机制研究进展

砷(Arsenic, As)是一种剧毒类金属(Metalloid), 在自然环境中主要以三价亚砷酸盐[Arsenite, AsO2-, As(III)]和五价砷酸盐[Arsenate, AsO43-, As(V)]的无机形式广泛存在。许多微生物在含砷环境的长期适应过程中, 进化了多种不同的砷解毒抗性机制。目前研究发现主要存在4种类型的砷抗性机理, 包括: As(III)氧化, 细胞质As(V)还原, 呼吸性As(V)还原, As(III)甲基化, 这些机制赋予微生物砷抗性并在砷的转化和地球化学循环中起着极     

Visualisation of gradients in arsenic concentrations around individual roots of Zea mays L. using agar-immobilized bioreporter bacteria

The classical concept of arsenic transfer into plants through arsenate uptake via phosphate transporters, reduction to arsenite, complexation and compartmentation within vacuoles is challenged by recent identification of bidirectional transporters for arsenite and their potential role in plant As status regulation. Soil-based studies with chemical analysis of soil solution require root mat formation amplifying root effects on their surroundings and additionally denying investigations along individual roots differing in age and function. We tried to overcome these shortcomings by using bioreporter bacteria to visualise the spatial distribution of inorganic arsenic along roots and to characterize inorganic arsenic gradients in the rhizosphere concurrent with root age and branching. Therefore we developed an agar-based carrier element ensuring intimate contact between bioreporters and root-soil system and enabling fast and easy reporter output analysis. We show that inorganic arsenic distribution is related to root development with the highest bioreporter signal induction around lateral roots, which are known to show the highest expression of transporters responsible for bidirectional arsenite flux. Since there is so far no evidence for an arsenate efflux mechanism this is a strong indicator that we observed rather arsenite than arsenate efflux. No signal was detected along the distal region of young adventitious roots, i.e. the region of extension growth and root hair formation. The novel bioreporter assay may thus complement conventional measurements by providing information on the spatial distribution of inorganic arsenic on mm to cm-scale.     

Microbial oxidation of arsenite in a subarctic environment: diversity of arsenite oxidase genes and identification of a psychrotolerant arsenite oxidiser

Background  

Arsenic is toxic to most living cells. The two soluble inorganic forms of arsenic are arsenite (+3) and arsenate (+5), with arsenite the more toxic. Prokaryotic metabolism of arsenic has been reported in both thermal and moderate environments and has been shown to be involved in the redox cycling of arsenic. No arsenic metabolism (either dissimilatory arsenate reduction or arsenite oxidation) has ever been reported in cold environments (i.e. < 10°C).     

Estimation of Multimedia Inorganic Arsenic Intake in the U.S. Population

Arsenic is widely distributed in the environment by natural and human means. The potential for adverse health effects from inorganic arsenic depends on the level and route of exposure. To estimate potential health risks of inorganic arsenic, the apportionment of exposure among sources of inorganic arsenic is critical. In this study, daily inorganic arsenic intake of U.S. adults from food, water, and soil ingestion and from airborne particle inhalation was estimated. To account for variations in exposure across the U.S., a Monte Carlo approach was taken using simulations for 100,000 individuals representing the age, gender, and county of residence of the U.S. population based on census data. Our analysis found that food is the greatest source of inorganic arsenic intake and that drinking water is the next highest contributor. Inhalation of airborne arsenic-containing particles and ingestion of arsenic-containing soils were negligible contributors. The exposure is best represented by the ranges of inorganic arsenic intake (at the 10^th and 90^th percentiles), which were 1.8 to 11.4 µg/day for males and 1.3 to 9.4 µg/day for females. Regional differences in inorganic arsenic exposure were due mostly to consumption of drinking water containing differing inorganic arsenic content rather than to food preferences.     

Sorption and desorption of arsenic from sandy soils: Column studies

Rate‐limited sorption/desorption can have a profound effect upon the transport of sorbing contaminants. Numerical and analytical models used to predict chemical movement through the subsurface rarely incorporate the effects of nonlinear sorption and desorption kinetics, resulting in potentially large overestimates of mass extractability. Mass transfer characteristics of arsenic‐contaminated soils at the site of a former arsenical herbicide manufacturer in Houston, Texas, were examined in the laboratory using soil columns. Unaffected soils comprised of silty sands to coarse sands were collected from the uppermost aquifer. Two soil columns were loaded with a known mass of mixed organic and inorganic forms of arsenic resident in site ground water. A third control column was prepared with dry 20 × 30 mesh ASTM silica sand. Leachate samples were collected from each void volume until arsenic breakthrough was achieved. The dynamic test applied a continuing head of water, operating in an upflow mode through 4‐in. diameter by 12‐in. long soil columns repacked to in situ density. A flow‐through velocity of one void volume per day was chosen for arsenic loading to the columns and 0.08 void volume per day during the desorption phase of the test. Uncontaminated ground water was then passed through the columns, and the tests were restarted in the desorption mode. Analysis of the leachate and resulting arsenic concentrations in the test columns allowed for the calculation of distribution coefficients that describe arsenic behavior. Measured distribution coefficients during desorption ranged from 0.26 after one void volume to 3.3 after six void volumes had been passed through the column.     

Toxicity,bioavailability and metal speciation

1. Environmental toxicology emphasizes the difference from traditional toxicology in which pure compounds of interest are added to purified diets, or injected into the test animals. When the objective is to study the fate and effects of trace elements in the environment, knowledge of the speciation of the elements and their physico-chemical forms is important.2. Cadmium salts such as the sulfides, carbonates or oxides, are practically insoluble in water. However, these can be converted to water-soluble salts in nature under the influence of oxygen and acids. Chronic exposure to Cd is associated with renal toxicity in humans once a critical body burden is reached.3. The solubility of As(III) oxide in water is fairly low, but high in either acid or alkali. In water, arsenic is usually in the form of the arsenate or arsenite. As(III) is systemically more poisonous than the As(V), and As(V) is reduced to the As(III) form before exerting any toxic effects. Organic arsenicals also exert their toxic effects in vivo in animals by first metabolizing to the trivalent arsenoxide form. Some methyl arsenic compounds, such as di- and trimethylarsines, occur naturally as a consequence of biological activity. The toxic effect of arsenite can be potentiated by dithiols, while As has a protective effect against the toxicity of a variety of forms of Se in several species.4. Selenium occurs in several oxidation states and many selenium analogues of organic sulfur compounds exist in nature. Selenium in selenate form occurs in alkaline soils, where it is soluble and easily available to plants. Selenite binds tightly to iron and aluminum oxides and thus is quite insoluble in soils. Hydrogen selenide is a very toxic gas at room temperature. The methylated forms of Se are much less toxic for the organism than selenite. However, the methylated Se derivatives have strong synergistic toxicity with other minerals such as arsenic.5. Aquatic organisms absorb and retain Hg in the tissues, as methylmercury, although most of the environmental Hg to which they are exposed is inorganic. The methylmercury in fish arises from the bacterial methylation of inorganic Hg. Methylmercury in the human diet is almost completely absorbed into the bloodstream. The nervous system is the principal target tissue affected by methylmercury in adult human beings, while kidney is the critical organ following the ingestion of Hg(II) salts.