Urinary arsenic profiles reveal exposures to inorganic arsenic from private drinking water supplies in Cornwall, UK.

PubMed

Middleton, D R S; Watts, M J; Hamilton, E M; Ander, E L; Close, R M; Exley, K S; Crabbe, H; Leonardi, G S; Fletcher, T; Polya, D A

2016-05-09

Private water supplies (PWS) in Cornwall, South West England exceeded the current WHO guidance value and UK prescribed concentration or value (PCV) for arsenic of 10 μg/L in 5% of properties surveyed (n = 497). In this follow-up study, the first of its kind in the UK, volunteers (n = 207) from 127 households who used their PWS for drinking, provided urine and drinking water samples for total As determination by inductively coupled plasma mass spectrometry (ICP-MS) and urinary As speciation by high performance liquid chromatography ICP-MS (HPLC-ICP-MS). Arsenic concentrations exceeding 10 μg/L were found in the PWS of 10% of the volunteers. Unadjusted total urinary As concentrations were poorly correlated (Spearman's ρ = 0.36 (P < 0.001)) with PWS As largely due to the use of spot urine samples and the dominance of arsenobetaine (AB) from seafood sources. However, the osmolality adjusted sum, U-As(IMM), of urinary inorganic As species, arsenite (As(III)) and arsenate (As(V)), and their metabolites, methylarsonate (MA) and dimethylarsinate (DMA), was found to strongly correlate (Spearman's ρ: 0.62 (P < 0.001)) with PWS As, indicating private water supplies as the dominant source of inorganic As exposure in the study population of PWS users.

Urinary arsenic profiles reveal exposures to inorganic arsenic from private drinking water supplies in Cornwall, UK

PubMed Central

Middleton, D. R. S.; Watts, M. J.; Hamilton, E. M.; Ander, E. L.; Close, R. M.; Exley, K. S.; Crabbe, H.; Leonardi, G. S.; Fletcher, T.; Polya, D. A.

2016-01-01

Private water supplies (PWS) in Cornwall, South West England exceeded the current WHO guidance value and UK prescribed concentration or value (PCV) for arsenic of 10 μg/L in 5% of properties surveyed (n = 497). In this follow-up study, the first of its kind in the UK, volunteers (n = 207) from 127 households who used their PWS for drinking, provided urine and drinking water samples for total As determination by inductively coupled plasma mass spectrometry (ICP-MS) and urinary As speciation by high performance liquid chromatography ICP-MS (HPLC-ICP-MS). Arsenic concentrations exceeding 10 μg/L were found in the PWS of 10% of the volunteers. Unadjusted total urinary As concentrations were poorly correlated (Spearman’s ρ = 0.36 (P < 0.001)) with PWS As largely due to the use of spot urine samples and the dominance of arsenobetaine (AB) from seafood sources. However, the osmolality adjusted sum, U-AsIMM, of urinary inorganic As species, arsenite (AsIII) and arsenate (AsV), and their metabolites, methylarsonate (MA) and dimethylarsinate (DMA), was found to strongly correlate (Spearman’s ρ: 0.62 (P < 0.001)) with PWS As, indicating private water supplies as the dominant source of inorganic As exposure in the study population of PWS users. PMID:27156998

Urinary arsenic profiles reveal exposures to inorganic arsenic from private drinking water supplies in Cornwall, UK

NASA Astrophysics Data System (ADS)

Middleton, D. R. S.; Watts, M. J.; Hamilton, E. M.; Ander, E. L.; Close, R. M.; Exley, K. S.; Crabbe, H.; Leonardi, G. S.; Fletcher, T.; Polya, D. A.

2016-05-01

Private water supplies (PWS) in Cornwall, South West England exceeded the current WHO guidance value and UK prescribed concentration or value (PCV) for arsenic of 10 μg/L in 5% of properties surveyed (n = 497). In this follow-up study, the first of its kind in the UK, volunteers (n = 207) from 127 households who used their PWS for drinking, provided urine and drinking water samples for total As determination by inductively coupled plasma mass spectrometry (ICP-MS) and urinary As speciation by high performance liquid chromatography ICP-MS (HPLC-ICP-MS). Arsenic concentrations exceeding 10 μg/L were found in the PWS of 10% of the volunteers. Unadjusted total urinary As concentrations were poorly correlated (Spearman’s ρ = 0.36 (P < 0.001)) with PWS As largely due to the use of spot urine samples and the dominance of arsenobetaine (AB) from seafood sources. However, the osmolality adjusted sum, U-AsIMM, of urinary inorganic As species, arsenite (AsIII) and arsenate (AsV), and their metabolites, methylarsonate (MA) and dimethylarsinate (DMA), was found to strongly correlate (Spearman’s ρ: 0.62 (P < 0.001)) with PWS As, indicating private water supplies as the dominant source of inorganic As exposure in the study population of PWS users.

Unusual arsenic metabolism in Giant Pandas.

PubMed

Braeuer, Simone; Dungl, Eveline; Hoffmann, Wiebke; Li, Desheng; Wang, Chengdong; Zhang, Hemin; Goessler, Walter

2017-12-01

The total arsenic concentration and the arsenic speciation in urine and feces samples of the two Giant Pandas living at Vienna zoo and of their feed, bamboo, were determined with ICPMS and HPLC-ICPMS. Urine was the main excretion route and accounted for around 90% of the ingested arsenic. The urinary arsenic concentrations were very high, namely up to 179 μg/L. Dimethylarsinic acid (DMA) was the dominating arsenic compound in the urine samples and ranged from 73 to 92% of the total arsenic, which is unusually high for a terrestrial mammal. The feces samples contained around 70% inorganic arsenic and 30% DMA. The arsenic concentrations in the bamboo samples were between 16 and 920 μg/kg dry mass. The main arsenic species in the bamboo extracts was inorganic arsenic. This indicates that the Giant Panda possesses a unique way of very efficiently methylating and excreting the provided inorganic arsenic. This could be essential for the survival of the animal in its natural habitat, because parts of this area are contaminated with arsenic. Copyright © 2017 Elsevier Ltd. All rights reserved.

APPLICATION OF SAMPLE PRE-OXIDATION OF ARSENITE IN HUMAN URINE PRIOR TO SPECIATON VIA ON-LINE PHOTO-OXIDATION WITH MEMBRANE HYDRIDE GENRATION AND ICP-MS DETECTION

EPA Science Inventory

A pre-oxidation procedure which converts arsenite (AS(III)) to arsenate (As(VVV)) was investigated in urinary arsenic speciation prior to on-line photo-oxidation hydride-generation with ICP-MS detection. This sample pre-oxidation method eliminates As(III) and As(V) preservation c...

Changes in serum thioredoxin among individuals chronically exposed to arsenic in drinking water.

PubMed

Li, Yuanyuan; Gao, Yanhui; Zhao, Lijun; Wei, Yudan; Feng, Hongqi; Wang, Cheng; Wei, Wei; Ding, Yunpeng; Sun, Dianjun

2012-02-15

It is well known that oxidative damage plays a key role in the development of chronic arsenicosis. There is a complex set of mechanisms of redox cycling in vivo to protect cells from the damage. In this study, we examined the differences in the levels of serum thioredoxin1 (TRX1) among individuals exposed to different levels of arsenic in drinking water and detected early biomarkers of arsenic poisoning before the appearance of skin lesions. A total of 157 subjects from endemic regions of China were selected and divided into arsenicosis group with skin lesions (total intake of arsenic: 8.68-45.71mg-year) and non-arsenicosis group without skin lesions, which further divided into low (0.00-1.06mg-year), medium (1.37-3.55mg-year), and high (4.26-48.13mg-year) arsenic exposure groups. Concentrations of serum TRX1 were analyzed by an ELISA method. Levels of water arsenic and urinary speciated arsenics, including inorganic arsenic (iAs), monomethylated arsenic (MMA), and dimethylated arsenic (DMA), were determined by hydride generation atomic absorption spectrometry. Our results showed that the levels of serum TRX1 in arsenicosis patients were significantly higher than that of the subjects who were chronically exposed to arsenic, but without skin lesions. A positive correlation was seen between the levels of serum TRX1 and the total water arsenic intake or the levels of urinary arsenic species. The results of this study indicate that arsenic exposure could significantly change the levels of human serum TRX1, which can be detected before arsenic-specific dermatological symptoms occur. This study provides further evidence on revealing the mechanism of arsenic toxicity. Copyright © 2011 Elsevier Inc. All rights reserved.

Arsenic Speciation in Groundwater: Role of Thioanions

EPA Science Inventory

The behavior of arsenic in groundwater environments is fundamentally linked to its speciation. Understanding arsenic speciation is important because chemical speciation impacts reactivity, bioavailability, toxicity, and transport and fate processes. In aerobic environments arsen...

A biological indicator of inorganic arsenic exposure using the sum of urinary inorganic arsenic and monomethylarsonic acid concentrations

PubMed Central

Hata, Akihisa; Kurosawa, Hidetoshi; Endo, Yoko; Yamanaka, Kenzo; Fujitani, Noboru; Endo, Ginji

2016-01-01

Objectives: The sum of urinary inorganic arsenic (iAs), monomethylarsonic acid (MMA), and dimethylarsinic acid (DMA) concentrations is used for the biological monitoring of occupational iAs exposure. Although DMA is a major metabolite of iAs, it is an inadequate index because high DMA levels are present in urine after seafood consumption. We estimated the urinary iAs+MMA concentration corresponding to iAs exposure. Methods: We used data from two arsenic speciation analyses of urine samples from 330 Bangladeshi with oral iAs exposure and 172 Japanese workers without occupational iAs exposure using high-performance liquid chromatography with inductively coupled plasma mass spectrometry. Results: iAs, MMA, and DMA, but not arsenobetaine (AsBe), were detected in the urine of the Bangladeshi subjects. The correlation between iAs+MMA+DMA and iAs+MMA was obtained as log (iAs+MMA) = 1.038 log (iAs+MMA+DMA) -0.658. Using the regression formula, the iAs+MMA value was calculated as 2.15 and 7.5 μg As/l, corresponding to 3 and 10 μg As/m3 of exposures, respectively. In the urine of the Japanese workers, arsenic was mostly excreted as AsBe. We used the 95th percentile of iAs+MMA (12.6 μg As/l) as the background value. The sum of the calculated and background values can be used as a biological indicator of iAs exposure. Conclusion: We propose 14.8 and 20.1 μg As/l of urinary iAs+MMA as the biological indicators of 3 and 10 μg As/m3 iAs exposure, respectively. PMID:27010090

Changes in serum thioredoxin among individuals chronically exposed to arsenic in drinking water

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Yuanyuan; Gao, Yanhui; Zhao, Lijun

2012-02-15

It is well known that oxidative damage plays a key role in the development of chronic arsenicosis. There is a complex set of mechanisms of redox cycling in vivo to protect cells from the damage. In this study, we examined the differences in the levels of serum thioredoxin1 (TRX1) among individuals exposed to different levels of arsenic in drinking water and detected early biomarkers of arsenic poisoning before the appearance of skin lesions. A total of 157 subjects from endemic regions of China were selected and divided into arsenicosis group with skin lesions (total intake of arsenic: 8.68–45.71 mg-year) andmore » non-arsenicosis group without skin lesions, which further divided into low (0.00–1.06 mg-year), medium (1.37–3.55 mg-year), and high (4.26–48.13 mg-year) arsenic exposure groups. Concentrations of serum TRX1 were analyzed by an ELISA method. Levels of water arsenic and urinary speciated arsenics, including inorganic arsenic (iAs), monomethylated arsenic (MMA), and dimethylated arsenic (DMA), were determined by hydride generation atomic absorption spectrometry. Our results showed that the levels of serum TRX1 in arsenicosis patients were significantly higher than that of the subjects who were chronically exposed to arsenic, but without skin lesions. A positive correlation was seen between the levels of serum TRX1 and the total water arsenic intake or the levels of urinary arsenic species. The results of this study indicate that arsenic exposure could significantly change the levels of human serum TRX1, which can be detected before arsenic-specific dermatological symptoms occur. This study provides further evidence on revealing the mechanism of arsenic toxicity. -- Highlights: ► Three regions are selected as the areas affected by endemic arsenicosis of China. ► We first examine changes in serum TRX1 among individuals exposed to arsenic. ► A positive correlation was seen between serum TRX1 and total water arsenic intake. ► The same relationship was seen between serum TRX1 and urinary arsenic species. ► TRX as early biomarker of arsenicosis can be detected before skin lesions occur.« less

ARSENIC SPECIATION ANALYSIS IN HUMAN SALIVA

EPA Science Inventory

Background: Determination of arsenic species in human saliva is potentially useful for biomonitoring of human exposure to arsenic and for studying arsenic metabolism. However, there is no report on the speciation analysis of arsenic in saliva. Methods: Arsenic species in saliva ...

Arsenic speciation in rice and risk assessment of inorganic arsenic in Taiwan population.

PubMed

Chen, Hsiu-Ling; Lee, Ching-Chang; Huang, Winn-Jung; Huang, Han-Ting; Wu, Yi-Chen; Hsu, Ya-Chen; Kao, Yi-Ting

2016-03-01

This study assessed the total arsenic content and arsenic speciation in rice to determine the health risks associated with rice consumption in various age-gender subgroups in Taiwan. The average total arsenic levels in white rice and brown rice were 116.6 ± 39.2 and 215.5 ± 63.5 ng/g weight (n = 51 and 13), respectively. The cumulative cancer risk among males was 10.4/100,000. The highest fraction of inorganic/total arsenic content in white rice ranged from 76.9 to 88.2 % and from 81.0 to 96.5 % in brown rice. The current study found different arsenic speciation of rice in southern Taiwan, where the famous blackfoot disease has been reported compared with arsenic speciation from other Taiwan areas. Therefore, rice and other grains should be further monitored in southern Taiwan to evaluate whether arsenic contamination is well controlled in this area.

Evaluation of arsenic speciation in rainbow trout and fathead minnows from dietary exposure

EPA Science Inventory

The concentration of total arsenic and various arsenic species were measured in food and fish tissue samples from two dietary arsenic exposures to juvenile fish. For arsenic speciation, samples were extracted with 10% MeOH and analyzed by HPLC/ICPMS. Total arsenic concentration...

Arsenic speciation and sorption in natural environments

USGS Publications Warehouse

Campbell, Kate M.; Nordstrom, D. Kirk

2014-01-01

Aqueous arsenic speciation, or the chemical forms in which arsenic exists in water, is a challenging, interesting, and complicated aspect of environmental arsenic geochemistry. Arsenic has the ability to form a wide range of chemical bonds with carbon, oxygen, hydrogen, and sulfur, resulting in a large variety of compounds that exhibit a host of chemical and biochemical properties. Besides the intriguing chemical diversity, arsenic also has the rare capacity to capture our imaginations in a way that few elements can duplicate: it invokes images of foul play that range from sinister to comedic (e.g., “inheritance powder” and arsenic-spiked elderberry wine). However, the emergence of serious large-scale human health problems from chronic arsenic exposure in drinking water has placed a high priority on understanding environmental arsenic mobility, toxicity, and bioavailability, and chemical speciation is key to these important questions. Ultimately, the purpose of arsenic speciation research is to predict future occurrences, mitigate contamination, and provide successful management of water resources.

In Vitro Model To Assess Arsenic Bioaccessibility and Speciation in Cooked Shrimp.

PubMed

Chi, Haifeng; Zhang, Youchi; Williams, Paul N; Lin, Shanna; Hou, Yanwei; Cai, Chao

2018-05-09

Shrimp, a popular and readily consumed seafood, contains high concentrations of arsenic. However, few studies have focused on whether arsenic in the shrimp could be transformed during the cooking process and gastrointestinal digestion. In this study, a combined in vitro model [Unified Bioaccessibility Research Group of Europe (BARGE) Method-Simulator of Human Intestinal Microbial Ecosystem (UBM-SHIME)] was used to investigate arsenic bioaccessibility and its speciation in raw and cooked shrimps. The results showed that the cooking practices had little effect on the arsenic content and speciation. Bioaccessibility of arsenic in raw shrimp was at a high level, averaging 76.9 ± 4.28 and 86.7 ± 3.74% in gastric and small intestinal phases, respectively. Arsenic speciation was stable in all of the shrimp digestions, with nontoxic arsenobetaine (AsB) being the dominated speciation. The cooking practice significantly increased the bioaccessibility of arsenate ( p < 0.05) in shrimp digests, indicating the increase of the potential health risks.

Arsenic Speciation of Terrestrial Invertebrates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Moriarty, M.M.; Koch, I.; Gordon, R.A.

2009-07-01

The distribution and chemical form (speciation) of arsenic in terrestrial food chains determines both the amount of arsenic available to higher organisms, and the toxicity of this metalloid in affected ecosystems. Invertebrates are part of complex terrestrial food webs. This paper provides arsenic concentrations and arsenic speciation profiles for eight orders of terrestrial invertebrates collected at three historical gold mine sites and one background site in Nova Scotia, Canada. Total arsenic concentrations, determined by inductively coupled plasma mass spectrometry (ICP-MS), were dependent upon the classification of invertebrate. Arsenic species were determined by high-performance liquid chromatography (HPLC) ICP-MS and X-ray absorptionmore » spectroscopy (XAS). Invertebrates were found by HPLC ICP-MS to contain predominantly arsenite and arsenate in methanol/water extracts, while XAS revealed that most arsenic is bound to sulfur in vivo. Examination of the spatial distribution of arsenic within an ant tissue highlighted the differences between exogenous and endogenous arsenic, as well as the extent to which arsenic is transformed upon ingestion. Similar arsenic speciation patterns for invertebrate groups were observed across sites. Trace amounts of arsenobetaine and arsenocholine were identified in slugs, ants, and spiders.« less

Examination of Arsenic Speciation in Sulfidic Solutions Using X-ray Absorption Spectroscopy

EPA Science Inventory

The chemical speciation of arsenic in sulfidic waters is complicated by the existence of thioarsenic species. The purpose of this research was to use advanced spectroscopy techniques along with speciation modeling and chromatography to elucidate the chemical speciation of As in ...

Binational arsenic exposure survey: methodology and estimated arsenic intake from drinking water and urinary arsenic concentrations.

PubMed

Roberge, Jason; O'Rourke, Mary Kay; Meza-Montenegro, Maria Mercedes; Gutiérrez-Millán, Luis Enrique; Burgess, Jefferey L; Harris, Robin B

2012-04-01

The Binational Arsenic Exposure Survey (BAsES) was designed to evaluate probable arsenic exposures in selected areas of southern Arizona and northern Mexico, two regions with known elevated levels of arsenic in groundwater reserves. This paper describes the methodology of BAsES and the relationship between estimated arsenic intake from beverages and arsenic output in urine. Households from eight communities were selected for their varying groundwater arsenic concentrations in Arizona, USA and Sonora, Mexico. Adults responded to questionnaires and provided dietary information. A first morning urine void and water from all household drinking sources were collected. Associations between urinary arsenic concentration (total, organic, inorganic) and estimated level of arsenic consumed from water and other beverages were evaluated through crude associations and by random effects models. Median estimated total arsenic intake from beverages among participants from Arizona communities ranged from 1.7 to 14.1 µg/day compared to 0.6 to 3.4 µg/day among those from Mexico communities. In contrast, median urinary inorganic arsenic concentrations were greatest among participants from Hermosillo, Mexico (6.2 µg/L) whereas a high of 2.0 µg/L was found among participants from Ajo, Arizona. Estimated arsenic intake from drinking water was associated with urinary total arsenic concentration (p < 0.001), urinary inorganic arsenic concentration (p < 0.001), and urinary sum of species (p < 0.001). Urinary arsenic concentrations increased between 7% and 12% for each one percent increase in arsenic consumed from drinking water. Variability in arsenic intake from beverages and urinary arsenic output yielded counter intuitive results. Estimated intake of arsenic from all beverages was greatest among Arizonans yet participants in Mexico had higher urinary total and inorganic arsenic concentrations. Other contributors to urinary arsenic concentrations should be evaluated.

Binational Arsenic Exposure Survey: Methodology and Estimated Arsenic Intake from Drinking Water and Urinary Arsenic Concentrations

PubMed Central

Roberge, Jason; O’Rourke, Mary Kay; Meza-Montenegro, Maria Mercedes; Gutiérrez-Millán, Luis Enrique; Burgess, Jefferey L.; Harris, Robin B.

2012-01-01

The Binational Arsenic Exposure Survey (BAsES) was designed to evaluate probable arsenic exposures in selected areas of southern Arizona and northern Mexico, two regions with known elevated levels of arsenic in groundwater reserves. This paper describes the methodology of BAsES and the relationship between estimated arsenic intake from beverages and arsenic output in urine. Households from eight communities were selected for their varying groundwater arsenic concentrations in Arizona, USA and Sonora, Mexico. Adults responded to questionnaires and provided dietary information. A first morning urine void and water from all household drinking sources were collected. Associations between urinary arsenic concentration (total, organic, inorganic) and estimated level of arsenic consumed from water and other beverages were evaluated through crude associations and by random effects models. Median estimated total arsenic intake from beverages among participants from Arizona communities ranged from 1.7 to 14.1 µg/day compared to 0.6 to 3.4 µg/day among those from Mexico communities. In contrast, median urinary inorganic arsenic concentrations were greatest among participants from Hermosillo, Mexico (6.2 µg/L) whereas a high of 2.0 µg/L was found among participants from Ajo, Arizona. Estimated arsenic intake from drinking water was associated with urinary total arsenic concentration (p < 0.001), urinary inorganic arsenic concentration (p < 0.001), and urinary sum of species (p < 0.001). Urinary arsenic concentrations increased between 7% and 12% for each one percent increase in arsenic consumed from drinking water. Variability in arsenic intake from beverages and urinary arsenic output yielded counter intuitive results. Estimated intake of arsenic from all beverages was greatest among Arizonans yet participants in Mexico had higher urinary total and inorganic arsenic concentrations. Other contributors to urinary arsenic concentrations should be evaluated. PMID:22690182

Sample preparation and storage can change arsenic speciation in human urine.

PubMed

Feldmann, J; Lai, V W; Cullen, W R; Ma, M; Lu, X; Le, X C

1999-11-01

Stability of chemical speciation during sample handling and storage is a prerequisite to obtaining reliable results of trace element speciation analysis. There is no comprehensive information on the stability of common arsenic species, such as inorganic arsenite [As(III)], arsenate [As(V)], monomethylarsonic acid, dimethylarsinic acid, and arsenobetaine, in human urine. We compared the effects of the following storage conditions on the stability of these arsenic species: temperature (25, 4, and -20 degrees C), storage time (1, 2, 4, and 8 months), and the use of additives (HCl, sodium azide, benzoic acid, benzyltrimethylammonium chloride, and cetylpyridinium chloride). HPLC with both inductively coupled plasma mass spectrometry and hydride generation atomic fluorescence detection techniques were used for the speciation of arsenic. We found that all five of the arsenic species were stable for up to 2 months when urine samples were stored at 4 and -20 degrees C without any additives. For longer period of storage (4 and 8 months), the stability of arsenic species was dependent on urine matrices. Whereas the arsenic speciation in some urine samples was stable for the entire 8 months at both 4 and -20 degrees C, other urine samples stored under identical conditions showed substantial changes in the concentration of As(III), As(V), monomethylarsonic acid, and dimethylarsinic acid. The use of additives did not improve the stability of arsenic speciation in urine. The addition of 0.1 mol/L HCl (final concentration) to urine samples produced relative changes in inorganic As(III) and As(V) concentrations. Low temperature (4 and -20 degrees C) conditions are suitable for the storage of urine samples for up to 2 months. Untreated samples maintain their concentration of arsenic species, and additives have no particular benefit. Strong acidification is not appropriate for speciation analysis.

Microbial-driven arsenic cycling in rice paddies amended with monosodium methanearsonate

NASA Astrophysics Data System (ADS)

Maguffin, S. C.; McClung, A.; Rohila, J. S.; Derry, L. A.; Huang, R.; Reid, M. C.

2017-12-01

Rice consumption is the second largest contributor to human arsenic exposure worldwide and is linked to many serious diseases. Because rice is uniquely adapted for agricultural production under flooded soils, arsenic species solubilized in such environments can be effectively transported into plant tissue via root transporters. Through this process, both inorganic and organic (methylated) arsenic species can accumulate to problematic concentrations and may affect grain yield as well as crop value. The distribution of these species in plant tissue is determined by arsenic sources, as well as enzymatic redox and methylation-demethylation reactions in soils and pore water. Historic use of organoarsenic-based pesticides in US agriculture may provide an enduring source of arsenic in rice paddies. However, it is unclear how persistent these organic species are in the adsorbed phase or how available they remain to rice cultivars throughout the growing season. We conducted a field experiment in a 2x2 factorial design examining the effects of irrigation methods (continuous flooding and alternate wetting and drying) and monosodium methanearsonate (MSMA) application on the abundance and speciation of arsenic in pore water, soil, and rice plant tissues. We monitored arsenic speciation and partitioning between these reservoirs at semi-weekly to semi-monthly frequencies. Pore water arsenic speciation was determined using LC-ICP-MS, and X-ray absorption near-edge structure (XANES) analysis was employed to speciate the arsenic within solid-phase soil and plant tissue throughout the growing season. These data help clarify the role of two irrigation methods and MSMA amendments for arsenic bioavailability and speciation in rice. Furthermore, the study illuminates the significance of microbial metabolism in the reapportionment of arsenic within the soil-plant-water system and its impact on arsenic levels in rice grains.

Speciation of arsenic in exfoliated urinary bladder epithelial cells from individuals exposed to arsenic in drinking water.

PubMed

Hernández-Zavala, Araceli; Valenzuela, Olga L; Matousek, Tomás; Drobná, Zuzana; Dĕdina, Jirí; García-Vargas, Gonzalo G; Thomas, David J; Del Razo, Luz M; Stýblo, Miroslav

2008-12-01

The concentration of arsenic in urine has been used as a marker of exposure to inorganic As (iAs). Relative proportions of urinary metabolites of iAs have been identified as potential biomarkers of susceptibility to iAs toxicity. However, the adverse effects of iAs exposure are ultimately determined by the concentrations of iAs metabolites in target tissues. In this study we examined the feasibility of analyzing As species in cells that originate in the urinary bladder, a target organ for As-induced cancer in humans. Exfoliated bladder epithelial cells (BECs) were collected from urine of 21 residents of Zimapan, Mexico, who were exposed to iAs in drinking water. We determined concentrations of iAs, methyl-As (MAs), and dimethyl-As (DMAs) in urine using conventional hydride generation-cryotrapping-atomic absorption spectrometry (HG-CT-AAS). We used an optimized HG-CT-AAS technique with detection limits of 12-17 pg As for analysis of As species in BECs. All urine samples and 20 of 21 BEC samples contained detectable concentrations of iAs, MAs, and DMAs. Sums of concentrations of these As species in BECs ranged from 0.18 to 11.4 ng As/mg protein and in urine from 4.8 to 1,947 ng As/mL. We found no correlations between the concentrations or ratios of As species in BECs and in urine. These results suggest that urinary levels of iAs metabolites do not necessarily reflect levels of these metabolites in the bladder epithelium. Thus, analysis of As species in BECs may provide a more effective tool for risk assessment of bladder cancer and other urothelial diseases associated with exposures to iAs.

SPECIATION OF ARSENIC IN SULFIDIC SOLUTIONS USING X-RAY ABSORPTION SPECTROSCOPY

EPA Science Inventory

The fate of arsenic in the environment is fundamentally linked to its speciation. Arsenic in aerobic environments is predominantly arsenate, however under reducing conditions arsenite species dominate. In sulfidic environments, thioarsenic species are known to exist and play key...

Whole-house arsenic water treatment provided more effective arsenic exposure reduction than point-of-use water treatment at New Jersey homes with arsenic in well water

PubMed Central

Spayd, Steven E.; Robson, Mark G.; Buckley, Brian T.

2014-01-01

A comparison of the effectiveness of whole house (point-of-entry) and point-of-use arsenic water treatment systems in reducing arsenic exposure from well water was conducted. The non-randomized observational study recruited 49 subjects having elevated arsenic in their residential home well water in New Jersey. The subjects obtained either point-of-entry or point-of-use arsenic water treatment. Prior ingestion exposure to arsenic in well water was calculated by measuring arsenic concentrations in the well water and obtaining water-use histories for each subject, including years of residence with the current well and amount of water consumed from the well per day. A series of urine samples were collected from the subjects, some starting before water treatment was installed and continuing for at least nine months after treatment had begun. Urine samples were analyzed and speciated for inorganic-related arsenic concentrations. A two-phase clearance of inorganic-related arsenic from urine and the likelihood of a significant body burden from chronic exposure to arsenic in drinking water were identified. After nine months of water treatment the adjusted mean of the urinary inorganic-related arsenic concentrations were significantly lower (p < 0.0005) in the point-of-entry treatment group (2.5 μg/g creatinine) than in the point-of-use treatment group (7.2 μg/g creatinine). The results suggest that whole house arsenic water treatment systems provide a more effective reduction of arsenic exposure from well water than that obtained by point-of-use treatment. PMID:24975493

Bioconcentration and arsenic speciation analysis in ragworm, Hediste diversicolor (Muller 1776).

PubMed

Gaion, Andrea; Scuderi, Alice; Pellegrini, David; Sartori, Davide

2013-01-01

This study focused on bioconcentrations of arsenic in Hediste diversicolor (Müller 1776) after exposure to three different molecule solutions: arsenate, dimethyl-arsinate and arsenobetaine. Speciation analysis was carried out after exposing the organisms to these solutions in order to investigate their arsenic biotransformation capacity. Arsenic reached to the maximum level in these tissues after 15 days' exposure to a solution of 100 μg L(-1) of arsenobetaine, although a significant increase was obtained in worms exposed to arsenate. Speciation analysis shows that trimethyl-arsine oxide is the slowest detoxification phase recorded in experiment.

Earth Abides Arsenic Biotransformations

NASA Astrophysics Data System (ADS)

Zhu, Yong-Guan; Yoshinaga, Masafumi; Zhao, Fang-Jie; Rosen, Barry P.

2014-05-01

Arsenic is the most prevalent environmental toxic element and causes health problems throughout the world. The toxicity, mobility, and fate of arsenic in the environment are largely determined by its speciation, and arsenic speciation changes are driven, at least to some extent, by biological processes. In this article, biotransformation of arsenic is reviewed from the perspective of the formation of Earth and the evolution of life, and the connection between arsenic geochemistry and biology is described. The article provides a comprehensive overview of molecular mechanisms of arsenic redox and methylation cycles as well as other arsenic biotransformations. It also discusses the implications of arsenic biotransformation in environmental remediation and food safety, with particular emphasis on groundwater arsenic contamination and arsenic accumulation in rice.

Arsenic speciation in edible mushrooms.

PubMed

Nearing, Michelle M; Koch, Iris; Reimer, Kenneth J

2014-12-16

The fruiting bodies, or mushrooms, of terrestrial fungi have been found to contain a high proportion of the nontoxic arsenic compound arsenobetaine (AB), but data gaps include a limited phylogenetic diversity of the fungi for which arsenic speciation is available, a focus on mushrooms with higher total arsenic concentrations, and the unknown formation and role of AB in mushrooms. To address these, the mushrooms of 46 different fungus species (73 samples) over a diverse range of phylogenetic groups were collected from Canadian grocery stores and background and arsenic-contaminated areas. Total arsenic was determined using ICP-MS, and arsenic speciation was determined using HPLC-ICP-MS and complementary X-ray absorption spectroscopy (XAS). The major arsenic compounds in mushrooms were found to be similar among phylogenetic groups, and AB was found to be the major compound in the Lycoperdaceae and Agaricaceae families but generally absent in log-growing mushrooms, suggesting the microbial community may influence arsenic speciation in mushrooms. The high proportion of AB in mushrooms with puffball or gilled morphologies may suggest that AB acts as an osmolyte in certain mushrooms to help maintain fruiting body structure. The presence of an As(III)-sulfur compound, for the first time in mushrooms, was identified in the XAS analysis. Except for Agaricus sp. (with predominantly AB), inorganic arsenic predominated in most of the store-bought mushrooms (albeit with low total arsenic concentrations). Should inorganic arsenic predominate in these mushrooms from contaminated areas, the risk to consumers under these circumstances should be considered.

Field Evaluation Of Arsenic Speciation In Sediments At The Ground Water/Surface Water Interface

EPA Science Inventory

The speciation and mineralogy of sediments contaminated with arsenic at the ground water/surface water interface of the Ft. Devens Super Fund Site in Ft. Devens, MA were determined using X-ray absorption fine structure and X-ray diffraction spectroscopy. Speciation and mineralog...

A review of recent developments in the speciation and location of arsenic and selenium in rice grain

PubMed Central

Carey, Anne-Marie; Lombi, Enzo; Donner, Erica; de Jonge, Martin D.; Punshon, Tracy; Jackson, Brian P.; Guerinot, Mary Lou; Price, Adam H.; Meharg, Andrew A.

2014-01-01

Rice is a staple food yet is a significant dietary source of inorganic arsenic, a class 1, nonthreshold carcinogen. Establishing the location and speciation of arsenic within the edible rice grain is essential for understanding the risk and for developing effective strategies to reduce grain arsenic concentrations. Conversely, selenium is an essential micronutrient and up to 1 billion people worldwide are selenium-deficient. Several studies have suggested that selenium supplementation can reduce the risk of some cancers, generating substantial interest in biofortifying rice. Knowledge of selenium location and speciation is important, because the anti-cancer effects of selenium depend on its speciation. Germanic acid is an arsenite/silicic acid analogue, and location of germanium may help elucidate the mechanisms of arsenite transport into grain. This review summarises recent discoveries in the location and speciation of arsenic, germanium, and selenium in rice grain using state-of-the-art mass spectrometry and synchrotron techniques, and illustrates both the importance of high-sensitivity and high-resolution techniques and the advantages of combining techniques in an integrated quantitative and spatial approach. PMID:22159463

Speciation And Distribution Of Arsenic In Fresh Water Pond Sediments Impacted By Contaminated Ground-Water Discharge

EPA Science Inventory

The speciation and mineralogy of sediments contaminated with arsenic due to arsenic enriched groundwater discharging into the pond at the Ft. Devens Super Fund Site in Ft. Devens, MA were determined using X-ray absorption fine structure and X-ray diffraction spectroscopy. Specia...

Arsenic Species in Drinking Water Wells in the USA with High Arsenic Concentrations

EPA Science Inventory

As part of the United States Environmental Protection Agency (USEPA) arsenic treatment demonstration program, 65 five well waters scattered across the US were speciated for As(III) and As(V). The speciation test data showed that most (60) well waters had one dominant species, but...

Field Evaluation Of Arsenic Transport Across The Ground Water/Surface Water Interface: Speciation In Sediment Material

EPA Science Inventory

The solubility and mobility of arsenic in ground water are influenced by a variety of processes in the northeastern US subjective to geogenic and anthropogenic sources. This presentation will discuss the speciation of arsenic in sediment profiles resulting from ground water disc...

Urinary total arsenic and 8-hydroxydeoxyguanosine are associated with renal cell carcinoma in an area without obvious arsenic exposure

DOE Office of Scientific and Technical Information (OSTI.GOV)

Huang, Chao-Yuan; Department of Urology, National Taiwan University Hospital, College of Medicine National Taiwan University, Taipei, Taiwan; Su, Chien-Tien

2012-08-01

8-Hydroxydeoxyguanosine (8-OHdG) is one of the most reliable and abundant markers of DNA damage. The study was designed to explore the relationship between urinary 8-OHdG and renal cell carcinoma (RCC) and to investigate whether individuals with a high level of 8-OHdG would have a modified odds ratio (OR) of arsenic-related RCC. This case–control study was conducted with 132 RCC patients and 245 age- and sex-matched controls from a hospital-based pool between November 2006 and May 2009. Pathological verification of RCC was completed by image-guided biopsy or surgical resection of renal tumors. Urinary 8-OHdG levels were determined using liquid chromatography withmore » tandem mass spectrometry (LC–MS/MS). Concentrations of urinary arsenic species, including inorganic arsenic, monomethylarsonic acid (MMA) and dimethylarsinic acid (DMA), were determined by a high performance liquid chromatography-linked hydride generator and atomic absorption spectrometry. Level of urinary 8-OHdG was significantly associated with the OR of RCC in a dose–response relationship after multivariate adjustment. Urinary 8-OHdG was significantly related to urinary total arsenic. The greatest OR (3.50) was seen in the individuals with high urinary 8-OHdG and high urinary total arsenic. A trend test indicated that the OR of RCC was increased with one of these factors and was further increased with both (p = 0.002). In conclusion, higher urinary 8-OHdG was a strong predictor of the RCC. High levels of 8-OHdG combined with urinary total arsenic might be indicative of arsenic-induced RCC. -- Highlights: ► Urinary 8-OHdG was significantly related to urinary total arsenic. ► Higher urinary 8-OHdG was a strong predictor of RCC risk. ► Urinary 8-OHdG may modify arsenic related RCC risk.« less

HPLC-ICP-MS speciation analysis and risk assessment of arsenic in Cordyceps sinensis.

PubMed

Zuo, Tian-Tian; Li, Yao-Lei; Jin, Hong-Yu; Gao, Fei; Wang, Qi; Wang, Ya-Dan; Ma, Shuang-Cheng

2018-01-01

Cordyceps sinensis , one of the most valued traditional herbal medicines in China, contains high amount of arsenic. Considering the adverse health effects of arsenic, this is of particular concern. The aim of this study was to determine and analyze arsenic speciation in C. sinensis , and to measure the associated human health risks. We used microwave extraction and high-performance liquid chromatography coupled with inductively coupled plasma mass spectrometry to determine and analyze the arsenic content in C. sinensis , and measured the associated human health risks according to the hazard index (HI), lifetime cancer risk (CR), and target hazard quotient (THQ). The main arsenic speciation in C. sinensis were not the four organic arsenic compounds, including dimethyl arsenic, monomethyl arsenic, arsenobetaine, and arsenocholine, but comprised inorganic arsenic and other unknown risk arsenic compounds. HI scores indicated that the risk of C. sinensis was acceptable. CR results suggested that the cancer risk was greater than the acceptable lifetime risk of 10 -5 , even at low exposure levels. THQ results indicated that at the exposure level < 2.0 months/year, the arsenic was not likely to harm human health during a lifetime; however, if the exposure rate was > 3.0 months/year, the systemic effects of the arsenic in C. sinensis was of great concern. The arsenic in C. sinensis might not be free of risks. The suggested C. sinensis consumption rate of 2.0 months/year provided important insights into the ways by which to minimize potential health risks. Our study not only played the role of "cast a brick to attract jade" by which to analyze arsenic speciation in C. sinensis but also offered a promising strategy of risk assessment for harmful residues in traditional herbal medicines.

Speciation And Distribution Of Arsenic In Fresh Water Pond Sediments Impacted By Contaminated Ground-Water Discharge (Presentation)

EPA Science Inventory

The speciation and mineralogy of sediments contaminated with arsenic due to arsenic enriched groundwater discharging into the pond at the Ft. Devens Super Fund Site in Ft. Devens, MA were determined using X-ray absorption fine structure and X-ray diffraction spectroscopy. Speci...

Urinary Arsenic in Human Samples from Areas Characterized by Natural or Anthropogenic Pollution in Italy.

PubMed

Minichilli, Fabrizio; Bianchi, Fabrizio; Ronchi, Anna Maria; Gorini, Francesca; Bustaffa, Elisa

2018-02-09

Arsenic is ubiquitous and has a potentially adverse impact on human health. We compared the distribution of concentrations of urinary inorganic arsenic plus methylated forms (uc(iAs+MMA+DMA)) in four Italian areas with other international studies, and we assessed the relationship between uc(iAs+MMA+DMA) and various exposure factors. We conducted a human biomonitoring study on 271 subjects (132 men) aged 20-44, randomly sampled and stratified by area, gender, and age. Data on environmental and occupational exposure and dietary habits were collected through a questionnaire. Arsenic was speciated using chromatographic separation and inductively coupled mass spectrometry. Associations between uc(iAs+MMA+DMA) and exposure factors were evaluated using the geometric mean ratio (GMR) with a 90% confidence interval by stepwise multiple regression analysis. The 95th percentile value of uc(iAs+MMA+DMA) for the whole sample (86.28 µg/L) was higher than other national studies worldwide. A statistical significant correlation was found between uc(iAs+MMA+DMA) and occupational exposure (GMR: 2.68 [1.79-4.00]), GSTT gene (GMR: 0.68 [0.52-0.80]), consumption of tap water (GMR: 1.35 [1.02-1.77]), seafood (GMR: 1.44 [1.11-1.88]), whole milk (GMR: 1.34 [1.04-1.73]), and fruit/vegetables (GMR: 1.37 [1.03-1.82]). This study demonstrated the utility of uc(iAs+MMA+DMA) as a biomarker to assess environmental exposure. In a public health context, this information could be used to support remedial action, to prevent individuals from being further exposed to environmental arsenic sources.

Urinary Arsenic in Human Samples from Areas Characterized by Natural or Anthropogenic Pollution in Italy

PubMed Central

Minichilli, Fabrizio; Bianchi, Fabrizio; Ronchi, Anna Maria; Gorini, Francesca; Bustaffa, Elisa

2018-01-01

Arsenic is ubiquitous and has a potentially adverse impact on human health. We compared the distribution of concentrations of urinary inorganic arsenic plus methylated forms (uc(iAs+MMA+DMA)) in four Italian areas with other international studies, and we assessed the relationship between uc(iAs+MMA+DMA) and various exposure factors. We conducted a human biomonitoring study on 271 subjects (132 men) aged 20–44, randomly sampled and stratified by area, gender, and age. Data on environmental and occupational exposure and dietary habits were collected through a questionnaire. Arsenic was speciated using chromatographic separation and inductively coupled mass spectrometry. Associations between uc(iAs+MMA+DMA) and exposure factors were evaluated using the geometric mean ratio (GMR) with a 90% confidence interval by stepwise multiple regression analysis. The 95th percentile value of uc(iAs+MMA+DMA) for the whole sample (86.28 µg/L) was higher than other national studies worldwide. A statistical significant correlation was found between uc(iAs+MMA+DMA) and occupational exposure (GMR: 2.68 [1.79–4.00]), GSTT gene (GMR: 0.68 [0.52–0.80]), consumption of tap water (GMR: 1.35 [1.02–1.77]), seafood (GMR: 1.44 [1.11–1.88]), whole milk (GMR: 1.34 [1.04–1.73]), and fruit/vegetables (GMR: 1.37 [1.03–1.82]). This study demonstrated the utility of uc(iAs+MMA+DMA) as a biomarker to assess environmental exposure. In a public health context, this information could be used to support remedial action, to prevent individuals from being further exposed to environmental arsenic sources. PMID:29425136

Potential application of SERS for arsenic speciation in biological matrices.

PubMed

Yang, Mingwei; Matulis, Shannon; Boise, Lawrence H; McGoron, Anthony J; Cai, Yong

2017-08-01

Speciation of arsenic is usually carried out using chromatography-based methods coupled with spectroscopic determination; however, the inevitable procedures involving sample preparation and separation could potentially alter the integrity of the arsenic metabolites present in biological samples. Surface-enhanced Raman spectroscopy (SERS) could be a promising alternative for providing a reliable arsenic analysis under the influence of a cellular matrix. A method for arsenic speciation using SERS in cellular matrix was developed in this study and four arsenicals were selected, including arsenite (As III ), arsenate (As V ), monomethylarsonic acid (MMA V ) and dimethylarsinic acid (DMA V ). Silver nanoparticles in the form of colliodal suspension with different surface charges, i.e., coated with citrate (AgNPs-Citrate) and spermine (AgNPs-Spermine) were employed as SERS substrates. Adsorption of arsenicals on nanoparticles in colloidal suspensions and the cellular matrix and the pH, size, and zeta potential of the colloidal suspensions were investigated for a better understanding of the SERS signal response of arsenicals in the colloidal suspensions or under the influence of cellular matrix. Arsenicals showed substantially different SERS responses in the two colloidal suspensions, mainly because of the distinct difference in the interaction between the arsenicals and the nanoparticles. Arsenic speciation in cell lysate could be successfully carried out in AgNPs-Spermine suspension, while AgNPs-Citrate could not yield significant SERS signals under the experimental conditions. This study proved that AgNPs-Spermine colloidal suspension could be a promising SERS substrate for studying arsenic metabolism in a biological matrix, reducing the bias caused by traditional techniques that involve sample extraction and pretreatment.

Selective speciation and determination of inorganic arsenic in water, food and biological samples.

PubMed

Tuzen, Mustafa; Saygi, Kadriye Ozlem; Karaman, Isa; Soylak, Mustafa

2010-01-01

A procedure for the speciation of arsenic(III) and arsenic(V) in natural water samples has been established in the presented work. Arsenic(III) ions were quantitatively recovered on Alternaria solani coated Diaion HP-2MG resin at pH 7, while the recoveries of arsenic(V) was below 10%. Arsenic(V) in the mixing solution containing As(III) and As(V) was reduced by using KI and L(+) ascorbic acid solution, then the procedure was applied to determination of total arsenic. Arsenic(V) was calculated as the difference between the total arsenic content and As(III) content. The determination of arsenic was performed by using hydride generation atomic absorption spectrometry. The influences of some alkali, earth alkali and transition metals on the biosorption of arsenic(III) were investigated. The preconcentration factor was 35. The detection limits for As(III) (N=20, k=3) was found as 11 ng L(-1). The relative standard deviation and relative error of the determinations were found to be lower than 7% and 4%, respectively. The accuracy of the method was confirmed with certified reference materials. The method was successively applied for the determination and speciation of inorganic arsenic in water, food and biological samples. Copyright 2009 Elsevier Ltd. All rights reserved.

Chronic Exposure to Arsenic and Markers of Cardiometabolic Risk: A Cross-Sectional Study in Chihuahua, Mexico.

PubMed

Mendez, Michelle A; González-Horta, Carmen; Sánchez-Ramírez, Blanca; Ballinas-Casarrubias, Lourdes; Cerón, Roberto Hernández; Morales, Damián Viniegra; Terrazas, Francisco A Baeza; Ishida, María C; Gutiérrez-Torres, Daniela S; Saunders, R Jesse; Drobná, Zuzana; Fry, Rebecca C; Buse, John B; Loomis, Dana; García-Vargas, Gonzalo G; Del Razo, Luz M; Stýblo, Miroslav

2016-01-01

Exposure to arsenic (As) concentrations in drinking water > 150 μg/L has been associated with risk of diabetes and cardiovascular disease, but little is known about the effects of lower exposures. This study aimed to examine whether moderate As exposure, or indicators of individual As metabolism at these levels of exposure, are associated with cardiometabolic risk. We analyzed cross-sectional associations between arsenic exposure and multiple markers of cardiometabolic risk using drinking-water As measurements and urinary As species data obtained from 1,160 adults in Chihuahua, Mexico, who were recruited in 2008-2013. Fasting blood glucose and lipid levels, the results of an oral glucose tolerance test, and blood pressure were used to characterize cardiometabolic risk. Multivariable logistic, multinomial, and linear regression were used to assess associations between cardiometabolic outcomes and water As or the sum of inorganic and methylated As species in urine. After multivariable adjustment, concentrations in the second quartile of water As (25.5 to < 47.9 μg/L) and concentrations of total speciated urinary As (< 55.8 μg/L) below the median were significantly associated with elevated triglycerides, high total cholesterol, and diabetes. However, moderate water and urinary As levels were also positively associated with HDL cholesterol. Associations between arsenic exposure and both dysglycemia and triglyceridemia were higher among individuals with higher proportions of dimethylarsenic in urine. Moderate exposure to As may increase cardiometabolic risk, particularly in individuals with high proportions of urinary dimethylarsenic. In this cohort, As exposure was associated with several markers of increased cardiometabolic risk (diabetes, triglyceridemia, and cholesterolemia), but exposure was also associated with higher rather than lower HDL cholesterol. Mendez MA, González-Horta C, Sánchez-Ramírez B, Ballinas-Casarrubias L, Hernández Cerón R, Viniegra Morales D, Baeza Terrazas FA, Ishida MC, Gutiérrez-Torres DS, Saunders RJ, Drobná Z, Fry RC, Buse JB, Loomis D, García-Vargas GG, Del Razo LM, Stýblo M. 2016. Chronic exposure to arsenic and markers of cardiometabolic risk: a cross-sectional study in Chihuahua, Mexico. Environ Health Perspect 124:104-111; http://dx.doi.org/10.1289/ehp.1408742.

Chronic Exposure to Arsenic and Markers of Cardiometabolic Risk: A Cross-Sectional Study in Chihuahua, Mexico

PubMed Central

Mendez, Michelle A.; González-Horta, Carmen; Sánchez-Ramírez, Blanca; Ballinas-Casarrubias, Lourdes; Cerón, Roberto Hernández; Morales, Damián Viniegra; Terrazas, Francisco A. Baeza; Ishida, María C.; Gutiérrez-Torres, Daniela S.; Saunders, R. Jesse; Drobná, Zuzana; Fry, Rebecca C.; Buse, John B.; Loomis, Dana; García-Vargas, Gonzalo G.; Del Razo, Luz M.

2015-01-01

Background Exposure to arsenic (As) concentrations in drinking water > 150 μg/L has been associated with risk of diabetes and cardiovascular disease, but little is known about the effects of lower exposures. Objective This study aimed to examine whether moderate As exposure, or indicators of individual As metabolism at these levels of exposure, are associated with cardiometabolic risk. Methods We analyzed cross-sectional associations between arsenic exposure and multiple markers of cardiometabolic risk using drinking-water As measurements and urinary As species data obtained from 1,160 adults in Chihuahua, Mexico, who were recruited in 2008–2013. Fasting blood glucose and lipid levels, the results of an oral glucose tolerance test, and blood pressure were used to characterize cardiometabolic risk. Multivariable logistic, multinomial, and linear regression were used to assess associations between cardiometabolic outcomes and water As or the sum of inorganic and methylated As species in urine. Results After multivariable adjustment, concentrations in the second quartile of water As (25.5 to < 47.9 μg/L) and concentrations of total speciated urinary As (< 55.8 μg/L) below the median were significantly associated with elevated triglycerides, high total cholesterol, and diabetes. However, moderate water and urinary As levels were also positively associated with HDL cholesterol. Associations between arsenic exposure and both dysglycemia and triglyceridemia were higher among individuals with higher proportions of dimethylarsenic in urine. Conclusions Moderate exposure to As may increase cardiometabolic risk, particularly in individuals with high proportions of urinary dimethylarsenic. In this cohort, As exposure was associated with several markers of increased cardiometabolic risk (diabetes, triglyceridemia, and cholesterolemia), but exposure was also associated with higher rather than lower HDL cholesterol. Citation Mendez MA, González-Horta C, Sánchez-Ramírez B, Ballinas-Casarrubias L, Hernández Cerón R, Viniegra Morales D, Baeza Terrazas FA, Ishida MC, Gutiérrez-Torres DS, Saunders RJ, Drobná Z, Fry RC, Buse JB, Loomis D, García-Vargas GG, Del Razo LM, Stýblo M. 2016. Chronic exposure to arsenic and markers of cardiometabolic risk: a cross-sectional study in Chihuahua, Mexico. Environ Health Perspect 124:104–111; http://dx.doi.org/10.1289/ehp.1408742 PMID:26068977

Interactions between arsenic species and marine algae

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sanders, J.G.

The arsenic concentration and speciation of marine algae varies widely, from 0.4 to 23 ng.mg/sup -1/, with significant differences in both total arsenic content and arsenic speciation occurring between algal classes. The Phaeophyceae contain more arsenic than other algal classes, and a greater proportion of the arsenic is organic. The concentration of inorganic arsenic is fairly constant in macro-algae, and may indicate a maximum level, with the excess being reduced and methylated. Phytoplankton take up As(V) readily, and incorporate a small percentage of it into the cell. The majority of the As(V) is reduced, methylated, and released to the surroundingmore » media. The arsenic speciation in phytoplankton and Valonia also changes when As(V) is added to cultures. Arsenate and phosphate compete for uptake by algal cells. Arsenate inhibits primary production at concentrations as low as 5 ..mu..g.1/sup -1/ when the phosphate concentration is low. The inhibition is competitive. A phosphate enrichment of > 0.3 ..mu..M alleviates this inhibition; however, the As(V) stress causes an increase in the cell's phosphorus requirement. Arsenite is also toxic to phytoplankton at similar concentrations. Methylated arsenic species did not affect cell productivity, even at concentrations of 25 ..mu..g.1/sup -1/. Thus, the methylation of As(V) by the cell produces a stable, non-reactive compound which is nontoxic. The uptake and subsequent reduction and methylation of As(V) is a significant factor in determining the arsenic biogeochemistry of productive systems, and also the effect that the arsenic may have on algal productivity. Therefore, the role of marine algae in determining the arsenic speciation of marine systems cannot be ignored. (ERB)« less

Linear Combination Fitting (LCF)-XANES analysis of As speciation in selected mine-impacted materials

EPA Pesticide Factsheets

This table provides sample identification labels and classification of sample type (tailings, calcinated, grey slime). For each sample, total arsenic and iron concentrations determined by acid digestion and ICP analysis are provided along with arsenic in-vitro bioaccessibility (As IVBA) values to estimate arsenic risk. Lastly, the table provides linear combination fitting results from synchrotron XANES analysis showing the distribution of arsenic speciation phases present in each sample along with fitting error (R-factor).This dataset is associated with the following publication:Ollson, C., E. Smith, K. Scheckel, A. Betts, and A. Juhasz. Assessment of arsenic speciation and bioaccessibility in mine-impacted materials. Diana Aga, Wonyong Choi, Andrew Daugulis, Gianluca Li Puma, Gerasimos Lyberatos, and Joo Hwa Tay JOURNAL OF HAZARDOUS MATERIALS. Elsevier Science Ltd, New York, NY, USA, 313: 130-137, (2016).

GSTO and AS3MT genetic polymorphisms and differences in urinary arsenic concentrations among residents in Bangladesh.

PubMed

Rodrigues, Ema G; Kile, Molly; Hoffman, Elaine; Quamruzzaman, Quazi; Rahman, Mahmuder; Mahiuddin, Golam; Hsueh, Yumei; Christiani, David C

2012-05-01

We determined whether single nucleotide polymorphisms (SNPs) in the glutathione S-transferase omega (GSTO) and arsenic(III)methyltransferase (AS3MT) genes were associated with concentrations of urinary arsenic metabolites among 900 individuals without skin lesions in Bangladesh. Four SNPs were assessed in these genes. A pathway analysis evaluated the association between urinary arsenic metabolites and SNPs. GSTO1 rs4925 homozygous wild type was significantly associated with higher monomethylarsonic acid (MMA) and dimethylarsinic acid urinary concentrations, whereas wild-type AS3MT rs11191439 had significantly lower levels of As(III) and MMA. Genetic polymorphisms GSTO and As3MT modify arsenic metabolism as evidenced by altered urinary arsenic excretion.

Aqueous and solid phase speciation of arsenic in a Bengali aquifer using IC-ICP-MS and EXAFS

NASA Astrophysics Data System (ADS)

Gault, A. G.; Davidson, L. E.; Lythgoe, P. R.; Charnock, J. M.; Chatterjee, D.; Abou-Shakra, F. R.; Walker, H. J.; Polya, D. A.

2003-04-01

Contamination of groundwater and drinking water supplies with arsenic has been reported in many parts of the world and constitutes a serious public health threat. Nowhere is this more apparent than in West Bengal and Bangladesh where arsenic concentrations exceed both World Health Organisation (WHO) and national limits in drinking water supplies leading to what has been described as the worst mass poisoning of a human population in history. Knowledge of both aqueous and solid phase speciation of arsenic in such hazardous arsenic-rich groundwaters is crucial to understanding the processes controlling arsenic release. We report here preliminary work involving the determination of dissolved arsenic speciation in West Bengali groundwaters and extended X-ray absorption fine structure (EXAFS) analysis of the associated sediment. Groundwater samples collected from Nadia district, West Bengal were analysed for arsenic speciation by ion chromatography-inductively coupled plasma-mass spectrometry (IC-ICP-MS) within 14 days of collection. Total arsenic concentrations exceeding 850 ug/L were determined; inorganic arsenic constituted the bulk of the dissolved arsenic burden with As(III) as the dominant form. Minor amounts of methylated arsenicals were also detected, however, their concentration did not exceed 5 ug/L. The local coordination environment of arsenic in sediment associated with such groundwaters was probed using K-edge As EXAFS. This revealed that arsenic exists predominantly in its oxidised form, As(V), most likely adsorbed as bidentate arsenate tetrahedra on metal (Fe and/or Al) oxide/hydroxide surfaces, although incorporation of arsenic into a metal oxide structure cannot be unequivocally ruled out. Arsenic was found to occur in several different coordination environments and this, together with the low concentration (< 5 ug/g) of arsenic in the sediment, prevented the unambiguous assignment of the second coordination sphere. The analysis of the trends of key groundwater constituents in our data suggest that arsenic is released due to the reductive dissolution of arsenic laden-hydrous ferric oxides, however, further work is required to fully evaluate the mode of arsenic release.

Intercomparison of analytical methods for arsenic speciation in human urine.

PubMed

Crecelius, E; Yager, J

1997-06-01

An intercomparison exercise was conducted for the quantification of arsenic species in spiked human urine. The primary objective of the exercise was to determine the variance among laboratories in the analysis of arsenic species such as inorganic As (As+3 and As+5), monomethylarsonic acid (MMA), and dimethylarsinic acid (DMA). Laboratories that participated had previous experience with arsenic speciation analysis. The results of this interlaboratory comparison are encouraging. There is relatively good agreement on the concentrations of these arsenic species in urine at concentrations that are relevant to research on the metabolism of arsenic in humans and other mammals. Both the accuracy and precision are relatively poor for arsenic concentrations of less than about 5 micrograms/l.

Urinary and dietary analysis of 18,470 bangladeshis reveal a correlation of rice consumption with arsenic exposure and toxicity.

PubMed

Melkonian, Stephanie; Argos, Maria; Hall, Megan N; Chen, Yu; Parvez, Faruque; Pierce, Brandon; Cao, Hongyuan; Aschebrook-Kilfoy, Briseis; Ahmed, Alauddin; Islam, Tariqul; Slavcovich, Vesna; Gamble, Mary; Haris, Parvez I; Graziano, Joseph H; Ahsan, Habibul

2013-01-01

We utilized data from the Health Effects of Arsenic Longitudinal Study (HEALS) in Araihazar, Bangladesh, to evaluate the association of steamed rice consumption with urinary total arsenic concentration and arsenical skin lesions in the overall study cohort (N=18,470) and in a subset with available urinary arsenic metabolite data (N=4,517). General linear models with standardized beta coefficients were used to estimate associations between steamed rice consumption and urinary total arsenic concentration and urinary arsenic metabolites. Logistic regression models were used to estimate prevalence odds ratios (ORs) and their 95% confidence intervals (CIs) for the associations between rice intake and prevalent skin lesions at baseline. Discrete time hazard models were used to estimate discrete time (HRs) ratios and their 95% CIs for the associations between rice intake and incident skin lesions. Steamed rice consumption was positively associated with creatinine-adjusted urinary total arsenic (β=0.041, 95% CI: 0.032-0.051) and urinary total arsenic with statistical adjustment for creatinine in the model (β=0.043, 95% CI: 0.032-0.053). Additionally, we observed a significant trend in skin lesion prevalence (P-trend=0.007) and a moderate trend in skin lesion incidence (P-trend=0.07) associated with increased intake of steamed rice. This study suggests that rice intake may be a source of arsenic exposure beyond drinking water.

Effects of biological and behavioral factors on urinary arsenic ...

EPA Pesticide Factsheets

Abstract In older men and women who were long-term residents of Churchill County, Nevada, we examined the relation between arsenic exposure from home tap water and urinary levels of inorganic arsenic and its methylated metabolites. Over a wide exposure range (up to 1850 ug of arsenic per liter), urinary concentrations of inorganic, monomethylated, and dimethylated arsenicals strongly correlated with home tap water arsenic concentrations. However, percentages of summed urinary concentrations of inorganic, monomethylated, and dimethylated arsenicals accounted for by each arsenical species were unaffected by arsenic concentration in home tap water, suggesting thc1t capacity for formation and excretion of methylated metabolites was not exceeded. Biological factors (gender, age, body mass index, and genotype) and a behavioral factor (smoking) influenced absolute and relative levels of arsenicals in urine. A multivariate regression model showed that both biological and behavioral factors were significant predictors of absolute and relative concentrations of inorganic arsenic and its methylated metabolites in urine. These findings suggest that analyses of dose-response relations in arsenic-exposed populations should account for these biological and behavioral factors. Furthermore, evidence of significant effects of these factors on arsenic metabolism may support mode of action studies in appropriate experimental models. Running title- Methylated arsenicals as urinary b

XAS Studies of Arsenic in the Environment

DOE Office of Scientific and Technical Information (OSTI.GOV)

Charnock, J. M.; School of Earth, Atmospheric and Environmental Sciences, University of Manchester, Oxford Road, Manchester, M13 9PL; Polya, D. A.

2007-02-02

Arsenic is present in low concentrations in much of the Earth's crust and changes in its speciation are vital to understanding its transport and toxicity in the environment. We have used X-ray absorption spectroscopy to investigate the coordination sites of arsenic in a wide variety of samples, including soil and earthworm tissues from arsenic-contaminated land, and human hair and nail samples from people exposed to arsenic in Cambodia. Our results confirm the effectiveness of using X-ray absorption near edge structure (XANES) and X-ray absorption fine structure (EXAFS) spectroscopy to determine speciation changes in environmental samples.

Determination and pharmacokinetic properties of arsenic speciation in Xiao-Er-Zhi-Bao-Wan by high-performance liquid chromatography with inductively coupled plasma mass spectrometry.

PubMed

Han, Xu; Luo, Jiaoyang; Zhou, Wenju; Yang, Shihai; Yang, Meihua

2016-10-01

A method of high performance liquid chromatography with a Hamilton PRP-X100 ion-exchange column (250 × 4.1 mm id, 10 μm) coupled to inductively coupled plasma mass spectrometry was employed to generate a full concentration-time profile of arsenic speciation after oral administration. The results exhibited good linearity and revealed that, in the pills, the average arsenic concentration was 10105.4 ± 380.7 mg/kg, and in the water extraction solution, the inorganic As(III) and As(V) concentrations were 220.1 ± 12.6 and 45.5 ± 2.3 mg/kg, respectively. No trace of monomethyl arsenic acid was detected in any of the plasma samples. We then successfully applied the established methodology to examine the pharmacokinetics of arsenic speciation. The resulting data revealed that, after oral administration in rats, the plasma concentration of each arsenic species reached C max shortly after initial dosing, and that the distribution and elimination of As(V) was faster than that of As(III) and dimethyl arsenic acid. Additionally, the t 1/2 values of As(V), As(III), and dimethyl arsenic acid were 3.4 ± 1.6, 14.3 ± 4.0, and 19.9 ± 1.6 h, respectively. This study provides references for the determination of arsenic speciation in mineral-containing medicines and could serve as a useful tool in measuring the true toxicity in traditional medicines that contain them. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Intercomparison of analytical methods for arsenic speciation in human urine.

PubMed Central

Crecelius, E; Yager, J

1997-01-01

An intercomparison exercise was conducted for the quantification of arsenic species in spiked human urine. The primary objective of the exercise was to determine the variance among laboratories in the analysis of arsenic species such as inorganic As (As+3 and As+5), monomethylarsonic acid (MMA), and dimethylarsinic acid (DMA). Laboratories that participated had previous experience with arsenic speciation analysis. The results of this interlaboratory comparison are encouraging. There is relatively good agreement on the concentrations of these arsenic species in urine at concentrations that are relevant to research on the metabolism of arsenic in humans and other mammals. Both the accuracy and precision are relatively poor for arsenic concentrations of less than about 5 micrograms/l. PMID:9288500

Urinary and Dietary Analysis of 18,470 Bangladeshis Reveal a Correlation of Rice Consumption with Arsenic Exposure and Toxicity

PubMed Central

Melkonian, Stephanie; Argos, Maria; Hall, Megan N.; Chen, Yu; Parvez, Faruque; Pierce, Brandon; Cao, Hongyuan; Aschebrook-Kilfoy, Briseis; Ahmed, Alauddin; Islam, Tariqul; Slavcovich, Vesna; Gamble, Mary; Haris, Parvez I.; Graziano, Joseph H.; Ahsan, Habibul

2013-01-01

Background We utilized data from the Health Effects of Arsenic Longitudinal Study (HEALS) in Araihazar, Bangladesh, to evaluate the association of steamed rice consumption with urinary total arsenic concentration and arsenical skin lesions in the overall study cohort (N=18,470) and in a subset with available urinary arsenic metabolite data (N=4,517). Methods General linear models with standardized beta coefficients were used to estimate associations between steamed rice consumption and urinary total arsenic concentration and urinary arsenic metabolites. Logistic regression models were used to estimate prevalence odds ratios (ORs) and their 95% confidence intervals (CIs) for the associations between rice intake and prevalent skin lesions at baseline. Discrete time hazard models were used to estimate discrete time (HRs) ratios and their 95% CIs for the associations between rice intake and incident skin lesions. Results Steamed rice consumption was positively associated with creatinine-adjusted urinary total arsenic (β=0.041, 95% CI: 0.032-0.051) and urinary total arsenic with statistical adjustment for creatinine in the model (β=0.043, 95% CI: 0.032-0.053). Additionally, we observed a significant trend in skin lesion prevalence (P-trend=0.007) and a moderate trend in skin lesion incidence (P-trend=0.07) associated with increased intake of steamed rice. Conclusions This study suggests that rice intake may be a source of arsenic exposure beyond drinking water. PMID:24260455

Ultra-Sensitive Elemental Analysis Using Plasmas 5.Speciation of Arsenic Compounds in Biological Samples by High Performance Liquid Chromatography-Inductively Coupled Plasma Mass Spectrometry System

NASA Astrophysics Data System (ADS)

Kaise, Toshikazu

Arsenic originating from the lithosphere is widely distributed in the environment. Many arsenicals in the environment are in organic and methylated species. These arsenic compounds in drinking water or food products of marine origin are absorbed in human digestive tracts, metabolized in the human body, and excreted viatheurine. Because arsenic shows varying biological a spects depending on its chemical species, the biological characteristics of arsenic must be determined. It is thought that some metabolic pathways for arsenic and some arsenic circulation exist in aqueous ecosystems. In this paper, the current status of the speciation analysis of arsenic by HPLC/ICP-MS (High Performance Liquid Chromatography-Inductively Coupled Plasma Mass spectrometry) in environmental and biological samples is summarized using recent data.

Urinary 8-hydroxydeoxyguanosine and urothelial carcinoma risk in low arsenic exposure area

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chung, C.-J.; Huang, C.-J.; Pu, Y.-S.

2008-01-01

Arsenic is a well-documented human carcinogen and is known to cause oxidative stress in cultured cells and animals. A hospital-based case-control study was conducted to evaluate the relationship among the levels of urinary 8-hydroxydeoxyguanosine (8-OHdG), the arsenic profile, and urothelial carcinoma (UC). Urinary 8-OHdG was measured by using high-sensitivity enzyme-linked immunosorbent assay (ELISA) kits. The urinary species of inorganic arsenic and their metabolites were analyzed by high-performance liquid chromatography (HPLC) and hydride generator-atomic absorption spectrometry (HG-AAS). This study showed that the mean urinary concentration of total arsenics was significantly higher, at 37.67 {+-} 2.98 {mu}g/g creatinine, for UC patients thanmore » for healthy controls of 21.10 {+-} 0.79 {mu}g/g creatinine (p < 0.01). Urinary 8-OHdG levels correlated with urinary total arsenic concentrations (r = 0.19, p < 0.01). There were significantly higher 8-OHdG levels, of 7.48 {+-} 0.97 ng/mg creatinine in UC patients, compared to healthy controls of 5.95 {+-} 0.21 ng/mg creatinine. Furthermore, female UC patients had higher 8-OHdG levels of 9.22 {+-} 0.75 than those of males at 5.76 {+-} 0.25 ng/mg creatinine (p < 0.01). Multiple linear regression analyses revealed that high urinary 8-OHdG levels were associated with increased total arsenic concentrations, inorganic arsenite, monomethylarsonic acid (MMA), and dimethylarsenate (DMA) as well as the primary methylation index (PMI) even after adjusting for age, gender, and UC status. The results suggest that oxidative DNA damage was associated with arsenic exposure, even at low urinary level of arsenic.« less

The Role of Arsenic Speciation in Dietary Exposure Assessment and the Need to Include Bioaccessibility and Biotransformation

EPA Science Inventory

Chemical form specific exposure assessment for arsenic has long been identified as a source of uncertainty in estimating the risk associated with the aggregate exposure for a population. Some speciation based assessments document occurrence within an exposure route; however, the...

Speciation And Distribution Of Arsenic And Localization Of Nutrients In Rice Grains

EPA Science Inventory

Arsenic (As) contamination of rice grains and the generally low concentration of micronutrients in rice have been recognized as a major concern for human health. Here, we investigated the speciation and localization of As and the distribution of (micro)nutrients in rice grains b...

SPECIATION OF ARSENIC COMPOUNDS IN DRINKING WATER BY CAPILLARY ELECTROPHORESIS WITH HYDRODYNAMICALLY MODIFIED ELECTROOSMOTIC FLOW DETECTED THROUGH HYDRIDE GENERATION INDUCTIVELY COUPLED PLASMA MASS..

EPA Science Inventory

Capillary electrophoresis (CE) was used to speciate four environmentally significant, toxic forms of arsenic: arsenite, arsenate, monomethylarsonic acid and dimethylarsinic acid. Hydride generation (HG) was used to convert the species into their respective hydrides. The hydride ...

Speciation analysis of arsenic in biological matrices by automated hydride generation-cryotrapping-atomic absorption spectrometry with multiple microflame quartz tube atomizer (multiatomizer).

EPA Science Inventory

This paper describes an automated system for the oxidation state specific speciation of inorganic and methylated arsenicals by selective hydride generation - cryotrapping- gas chromatography - atomic absorption spectrometry with the multiatomizer. The corresponding arsines are ge...

SPECIATION AND PRESERVATION OF INORGANIC ARSENIC IN DRINKING WATER SUPPLIES WITH IC-ICP-MS

EPA Science Inventory

The speciation of inorganic arsenic in drinking water supplies is an essential part of devising an appropriate treatment process. Arsenate, because of its anion characteristics at drinking water pHs, is effectively removed by anion exchange treatment while arsenite remains in the...

ARSENIC SPECIATION IN CARROT EXTRACTS WITH AN EMPHASIS ON THE DETECTION OF MMA(III) AND MMTA

EPA Science Inventory

The two predominant routes of arsenic exposure are dietary ingestion and drinking water consumption. Dietary arsenic, unlike drinking water arsenic, contains a variety of arsenicals with dramatically different toxicities. The list of arsenicals detected in dietary samples conti...

DNA repair gene XPD and susceptibility to arsenic-induced hyperkeratosis.

PubMed

Ahsan, Habibul; Chen, Yu; Wang, Qiao; Slavkovich, Vesna; Graziano, Joseph H; Santella, Regina M

2003-07-20

Chronic exposure to inorganic arsenic is known to cause non-melanocytic skin and internal cancers in humans. An estimated 50-70 million people in Bangladesh have been chronically exposed to arsenic from drinking water and are at risk of skin and other cancers. We undertook the first study to examine whether genetic susceptibility, as determined by the codon 751 SNP (A-->C) of the DNA repair gene XPD, influences the risk of arsenic-induced hyperkeratotic skin lesions, precursors of skin cancer, in a case-control study of 29 hyperkeratosis cases and 105 healthy controls from the same community in an area of Bangladesh. As expected, there was a monotonic increase in risk of hyperkeratosis in relation to urinary arsenic measures but the XPD genotype was not independently associated with the risk. However, the increase in hyperkeratosis risk in relation to urinary arsenic measures genotype was borderline significant for urinary total arsenic (P for trend=0.06) and statistically significant for urinary creatinine adjusted arsenic (P for trend=0.01) among subjects with the XPD A allele (AA) but not among subjects with the other XPD genotypes. Among AA carriers, the risk for the highest arsenic exposed group compared with the lowest was more than 7-fold for urinary total arsenic and about 11-fold for urinary creatinine adjusted arsenic. In conclusion, our findings suggest that the DNA repair gene XPD may influence the risk of arsenic-induced premalignant hyperkeratotic skin lesions. Future larger studies are needed to confirm this novel finding and investigate how combinations of different candidate genes and/or other host and environmental factors may influence the risk of arsenic induced skin and other cancers.

Arsenic Speciation and Accumulation in Selected Organs after Oral Administration of Rice Extracts in Wistar Rats.

PubMed

Lewchalermvong, Kittima; Rangkadilok, Nuchanart; Nookabkaew, Sumontha; Suriyo, Tawit; Satayavivad, Jutamaad

2018-03-28

Despite its nutritional values, rice also contains arsenic. There has been increasing concern about health implications associated with exposure to arsenic through rice consumption. The present study evaluated arsenic accumulation and its speciation in selected organs of Wistar rats after 28 day repeated oral administrations of polished or unpolished rice and their control arsenic compounds (sodium arsenite or dimethylarsinic acid; DMA). Only the treatment of sodium arsenite (2 μg/kg body weight), significantly increased total arsenic concentrations in blood when compared to the distilled water control group. In all groups, total arsenic concentrations were highest in kidney (1.54-1.90 mg/kg) followed by liver (0.85-1.52 mg/kg), and the predominant arsenic form in these organs was DMA. However, there was no significant difference in arsenic accumulation in the measured organs among the control and rice-treated groups. Therefore, the repeated 28 day administration of arsenic-contaminated rice did not cause significant arsenic accumulation in the animal organs.

Arsenic, Antimony, Chromium, and Thallium Speciation in Water and Sediment Samples with the LC-ICP-MS Technique

PubMed Central

Jabłońska-Czapla, Magdalena

2015-01-01

Chemical speciation is a very important subject in the environmental protection, toxicology, and chemical analytics due to the fact that toxicity, availability, and reactivity of trace elements depend on the chemical forms in which these elements occur. Research on low analyte levels, particularly in complex matrix samples, requires more and more advanced and sophisticated analytical methods and techniques. The latest trends in this field concern the so-called hyphenated techniques. Arsenic, antimony, chromium, and (underestimated) thallium attract the closest attention of toxicologists and analysts. The properties of those elements depend on the oxidation state in which they occur. The aim of the following paper is to answer the question why the speciation analytics is so important. The paper also provides numerous examples of the hyphenated technique usage (e.g., the LC-ICP-MS application in the speciation analysis of chromium, antimony, arsenic, or thallium in water and bottom sediment samples). An important issue addressed is the preparation of environmental samples for speciation analysis. PMID:25873962

Field and laboratory arsenic speciation methods and their application to natural-water analysis

USGS Publications Warehouse

Bednar, A.J.; Garbarino, J.R.; Burkhardt, M.R.; Ranville, J.F.; Wildeman, T.R.

2004-01-01

The toxic and carcinogenic properties of inorganic and organic arsenic species make their determination in natural water vitally important. Determination of individual inorganic and organic arsenic species is critical because the toxicology, mobility, and adsorptivity vary substantially. Several methods for the speciation of arsenic in groundwater, surface-water, and acid mine drainage sample matrices using field and laboratory techniques are presented. The methods provide quantitative determination of arsenite [As(III)], arsenate [As(V)], monomethylarsonate (MMA), dimethylarsinate (DMA), and roxarsone in 2-8min at detection limits of less than 1??g arsenic per liter (??g AsL-1). All the methods use anion exchange chromatography to separate the arsenic species and inductively coupled plasma-mass spectrometry as an arsenic-specific detector. Different methods were needed because some sample matrices did not have all arsenic species present or were incompatible with particular high-performance liquid chromatography (HPLC) mobile phases. The bias and variability of the methods were evaluated using total arsenic, As(III), As(V), DMA, and MMA results from more than 100 surface-water, groundwater, and acid mine drainage samples, and reference materials. Concentrations in test samples were as much as 13,000??g AsL-1 for As(III) and 3700??g AsL-1 for As(V). Methylated arsenic species were less than 100??g AsL-1 and were found only in certain surface-water samples, and roxarsone was not detected in any of the water samples tested. The distribution of inorganic arsenic species in the test samples ranged from 0% to 90% As(III). Laboratory-speciation method variability for As(III), As(V), MMA, and DMA in reagent water at 0.5??g AsL-1 was 8-13% (n=7). Field-speciation method variability for As(III) and As(V) at 1??g AsL-1 in reagent water was 3-4% (n=3). ?? 2003 Elsevier Ltd. All rights reserved.

Arsenic speciation and trace element analysis of the volcanic río Agrio and the geothermal waters of Copahue, Argentina.

PubMed

Farnfield, Hannah R; Marcilla, Andrea L; Ward, Neil I

2012-09-01

Surface water originating from the Copahue volcano crater-lake was analysed for total arsenic and four arsenic species: arsenite (iAs(III)), arsenate (iAs(V)), monomethylarsonic acid (MA(V)) and dimethylarsinic acid (DMA(V)) and other trace elements (Fe, Mn, V, Cr, Ni, Zn). A novel in-field technique for the preconcentration and separation of four arsenic species was, for the first time, used for the analysis of geothermal and volcanic waters. Total arsenic levels along the río Agrio ranged from <0.2-3783 μg/l As(T). The highest arsenic levels were recorded in the el Vertedero spring (3783 μg/l As(T)) on the flank of the Copahue volcano, which feeds the acidic río Agrio. Arsenite (H(3)AsO(3)) predominated along the upper río Agrio (78.9-81.2% iAs(III)) but the species distribution changed at lago Caviahue and arsenate (H(2)AsO(4)(-)) became the main species (51.4-61.4% iAs(V)) up until Salto del Agrio. The change in arsenic species is potentially a result of an increase in redox potential and the formation of iron-based precipitates. Arsenic speciation showed a statistically significant correlation with redox potential (r=0.9697, P=0.01). Both total arsenic and arsenic speciation displayed a statistically significant correlation with vanadium levels along the river (r=0.9961, P=0.01 and r=0.8488, P=0.05, respectively). This study highlights that chemical speciation analysis of volcanic waters is important in providing ideas on potential chemical toxicity. Furthermore there is a need for further work evaluating how arsenic (and other trace elements), released in volcanic and geothermal streams/vents, impacts on both biota and humans (via exposure in thermal pools or consuming commercial drinking water). Copyright © 2012 Elsevier B.V. All rights reserved.

Effects of iron on arsenic speciation and redox chemistry in acid mine water

USGS Publications Warehouse

Bednar, A.J.; Garbarino, J.R.; Ranville, J.F.; Wildeman, T.R.

2005-01-01

Concern about arsenic is increasing throughout the world, including areas of the United States. Elevated levels of arsenic above current drinking-water regulations in ground and surface water can be the result of purely natural phenomena, but often are due to anthropogenic activities, such as mining and agriculture. The current study correlates arsenic speciation in acid mine drainage and mining-influenced water with the important water-chemistry properties Eh, pH, and iron(III) concentration. The results show that arsenic speciation is generally in equilibrium with iron chemistry in low pH AMD, which is often not the case in other natural-water matrices. High pH mine waters and groundwater do not always hold to the redox predictions as well as low pH AMD samples. The oxidation and precipitation of oxyhydroxides deplete iron from some systems, and also affect arsenite and arsenate concentrations through sorption processes. ?? 2004 Elsevier B.V. All rights reserved.

Biologically based modeling of multimedia, multipathway, multiroute population exposures to arsenic

PubMed Central

Georgopoulos, Panos G.; Wang, Sheng-Wei; Yang, Yu-Ching; Xue, Jianping; Zartarian, Valerie G.; Mccurdy, Thomas; Özkaynak, Halûk

2011-01-01

This article presents an integrated, biologically based, source-to-dose assessment framework for modeling multimedia/multipathway/multiroute exposures to arsenic. Case studies demonstrating this framework are presented for three US counties (Hunderton County, NJ; Pima County, AZ; and Franklin County, OH), representing substantially different conditions of exposure. The approach taken utilizes the Modeling ENvironment for TOtal Risk studies (MENTOR) in an implementation that incorporates and extends the approach pioneered by Stochastic Human Exposure and Dose Simulation (SHEDS), in conjunction with a number of available databases, including NATA, NHEXAS, CSFII, and CHAD, and extends modeling techniques that have been developed in recent years. Model results indicate that, in most cases, the food intake pathway is the dominant contributor to total exposure and dose to arsenic. Model predictions are evaluated qualitatively by comparing distributions of predicted total arsenic amounts in urine with those derived using biomarker measurements from the NHEXAS — Region V study: the population distributions of urinary total arsenic levels calculated through MENTOR and from the NHEXAS measurements are in general qualitative agreement. Observed differences are due to various factors, such as interindividual variation in arsenic metabolism in humans, that are not fully accounted for in the current model implementation but can be incorporated in the future, in the open framework of MENTOR. The present study demonstrates that integrated source-to-dose modeling for arsenic can not only provide estimates of the relative contributions of multipathway exposure routes to the total exposure estimates, but can also estimate internal target tissue doses for speciated organic and inorganic arsenic, which can eventually be used to improve evaluation of health risks associated with exposures to arsenic from multiple sources, routes, and pathways. PMID:18073786

Recent Advances in the Measurement of Arsenic, Cadmium, and Mercury in Rice and Other Foods

PubMed Central

Punshon, Tracy

2015-01-01

Trace element analysis of foods is of increasing importance because of raised consumer awareness and the need to evaluate and establish regulatory guidelines for toxic trace metals and metalloids. This paper reviews recent advances in the analysis of trace elements in food, including challenges, state-of-the art methods, and use of spatially resolved techniques for localizing the distribution of As and Hg within rice grains. Total elemental analysis of foods is relatively well-established but the push for ever lower detection limits requires that methods be robust from potential matrix interferences which can be particularly severe for food. Inductively coupled plasma mass spectrometry (ICP-MS) is the method of choice, allowing for multi-element and highly sensitive analyses. For arsenic, speciation analysis is necessary because the inorganic forms are more likely to be subject to regulatory limits. Chromatographic techniques coupled to ICP-MS are most often used for arsenic speciation and a range of methods now exist for a variety of different arsenic species in different food matrices. Speciation and spatial analysis of foods, especially rice, can also be achieved with synchrotron techniques. Sensitive analytical techniques and methodological advances provide robust methods for the assessment of several metals in animal and plant-based foods, in particular for arsenic, cadmium and mercury in rice and arsenic speciation in foodstuffs. PMID:25938012

Arsenic Toxicity to Juvenile Fish: Effects of Exposure Route, Arsenic Speciation, and Fish Species

EPA Science Inventory

Arsenic toxicity to juvenile rainbow trout and fathead minnows was evaluated in 28-day tests using both dietborne and waterborne exposures, both inorganic and organic arsenic species, and both a live diet and an arsenic-spiked pellet diet. Effects of inorganic arsenic on rainbow...

ARSENIC REMOVAL

EPA Science Inventory

Presentation covered five topics; arsenic chemistry, best available technology (BAT), surface water technology, ground water technology and case studies of arsenic removal. The discussion on arsenic chemistry focused on the need and method of speciation for AsIII and AsV. BAT me...

SPECIATION OF ARSENIC COMPOUNDS IN DRINKING WATER BY CAPILLARY ELECTROPHORESIS WITH HYDRODYNAMICALLY MODIFIED ELECTROOSMOTIC FLOW DETECTED THROUGH HYDRIDE GENERATION INDUCTIVELY COUPLED PLASMA MASS...

EPA Science Inventory

Capillary electrophoresis (CE) was used to speciate four environmentally significant, toxic forms of arsenic: arsenite, arsenate, monomethylarsonic acid and dimethylarsinic acid. Hydride generation (HG) was used to convert the species into their respective hydrides. The hydride s...

Methods of analysis by the U.S. Geological Survey National Water Quality Laboratory; arsenic speciation in natural-water samples using laboratory and field methods

USGS Publications Warehouse

Garbarino, John R.; Bednar, Anthony J.; Burkhardt, Mark R.

2002-01-01

Analytical methods for the determination of arsenite [As(III)], arsenate [As(V)], dimethylarsinate (DMA), monomethylarsonate (MMA), and roxarsone in filtered natural-water samples are described. Various analytical methods can be used for the determination, depending on the arsenic species being determined. Arsenic concentration is determined by using inductively coupled plasma-mass spectrometry (ICP-MS) as an arsenic-specific detector for all methods. Laboratory-speciation methods are described that use an ion chromatographic column to separate the arsenic species; the column length, column packing, and mobile phase are dependent on the species of interest. Regardless of the separation technique, the arsenic species are introduced into plasma by eithe rpneumatic nebulization or arsine generation. Analysis times range from 2 to 8 minutes and method detection limits range from 0.1 to 0.6 microgram-arsenic per liter (ug-As/L), 10 to 60 picograms absolute (for a 100-microliter injection), depending on the arsenic species determined and the analytical method used. A field-generation specciation method also is described that uses a strong anion exchange cartridge to separate As(III) from As(V) in the field. As(III) in the eluate and the As(V) in the cartridge extract are determined by direct nebulization ICP-MS. Methylated arsenic species that also are retained on the cartridge will positively bias As(V) results without further laboratory separations. The method detection limit for field speciation is 0.3 ug-As/L. The distribution of arsenic species must be preserved in the field to eliminate changes caused by photochemical oxidation or metal oxyhydroxide precipitation. Preservation techniques, such as refrigeration, the addition of acides, or the additoin of ethylene-diaminetetraacetic acid (EDTA) and the effects of ambient light were tested. Of the preservatives evaluated, EDTA was found to work best with the laboratory- and field-speciation methods for all sample matrices tested. Storing the samples in opaque polytethylene bottles eliminated the effects of photochemical oxidation. The percentage change in As(III):As(V) ratios for an EDTA-preserved acid mine drainage (AMD) sample and ground-water sample during a 3-month period was -5 percent and +3 percent, respectively. The bias and variability of the methods were evaluated by comparing results for total arsenic and As(III), As(V), DMA, and MMA concentrations in ground water, AMD, and surface water. Seventy-one ground-water, 10 AMD, and 24 surface-water samples were analyzed. Concentrations in ground-water samples reached 720 ug-As/L for As(III) and 1080 ug-As/L for As(V); AMD samples reached 12800 ug-As/L for As(III) and 7050 ug-As/L for As(V); and surface-water samples reached 5 ug-As/L for As(III) and As(V). Inorganic arsenic species distribution in the samples ranged from 0 to 90 percent As(III). DMA and MMA were present only in surface-water samples from agricultural areas where the herbicide monosodium methylarsonate was applied; concentrations never exceeded 6 ug-As/L. Statistical analyses indicated that the difference between As(III) and As(V) concentrations for samples preserved with EDTA in opaque bottles and field-speciation results were analytically insignificant at the 95-percent confidence interval. There was no significant difference among the methods tested for total arsenic concentration. Percentage recovery for field samples spiked at 50 ug-As/L and analyzed by the laboratory-speciation method (n=2) ranged from 82 to 100 percent for As(III), 97 to 102 percent for As(V), 90 to 104 percent for DMA, and 81 to 96 percent for MMA; recoveries for samples spiked at 100 ug-As/L and analyzed by the field-speciation method ranged from 102 to 107 percent for As(III) and 105 to 106 percent for As(V). Laboratory-speciation results for Environment Canada reference material SLRS-2 closely matched reported concentrations. Laboratory-speciation metho

Characterization and measurement of natural gas trace constituents. Volume 1. Arsenic. Final report, June 1989-October 1993

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chao, S.S.; Attari, A.

1995-01-01

The discovery of arsenic compounds, as alkylarsines, in natural gas prompted this research program to develop reliable measurement techniques needed to assess the efficiency of removal processes for these environmentally sensitive substances. These techniques include sampling, speciation, quantitation and on-line instrumental methods for monitoring the total arsenic concentration. The current program has yielded many products, including calibration standards, arsenic-specific sorbents, sensitive analytical methods and instrumentation. Four laboratory analytical methods have been developed and successfully employed for arsenic determination in natural gas. These methods use GC-AED and GC-MS instruments to speciate alkylarsines, and peroxydisulfate extraction with FIAS, special carbon sorbent withmore » XRF and an IGT developed sorbent with GFAA for total arsenic measurement.« less

Airborne arsenic and urinary excretion of arsenic metabolites during boiler cleaning operations in a Slovak coal-fired power plant.

PubMed Central

Yager, J W; Hicks, J B; Fabianova, E

1997-01-01

Little information is available on the relationship between occupational exposure to inorganic arsenic in coal fly ash and urinary excretion of arsenic metabolites. This study ws undertaken in a coal-fired power plant in Slovakia during a routine maintenance outage. Arsenic was measured in the breathing zone of workers during 5 consecutive workdays, and urine samples were obtained for analysis of arsenic metabolites--inorganic arsenic (Asi), monomethylarsonic acid (MMA), and dimethylarsinic acid (DMA)--prior to the start of each shift. Results from a small number of cascade impactor air samples indicated that approximately 90% of total particle mass and arsenic was present in particle size fractions >/= 3.5 micron. The 8-hr time-weighted average (TWA) mean arsenic air concentration was 48.3 microg/m3 (range 0.17-375.2) and the mean sum of urinary arsenic (SigmaAs) metabolites was 16.9 microg As/g creatinine (range 2.6-50.8). For an 8-hr TWA of 10 microg/m3 arsenic from coal fly ash, the predicted mean concentration of the SigmaAs urinary metabolites was 13.2 microg As/G creatinine [95% confidence interval (CI), 10.1-16.3). Comparisons with previously published studies of exposure to arsenic trioxide vapors and dusts in copper smelters suggest that bioavailability of arsenic from airborne coal fly ash (as indicated by urinary excretion) is about one-third that seen in smelters and similar settings. Arsenic compound characteristics, matrix composition, and particle size distribution probably play major roles in determining actual uptake of airborne arsenic. Images Figure 1. A Figure 1. B Figure 2. PMID:9347899

Availability of arsenic in human milk in women and its correlation with arsenic in urine of breastfed children living in arsenic contaminated areas in Bangladesh.

PubMed

Islam, Md Rafiqul; Attia, John; Alauddin, Mohammad; McEvoy, Mark; McElduff, Patrick; Slater, Christine; Islam, Md Monirul; Akhter, Ayesha; d'Este, Catherine; Peel, Roseanne; Akter, Shahnaz; Smith, Wayne; Begg, Stephen; Milton, Abul Hasnat

2014-12-04

Early life exposure to inorganic arsenic may be related to adverse health effects in later life. However, there are few data on postnatal arsenic exposure via human milk. In this study, we aimed to determine arsenic levels in human milk and the correlation between arsenic in human milk and arsenic in mothers and infants urine. Between March 2011 and March 2012, this prospective study identified a total of 120 new mother-baby pairs from Kashiani (subdistrict), Bangladesh. Of these, 30 mothers were randomly selected for human milk samples at 1, 6 and 9 months post-natally; the same mother baby pairs were selected for urine sampling at 1 and 6 months. Twelve urine samples from these 30 mother baby pairs were randomly selected for arsenic speciation. Arsenic concentration in human milk was low and non-normally distributed. The median arsenic concentration in human milk at all three time points remained at 0.5 μg/L. In the mixed model estimates, arsenic concentration in human milk was non-significantly reduced by -0.035 μg/L (95% CI: -0.09 to 0.02) between 1 and 6 months and between 6 and 9 months. With the progression of time, arsenic concentration in infant's urine increased non-significantly by 0.13 μg/L (95% CI: -1.27 to 1.53). Arsenic in human milk at 1 and 6 months was not correlated with arsenic in the infant's urine at the same time points (r = -0.13 at 1 month and r = -0.09 at 6 month). Arsenite (AsIII), arsenate (AsV), monomethyl arsonic acid (MMA), dimethyl arsinic acid (DMA) and arsenobetaine (AsB) were the constituents of total urinary arsenic; DMA was the predominant arsenic metabolite in infant urine. We observed a low arsenic concentration in human milk. The concentration was lower than the World Health Organization's maximum permissible limit (WHO Permissible Limit 15 μg/kg-bw/week). Our findings support the safety of breastfeeding even in arsenic contaminated areas.

APPROACHES TO CHARACTERIZING SOLID PHASE ARSENIC SPECIATION IN SOILS

EPA Science Inventory

The partitioning of arsenic to soil solids is an important process controlling the stabilization of arsenic wastes and mobility of arsenic in the environment. Identification of the physicochemical characteristics of the partitioning mechanism(s) is important for treatment op...

Correlation of arsenic exposure through drinking groundwater and urinary arsenic excretion among adults in Pakistan.

PubMed

Ahmed, Mubashir; Fatmi, Zafar; Ali, Arif

2014-01-01

Long-term exposure to arsenic has been associated with manifestation of skin lesions (melanosis/keratosis) and increased risk of internal cancers (lung/bladder). The objective of the study described here was to determine the relationship between exposure of arsenic through drinking groundwater and urinary arsenic excretion among adults > or =15 years of age living in Khairpur district, Pakistan. Total arsenic was determined in drinking groundwater and in spot urine samples of 465 randomly selected individuals through hydride generation-atomic absorption spectrometry. Spearman's rank correlation coefficient was calculated between arsenic in drinking groundwater and arsenic excreted in urine. The median arsenic concentration in drinking water was 2.1 microg/L (range: 0.1-350), and in urine was 28.5 microg/L (range: 0.1-848). Positive correlation was found between total arsenic in drinking water and in urine (r = .52, p < .01). Urinary arsenic may be used as a biomarker of arsenic exposure through drinking water.

INFLUENCE OF DIETARY ARSENIC ON URINARY ARSENIC METABOLITE EXCRETION

EPA Science Inventory

Influence of Dietary Arsenic on Urinary Arsenic Metabolite Excretion

Cara L. Carty, M.S., Edward E. Hudgens, B.Sc., Rebecca L. Calderon, Ph.D., M.S.P.H., Richard Kwok, M.S.P.H., Epidemiology and Biomarkers Branch/HSD, NHEERL/US EPA; David J. Thomas, Ph.D., Pharmacokinetics...

Arsenic speciation and fucoxanthin analysis from seaweed dietary supplements using LC-MS

USDA-ARS?s Scientific Manuscript database

Inorganic species are considered more toxic to humans than organic arsenic and total arsenic. Analysis of total arsenic in metallic form, organic and inorganic arsenic species from seaweeds and dietary supplements using LC-ICP-MS was developed. Solvent extraction with sonication and microwave extr...

Voltammetric determination of arsenic in high iron and manganese groundwaters.

PubMed

Gibbon-Walsh, Kristoff; Salaün, Pascal; Uroic, M Kalle; Feldmann, Joerg; McArthur, John M; van den Berg, Constant M G

2011-09-15

Determination of the speciation of arsenic in groundwaters, using cathodic stripping voltammetry (CSV), is severely hampered by high levels of iron and manganese. Experiments showed that the interference is eliminated by addition of EDTA, making it possible to determine the arsenic speciation on-site by CSV. This work presents the CSV method to determine As(III) in high-iron or -manganese groundwaters in the field with only minor sample treatment. The method was field-tested in West-Bengal (India) on a series of groundwater samples. Total arsenic was subsequently determined after acidification to pH 1 by anodic stripping voltammetry (ASV). Comparative measurements by ICP-MS as reference method for total As, and by HPLC for its speciation, were used to corroborate the field data in stored samples. Most of the arsenic (78±0.02%) was found to occur as inorganic As(III) in the freshly collected waters, in accordance with previous studies. The data shows that the modified on-site CSV method for As(III) is a good measure of water contamination with As. The EDTA was also found to be effective in stabilising the arsenic speciation for longterm sample storage at room temperature. Without sample preservation, in water exposed to air and sunlight, the As(III) was found to become oxidised to As(V), and Fe(II) oxidised to Fe(III), removing the As(V) by adsorption on precipitating Fe(III)-hydroxides within a few hours. Copyright © 2011 Elsevier B.V. All rights reserved.

SPECIATION OF ARSENIC IN EXPOSURE ASSESSMENT MATRICES

EPA Science Inventory

The speciaton of arsenic in water, food and urine are analytical capabilities which are an essential part in arsenic risk assessment. The cancer risk associated with arsenic has been the driving force in generating the analytical research in each of these matrices. This presentat...

DETERMINATION OF URINARY TRIVALENT ARSENICALS (MMASIII AND DMASIII) IN INDIVIDUALS CHRONICALLY EXPOSED TO ARSENIC

EPA Science Inventory

DETERMINATION OF URINARY TRIVALENT ARSENICALS (MMAsIII and DMAsIII) IN INDIVIDUALS CHRONICALLY EXPOSED TO ARSENIC.
L. M. Del Razo1, M. Styblo2, W. R. Cullen3, and D.J. Thomas4.
1Toxicology Section, Cinvestav-IPN, Mexico, D.F., 2Univ. North Carolina, Chapel Hill, NC; 3Uni...

ARE ALL ARSENIC EXPOSURES TOXIC? SUPPORTING REGIONAL RISK ASSESSMENTS THROUGH IMPROVED ARSENIC SPECIATION METHODOLOGY

EPA Science Inventory

Arsenic exposure assessments require the evaluation of the relative contribution of both media (water, food, etc.) and routes of exposure (ingestion, inhalation, dermal). For arsenic, the important media are predominately water and food and therefore, the route of concern for ...

Urinary arsenic profiles and the risks of cancer mortality: A population-based 20-year follow-up study in arseniasis-endemic areas in Taiwan

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chung, Chi-Jung; Department of Medical Research, China Medical Hospital, Taichung, Taiwan; Huang, Ya-Li

2013-04-15

Few studies investigated the association between chronic arsenic exposure and the mortality of cancers by estimating individual urinary arsenic methylation profiles. Therefore, we compared with the general population in Taiwan to calculate the standardized mortality ratio (SMR) in arseniasis-endemic area of Taiwan from 1996 to 2010 and evaluated the dose-response relationships between environmental arsenic exposure indices or urinary arsenic profiles and the mortality of cause-specific cancer. A cohort of 1563 residents was conducted and collected their urine sample and information regarding arsenic exposure from a questionnaire. All-cause death was identified using the National Death Registry of Taiwan. Urinary arsenic profilesmore » were measured using high performance liquid chromatography–hydride generator–atomic absorption spectrometry. We used Cox proportional hazard models to evaluate the mortality risks. In results, 193 all-site cancer deaths, and 29, 71, 43 deaths respectively for liver, lung and bladder cancers were ascertained. The SMRs were significantly high in arseniasis-endemic areas for liver, lung, and bladder cancers. People with high urinary InAs% or low DMA% or low secondary methylation index (SMI) were the most likely to suffer bladder cancer after adjusting other risk factors. Even stopping exposure to arsenic from the artesian well water, the mortality rates of the residents were higher than general population. Finally, urinary InAs%, DMA% and SMI could be the potential biomarkers to predict the mortality risk of bladder cancer. -- Highlights: ► The SMRs were significantly high in arseniasis-endemic areas for liver, lung, and bladder cancers. ► People with high urinary InAs% were the most likely to suffer bladder cancer. ► People with low DMA% or low SMI were the most likely to suffer bladder cancer.« less

Arsenic Speciation and Cadmium Determination in Tobacco Leaves, Ash and Smoke.

PubMed

Iwai, Takahiro; Chiba, Koichi; Narukawa, Tomohiro

2016-01-01

The concentrations of arsenic (As) and cadmium (Cd) in the tobacco leaves, ash and smoke of 10 kinds of cigarettes collected from different countries worldwide were determined by ICP-MS after microwave-assisted digestion. Total As and Cd concentrations in the tobacco leaves ranged from 0.20 to 0.63 and 1.8 to 9.9 mg kg(-1), respectively. By the speciation analysis of As in tobacco leaves and ash by HPLC-ICP-MS following acid extraction, arsenite [As(III)] and arsenate [As(V)] were determined and trace amounts of monomethylarsonic acid (MMAA), dimethylarsinic acid (DMAA), trimethylarsine oxide (TMAO), tetramethylarsonium (TeMA) and some unidentified As species were also found. Arsenic speciation for smoke absorbed in an aqueous solution was carried out. The sum of the As species in tobacco leaves, ash and smoke was in good agreement with the result of total As determination in each sample, and the recoveries of speciation were 100 ± 10%. The distributions and the behaviors of As species were clarified.

Speciation of volatile arsenic at geothermal features in Yellowstone National Park

USGS Publications Warehouse

Planer-Friedrich, B.; Lehr, C.; Matschullat, J.; Merkel, B.J.; Nordstrom, D. Kirk; Sandstrom, M.W.

2006-01-01

Geothermal features in the Yellowstone National Park contain up to several milligram per liter of aqueous arsenic. Part of this arsenic is volatilized and released into the atmosphere. Total volatile arsenic concentrations of 0.5-200 mg/m3 at the surface of the hot springs were found to exceed the previously assumed nanogram per cubic meter range of background concentrations by orders of magnitude. Speciation of the volatile arsenic was performed using solid-phase micro-extraction fibers with analysis by GC-MS. The arsenic species most frequently identified in the samples is (CH3)2AsCl, followed by (CH3)3As, (CH3)2AsSCH3, and CH3AsCl2 in decreasing order of frequency. This report contains the first documented occurrence of chloro- and thioarsines in a natural environment. Toxicity, mobility, and degradation products are unknown. ?? 2006 Elsevier Inc. All rights reserved.

Arsenic Metabolites and Methylation Capacity Among Individuals Living in a Rural Area with Endemic Arseniasis in Inner Mongolia, China.

PubMed

Wei, Binggan; Yu, Jiangping; Li, Hairong; Yang, Linsheng; Xia, Yajuan; Wu, Kegong; Gao, Jianwei; Guo, Zhiwei; Cui, Na

2016-04-01

More than 0.3 million individuals are subject to chronic exposure to arsenic via their drinking water in Inner Mongolia, China. To determine arsenic methylation capacity profiles for such individuals, concentrations of urinary arsenic metabolites were measured for 548 subjects using high-performance liquid chromatography and a hydride generator combined with inductively coupled plasma-mass spectrometry. Mean urinary concentrations of dimethylarsonic acid (DMA), monomethylarsonic acid (MMA), inorganic arsenic (iAs), and total arsenic (TAs) were 200.50, 46.71, 52.96, and 300.17 μg/L, respectively. The %iAs, %DMA, and %MMA were 15.98, 69.72, and 14.29%. Mean urinary %iAs and %MMA were higher in males, while urinary %DMA was higher in females. There was a strong positive correlation between %iAs and %MMA, with negative correlations between %iAs and %DMA, and %iAs and %MMA. In addition, %iAs and %MMA were positively associated with total arsenic in drinking water (WAs), while %DMA was negatively related with WAs. Regression analysis indicated that the primary methylation index (PMI) and secondary methylation index (SMI) generally decreased with increasing WAs. Females had a higher arsenic methylation capacity compared to males. Younger subjects had lower primary arsenic methylation capacity. However, the secondary arsenic methylation capacity was hardly affected by age. Moreover, both primary and secondary arsenic methylation capacities were negatively related to WAs.

Urinary arsenic levels influenced by abandoned mine tailings in the Southernmost Baja California Peninsula, Mexico.

PubMed

Colín-Torres, Carlos G; Murillo-Jiménez, Janette M; Del Razo, Luz M; Sánchez-Peña, Luz C; Becerra-Rueda, Oscar F; Marmolejo-Rodríguez, Ana J

2014-10-01

Gold has been mined at San Antonio-El Triunfo, (Baja California Sur, Mexico) since the 18th century. This area has approximately 5,700 inhabitants living in the San Juan de Los Planes and El Carrizal hydrographic basins, close to more than 100 abandoned mining sites containing tailings contaminated with potentially toxic elements such as arsenic. To evaluate the arsenic exposure of humans living in the surrounding areas, urinary arsenic species, such as inorganic arsenic (iAs) and the metabolites mono-methylated (MMA) and di-methylated arsenic acids (DMA), were evaluated in 275 residents (18-84 years of age). Arsenic species in urine were analyzed by hydride generation-cryotrapping-atomic absorption spectrometry, which excludes the non-toxic forms of arsenic such as those found in seafood. Urinary samples contained a total arsenic concentration (sum of arsenical species) which ranged from 1.3 to 398.7 ng mL(-1), indicating 33% of the inhabitants exceeded the biological exposition index (BEI = 35 ng mL(-1)), the permissible limit for occupational exposure. The mean relative urinary arsenic species were 9, 11 and 80% for iAs, MMA and DMA, respectively, in the Los Planes basin, and 17, 10 and 73%, respectively, in the El Carrizal basin. These data indicated that environmental intervention is required to address potential health issues in this area.

Association between Arsenic Exposure from Drinking Water and Longitudinal Change in Blood Pressure among HEALS Cohort Participants.

PubMed

Jiang, Jieying; Liu, Mengling; Parvez, Faruque; Wang, Binhuan; Wu, Fen; Eunus, Mahbub; Bangalore, Sripal; Newman, Jonathan D; Ahmed, Alauddin; Islam, Tariqul; Rakibuz-Zaman, Muhammad; Hasan, Rabiul; Sarwar, Golam; Levy, Diane; Slavkovich, Vesna; Argos, Maria; Scannell Bryan, Molly; Farzan, Shohreh F; Hayes, Richard B; Graziano, Joseph H; Ahsan, Habibul; Chen, Yu

2015-08-01

Cross-sectional studies have shown associations between arsenic exposure and prevalence of high blood pressure; however, studies examining the relationship of arsenic exposure with longitudinal changes in blood pressure are lacking. We evaluated associations of arsenic exposure in relation to longitudinal change in blood pressure in 10,853 participants in the Health Effects of Arsenic Longitudinal Study (HEALS). Arsenic was measured in well water and in urine samples at baseline and in urine samples every 2 years after baseline. Mixed-effect models were used to estimate the association of baseline well and urinary creatinine-adjusted arsenic with annual change in blood pressure during follow-up (median, 6.7 years). In the HEALS population, the median water arsenic concentration at baseline was 62 μg/L. Individuals in the highest quartile of baseline water arsenic or urinary creatinine-adjusted arsenic had a greater annual increase in systolic blood pressure compared with those in the reference group (β = 0.48 mmHg/year; 95% CI: 0.35, 0.61, and β = 0.43 mmHg/year; 95% CI: 0.29, 0.56 for water arsenic and urinary creatinine-adjusted arsenic, respectively) in fully adjusted models. Likewise, individuals in the highest quartile of baseline arsenic exposure had a greater annual increase in diastolic blood pressure for water arsenic and urinary creatinine-adjusted arsenic, (β = 0.39 mmHg/year; 95% CI: 0.30, 0.49, and β = 0.45 mmHg/year; 95% CI: 0.36, 0.55, respectively) compared with those in the lowest quartile. Our findings suggest that long-term arsenic exposure may accelerate age-related increases in blood pressure. These findings may help explain associations between arsenic exposure and cardiovascular disease.

Total arsenic determination and speciation in infant food products by ion chromatography-inductively coupled plasma-mass spectrometry.

PubMed

Vela, Nohora P; Heitkemper, Douglas T

2004-01-01

Health risk associated with dietary arsenic intake may be different for infants and adults. Seafood is the main contributor to arsenic intake for adults while terrestrial-based food is the primary source for infants. Processed infant food products such as rice-based cereals, mixed rice/formula cereals, milk-based infant formula, applesauce and puree of peaches, pears, carrots, sweet potatoes, green beans, and squash were evaluated for total and speciated arsenic content. Arsenic concentrations found in rice-based cereals (63-320 ng/g dry weight) were similar to those reported for raw rice. Results for the analysis of powdered infant formula by inductively coupled plasma-mass spectrometry (ICP-MS) indicated a narrow and low arsenic concentration range (12 to 17 ng/g). Arsenic content in puree infant food products, including rice cereals, fruits, and vegetables, varies from <1 to 24 ng/g wet weight. Sample treatment with trifluoroacetic acid at 100 degrees C were an efficient and mild method for extraction of arsenic species present in different food matrixes as compared to alternative methods that included sonication and accelerated solvent extraction. Extraction recoveries from 94 to 128% were obtained when the summation of species was compared to total arsenic. The ion chromatography (IC)-ICP-MS method selected for arsenic speciation allowed for the quantitative determination of inorganic arsenic [As(III) + As(V)], dimethylarsinic acid (DMA), and methylarsonic acid (MMA). Inorganic arsenic and DMA are the main species found in rice-based and mixed rice/formula cereals, although traces of MMA were also detected. Inorganic arsenic was present in freeze-dried sweet potatoes, carrots, green beans, and peaches. MMA and DMA were not detected in these samples. Arsenic species in squash, pears, and applesauce were not detected above the method detection limit [5 ng/g dry weight for As(III), MMA, and DMA and 10 ng/g dry weight for As(V)].

DEVELOPMENT OF ARSENIC SPECIATION METHODOLOGY FOR DETERMINING BACKGROUND EXPOSURE LEVELS OF INORGANIC ARSENIC IN DIETARY SAMPLES AND APPLICATION TO IN VITRO BIOACCESSIBILITY STUDIES

EPA Science Inventory

Ingestion of arsenic is the primary route of exposure for most people, with dietary intake and drinking water as the primary sources of that exposure. Traditionally, measurements of arsenic dietary intake are based on food consumption data coupled with total arsenic data from a ...

Arsenic leaching and speciation in C&D debris landfills and the relationship with gypsum drywall content.

PubMed

Zhang, Jianye; Kim, Hwidong; Dubey, Brajesh; Townsend, Timothy

2017-01-01

The effects of sulfide levels on arsenic leaching and speciation were investigated using leachate generated from laboratory-scale construction and demolition (C&D) debris landfills, which were simulated lysimeters containing various percentages of gypsum drywall. The drywall percentages in lysimeters were 0, 1, 6, and 12.4wt% (weight percent) respectively. With the exception of a control lysimeter that contained 12.4wt% of drywall, each lysimeter contained chromated copper arsenate (CCA) treated wood, which accounts for 10wt% of the C&D waste. During the period of study, lysimeters were mostly under anaerobic conditions. Leachate analysis results showed that sulfide levels increased as the percentage of drywall increased in landfills, but arsenic concentrations in leachate were not linearly correlated with sulfide levels. Instead, the arsenic concentrations decreased as sulfide increased up to approximately 1000μg/L, but had an increase with further increase in sulfide levels, forming a V-shape on the arsenic vs. sulfide plot. The analysis of arsenic speciation in leachate showed different species distribution as sulfide levels changed; the fraction of arsenite (As(III)) increased as the sulfide level increased, and thioarsenate anions (As(V)) were detected when the sulfide level further increased (>10 4 μg/L). The formation of insoluble arsenic sulfide minerals at a lower range of sulfide and soluble thioarsenic anionic species at a higher range of sulfide likely contributed to the decreasing and increasing trend of arsenic leaching. Copyright © 2016. Published by Elsevier Ltd.

DNA methylation changes in Mexican children exposed to arsenic from two historic mining areas in San Luis potosí.

PubMed

Alegría-Torres, Jorge Alejandro; Carrizales-Yánez, Leticia; Díaz-Barriga, Fernando; Rosso-Camacho, Fernando; Motta, Valeria; Tarantini, Letizia; Bollati, Valentina

2016-12-01

Arsenic is a carcinogen and epimutagen that threatens the health of exposed populations worldwide. In this study, we examined the methylation status of Alu and long interspersed nucleotide elements (LINE-1) and their association with levels of urinary arsenic in 84 Mexican children between 6 and 12 years old from two historic mining areas in the State of San Luis Potosí, Mexico. Urinary arsenic levels were determined by atomic absorption spectrophotometry and DNA methylation analysis was performed in peripheral blood leukocytes by bisulfite-pyrosequencing. The geometric mean of urinary arsenic was 26.44 µg/g Cr (range 1.93-139.35). No significant differences in urinary arsenic or methylation patterns due to gender were observed. A positive correlation was found between urinary arsenic and the mean percentage of methylated cytosines in Alu sequences (Spearman correlation coefficient r = 0.532, P < 0.001), and a trend of LINE-1 hypomethylation was also observed (Spearman correlation coefficient r = -0.232, P = 0.038) after adjustment for sex and age. A linear regression model showed an association with log-normalized urinary arsenic for Alu (β = 1.05, 95% CI: 0.67; 1.43, P < 0.001) and LINE-1 (β = -0.703, 95% CI: -1.36; -0.38, P = 0.038). Despite the low-level arsenic exposure, a subtle epigenetic imbalance measured as DNA methylation was detected in the leukocytes of Mexican children living in two historic mining areas. Environ. Mol. Mutagen. 57:717-723, 2016. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

INTRODUCTION AND OVERVIEW OF WORKSHOP ON MANAGING ARSENIC RISKS TO THE ENVIRONMENT

EPA Science Inventory

The purpose of this workshop will be to serve as a technical forum for the exchange of information on treating arsenic and arsenic compounds. The goals of the workshop are 1) to examine the chemical fundamentals related to arsenic chemistry, speciation, and analytical issues, 2) ...

ADVANCED APPROACHES TO ARSINE ATOMIZATION FOR AS SPECIATION BY CRYOFOCUSING WITH ATOMIC ABSORPTION AND ATOMIC FLUORESCENCE DETECTORS

EPA Science Inventory

Human metabolism of inorganic arsenic (iAs) yields methylated arsenicals that contain arsenic in +3 or +5 oxidation state. Trivalent methylated arsenicals are significantly more toxic than their pentavalent counterparts. Therefore, determination of tri- and pentavalent forms of m...

Arsenic speciation and transport associated with the release of spent geothermal fluids in Mutnovsky field (Kamchatka, Russia)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ilgen, Anastasia G.; Rychagov, Sergey N.; Trainor, Thomas P.

The use of geothermal fluids for the production of electricity poses a risk of contaminating surface waters when spent fluids are discharged into (near) surface environments. Arsenic (As) in particular is a common component in geothermal fluids and leads to a degradation of water quality when present in mobile and bioavailable forms. We have examined changes in arsenic speciation caused by quick transition from high temperature reducing conditions to surface conditions, retention mechanisms, and the extent of transport associated with the release of spent geothermal fluids at the Dachny geothermal fields (Mutnovsky geothermal region), Kamchatka, Russia -- a high temperaturemore » field used for electricity production. In the spent fluids, the arsenic concentration reaches 9 ppm, while in natural hot springs expressed in the vicinity of the field, the As concentration is typically below 10 ppb. The aqueous phase arsenic speciation was determined using Liquid Chromatography (LC) coupled to an Inductively Coupled Plasma Mass Spectrometer (ICP-MS). The arsenic speciation in the bottom sediments (< 65 {mu}m fraction) of the local surface waters was analyzed using X-ray Absorption Spectroscopy (XAS). Arsenic in the geothermal source fluids is predominantly found as As(III), while a mixture of As(III)/As(V) is found in the water and sediment of the Falshivaia River downstream from the power plant. The extent of elevated arsenic concentrations in water is limited by adsorption to the bottom sediment and dilution, as determined using Cl{sup -} from the deep well fluids as a tracer. Analysis of the Extended X-ray Absorption Fine Structure (EXAFS) spectra shows that sediment phase arsenic is associated with both Al- and Fe-rich phases with a bi-dentate corner sharing local geometry. The geothermal waste fluids released in the surface water create a localized area of arsenic contamination. The extent of transport of dissolved As is limited to {approx}7 km downstream from the source, while As associated with bottom sediment travels {approx}3 km farther.« less

REACTION PROCESSES OF ARSENIC IN SULFIDIC SOLUTIONS

EPA Science Inventory

The fate of arsenic in the environment is fundamentally linked to its speciation. Arsenic in aerobic environments is predominantly arsenate, however under reducing conditions arsenite species dominate. In anoxic or sulfidic environments thioarsenite ((As(OH)x(SH)yz-) species alon...

Arsenic speciation in manufactured seafood products.

PubMed

Vélez, D; Montoro, R

1998-09-01

The literature on the speciation of arsenic (As) in seafoods was critically reviewed. Most research has been directed toward fresh seafood products with few papers dealing with As speciation in manufactured seafoods. Predictions concerning As species made on the basis of fresh seafood products cannot be extrapolated to manufactured seafoods. Therefore, due to the numerous species of As, the scarcity of data concerning their presence in foods, the transformations each species may undergo during industrial processing and cooking, and the lack of legislation on permitted As levels in seafood products, As species in manufactured seafood products need to be determined and quantified.

Levels of plasma selenium and urinary total arsenic interact to affect the risk for prostate cancer.

PubMed

Hsueh, Yu-Mei; Su, Chien-Tien; Shiue, Horng-Sheng; Chen, Wei-Jen; Pu, Yeong-Shiau; Lin, Ying-Chin; Tsai, Cheng-Shiuan; Huang, Chao-Yuan

2017-09-01

This study investigated whether plasma selenium levels modified the risk for prostate cancer (PC) related to arsenic exposure. We conducted a case-control study that included 318 PC patients and 318 age-matched, healthy control subjects. Urinary arsenic profiles were examined using HPLC-HG-AAS and plasma selenium levels were measured by ICP-MS. We found that plasma selenium levels displayed a significant dose-dependent inverse association with PC. The odds ratio (OR) and 95% confidence interval (CI) for PC was 0.07 (0.04-0.13) among participants with a plasma selenium level >28.06 μg/dL vs. ≤19.13 μg/dL. A multivariate analysis showed that participants with a urinary total arsenic concentration >29.28 μg/L had a significantly higher OR (1.75, 1.06-2.89) for PC than participants with ≤29.89 μg/L. The combined presence of a low plasma selenium level and a high urinary total arsenic concentration exponentially increased the OR for PC, and additively interacted with PSA at levels ≥20 ng/mL. This is the first epidemiological study to examine the combined effects of plasma selenium and urinary total arsenic levels on the OR for PC. Our data suggest a low plasma selenium level coupled with a high urinary total arsenic concentration creates a significant risk for aggressive PC. Copyright © 2017 Elsevier Ltd. All rights reserved.

Arsenic speciation in food chains from mid-Atlantic hydrothermal vents

USGS Publications Warehouse

Taylor, Vivien F.; Jackson, Brian P.; Siegfried, Matthew R.; Navratilova, Jana; Francesconi, Kevin A.; Kirshtein, Julie; Voytek, Mary

2012-01-01

Arsenic concentration and speciation were determined in benthic fauna collected from the Mid-Atlantic Ridge hydrothermal vents. The shrimp species, Rimicaris exoculata, the vent chimney-dwelling mussel, Bathymodiolus azoricus, Branchipolynoe seepensis, a commensal worm of B. azoricus and the gastropod Peltospira smaragdina showed variations in As concentration and in stable isotope (δ13C and δ15N) signature between species, suggesting different sources of As uptake. Arsenic speciation showed arsenobetaine to be the dominant species in R. exoculata, whereas in B. azoricus and B. seepensis arsenosugars were most abundant, although arsenobetaine, dimethylarsinate and inorganic arsenic were also observed, along with several unidentified species. Scrape samples from outside the vent chimneys covered with microbial mat, which is a presumed food source for many vent organisms, contained high levels of total As, but organic species were not detectable. The formation of arsenosugars in pelagic environments is typically attributed to marine algae, and the pathway to arsenobetaine is still unknown. The occurrence of arsenosugars and arsenobetaine in these deep sea organisms, where primary production is chemolithoautotrophic and stable isotope analyses indicate food sources are of vent origin, suggests that organic arsenicals can occur in a foodweb without algae or other photosynthetic life.

Arsenic speciation in food chains from mid-Atlantic hydrothermal vents.

PubMed

Taylor, Vivien F; Jackson, Brian P; Siegfried, Matthew; Navratilova, Jana; Francesconi, Kevin A; Kirshtein, Julie; Voytek, Mary

2012-05-04

Arsenic concentration and speciation were determined in benthic fauna collected from the Mid-Atlantic Ridge hydrothermal vents. The shrimp species, Rimicaris exoculata , the vent chimney-dwelling mussel, Bathymodiolus azoricus , Branchipolynoe seepensis , a commensal worm of B. azoricus , and the gastropod Peltospira smaragdina showed variations in As concentration and in stable isotope (δ 13 C and δ 15 N) signature between species, suggesting different sources of As uptake. Arsenic speciation showed arsenobetaine to be the dominant species in R. exoculata , whereas in B. azoricus and B. seepensis arsenosugars were most abundant, although arsenobetaine, dimethylarsinate, and inorganic arsenic were also observed, along with several unidentified species. Scrape samples from outside the vent chimneys, covered with microbial mat, which is a presumed food source for many vent organisms, contained high levels of total As, but organic species were not detectable. The formation of arsenosugars in pelagic environments is typically attributed to marine algae, and the pathway to arsenobetaine is still unknown. The occurrence of arsenosugars and arsenobetaine in these deep sea organisms, where primary production is chemolithoautotrophic and stable isotope analyses indicate food sources are of vent origin, suggests that organic arsenicals can occur in a food web without algae or other photosynthetic life.

Urinary porphyrins as biomarkers for arsenic exposure among susceptible populations in Guizhou Province, China

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ng, J.C.; Wang, J.P.; Zheng, B.S.

2005-08-07

Coal from some areas in Guizhou Province contains elevated levels of arsenic. This has caused arsenicosis in individuals who use arsenic-contaminated coal for the purposes of heating, cooking and drying of food in poorly ventilated dwellings. The population at risk has been estimated to be approximately 200,000 people. We analyzed the porphyrin excretion profile using a HPLC method in urine samples collected from 113 villagers who lived in Xing Ren district, a coal-borne arsenicosis endemic area and from 30 villagers from Xing Yi where arsenicosis is not prevalent. Urinary porphyrins were higher in the arsenic exposed group than those inmore » the control group. The correlation between urinary arsenic and porphyrin concentrations demonstrated the effect of arsenic on heme biosynthesis resulting in increased porphyrin excretion. Both uroporphyrin and coproporphyrin III showed significant increases in the excretion profile of the younger age ({lt} 20 years) arsenic-exposed group, suggesting that porphyrins could be used as early warning biomarkers of chronic arsenic exposure in humans. Greater increases of urinary arsenic and porphyrins in women, children and older age groups who spend much of their time indoors suggest that they might be at a higher risk. Whether elevated porphyrins could predict adverse health effects associated with both cancer and non-cancer end-points in chronically arsenic-exposed populations need further investigation.« less

Dietary administration of sodium arsenite to rats: Relations between dose and urinary concentrations of methylated and thio-metabolites and effects on the rat urinary bladder epithelium

DOE Office of Scientific and Technical Information (OSTI.GOV)

Suzuki, Shugo; Arnold, Lora L.; Pennington, Karen L.

2010-04-15

Based on epidemiological data, chronic exposure to high levels of inorganic arsenic in drinking water is carcinogenic to humans, inducing skin, urinary bladder and lung tumors. In vivo, inorganic arsenic is metabolized to organic methylated arsenicals including the highly toxic dimethylarsinous acid (DMA{sup III}) and monomethylarsonous acid (MMA{sup III}). Short-term treatment of rats with 100 mug/g trivalent arsenic (As{sup III}) as sodium arsenite in the diet or in drinking water induced cytotoxicity and necrosis of the urothelial superficial layer, with increased cell proliferation and hyperplasia. The objectives of this study were to determine if these arsenic-induced urothelial effects are dosemore » responsive, the dose of arsenic at which urothelial effects are not detected, and the urinary concentrations of the arsenical metabolites. We treated female F344 rats for 5 weeks with sodium arsenite at dietary doses of 0, 1, 10, 25, 50, and 100 ppm. Cytotoxicity, cell proliferation and hyperplasia of urothelial superficial cells were increased in a dose-responsive manner, with maximum effects found at 50 ppm As{sup III}. There were no effects at 1 ppm As{sup III}. The main urinary arsenical in As{sup III}-treated rats was the organic arsenical dimethylarsinic acid (DMA{sup V}). The thio-metabolites dimethylmonothioarsinic acid (DMMTA{sup V}) and monomethylmonothioarsinic acid (MMMTA{sup V}) were also found in the urine of As{sup III}-treated rats. The LC{sub 50} concentrations of DMMTA{sup V} for rat and human urothelial cells in vitro were similar to trivalent oxygen-containing arsenicals. These data suggest that dietary As{sup III}-induced urothelial cytotoxicity and proliferation are dose responsive, and the urothelial effects have a threshold corresponding to the urinary excretion of measurable reactive metabolites.« less

ARSENIC SPECIATION IN WATER AND DIETARY SAMPLES BY IC-ICP-MS WITH STRUCTURAL VERIFICATION VIA IC-ESI-MS/MS

EPA Science Inventory

The two predominate sources of arsenic exposure are water and dietary ingestion. Dietary sources can easily exceed drinking water exposures based on "total" arsenic measurements. This can be deceiving because arsenic's toxicity is strongly dependent on its chemical form and the...

SPECIATION OF ARSENIC IN EDIBLE BIOTA TO SUPPORT RISK ASSESSMENT DETERMINATION OF RELATIVE SOURCE CONTRIBUTION FOR ARSENIC

EPA Science Inventory

The Office of Research and Development has designated the study of arsenic as a high priority research area because of the health risk associated from exposure to this element. Present monitoring efforts are primarily focused on total concentration of arsenic in drinking water. ...

Performance of a Zerovalent Iron Reactive Barrier for the Treatment of Arsenic in Groundwater: Part 2. Geochemical Modeling and Solid Phase Studies

EPA Science Inventory

Arsenic uptake processes were evaluated in a zerovalent iron reactive barrier installed at a lead smelting facility using geochemical modeling, solid-phase analysis, and X-ray absorption spectroscopy techniques. Aqueous speciation of arsenic plays a key role in directing arsenic...

Analysis of Arsenicals and Their Sulfur Analogs in Biological Samples Using HPLC with Collision Cell ICP-MS and ESI-MS/MS

EPA Science Inventory

Recent arsenic speciation studies have indicated that the sulfur analogs of the more common arsenic oxides are present in environmental and biological systems. This discovery was previously impeded due to the strong affinity of these arsenic-sulfides for the stationary phases typ...

Biological and behavioral modifiers of urinary arsenic metabolic profiles in a U.S. population

EPA Science Inventory

Biological and behavioral modifiers of urinary arsenic metabolic profiles in a U.S. population David J. Thomas – ISTD, NHEERL Edward F. Hudgens – EHPD, NHEERL John Rogers - Westat Relations between intensity of arsenic exposure from home tap water and levels of inorganic As ...

Arsenic exposure and type 2 diabetes: results from the 2007-2009 Canadian Health Measures Survey.

PubMed

Feseke, S K; St-Laurent, J; Anassour-Sidi, E; Ayotte, P; Bouchard, M; Levallois, P

2015-06-01

Inorganic arsenic and its metabolites are considered dangerous to human health. Although several studies have reported associations between low-level arsenic exposure and diabetes mellitus in the United States and Mexico, this association has not been studied in the Canadian population. We evaluated the association between arsenic exposure, as measured by total arsenic concentration in urine, and the prevalence of type 2 diabetes (T2D) in 3151 adult participants in Cycle 1 (2007-2009) of the Canadian Health Measures Survey (CHMS). All participants were tested to determine blood glucose and glycated hemoglobin. Urine analysis was also performed to measure total arsenic. In addition, participants answered a detailed questionnaire about their lifestyle and medical history. We assessed the association between urinary arsenic levels and T2D and prediabetes using multivariate logistic regression while adjusting for potential confounders. Total urinary arsenic concentration was positively associated with the prevalence of T2D and prediabetes: adjusted odds ratios were 1.81 (95% CI: 1.12-2.95) and 2.04 (95% CI: 1.03-4.05), respectively, when comparing the highest (fourth) urinary arsenic concentration quartile with the lowest (first) quartile. Total urinary arsenic was also associated with glycated hemoglobin levels in people with untreated diabetes. We found significant associations between arsenic exposure and the prevalence of T2D and prediabetes in the Canadian population. Causal inference is limited due to the cross-sectional design of the study and the absence of long-term exposure assessment.

In utero and early childhood exposure to arsenic decreases lung function in children

PubMed Central

Recio-Vega, Rogelio; Gonzalez-Cortes, Tania; Olivas-Calderon, Edgar; Lantz, R. Clark; Gandolfi, A. Jay; Gonzalez-De Alba, Cesar

2016-01-01

Background The lung is a target organ for adverse health outcomes following exposure to arsenic. Several studies have reported a high prevalence of respiratory symptoms and diseases in subjects highly exposed to arsenic through drinking water, however, most studies to date has been performed in exposed adults, with little information on respiratory effects in children. The objective of the study was to evaluate the association between urinary levels of arsenic and its metabolites with lung function in children exposed in utero and in early childhood to high arsenic levels through drinking water. Methods A total of 358 healthy children were included in our study. Individual exposure was assessed based on urinary concentration of inorganic arsenic. Lung function was assessed by spirometry. Results Participants were exposed since pregnancy until early childhood to an average water As concentration of 152.13 μg/L. The mean urinary arsenic level registered in the studied subjects was 141.2 μg/L and only 16.7% had a urinary concentration below the national concern level. Forced vital capacity was significantly decreased in the studied population and it was negatively associated with the percent of inorganic arsenic. More than 57% of the subjects had a restrictive spirometric pattern. The urinary As level was higher in those children with restrictive lung patterns when compared with the levels registered in subjects with normal spirometric patterns. Conclusion Exposure to arsenic through drinking water during in utero and early life was associated with a decrease in FVC and with a restrictive spirometric pattern in the children evaluated. PMID:25131850

Microbial contributions to coupled arsenic and sulfur cycling in the acid-sulfide hot spring Champagne Pool, New Zealand.

PubMed

Hug, Katrin; Maher, William A; Stott, Matthew B; Krikowa, Frank; Foster, Simon; Moreau, John W

2014-01-01

Acid-sulfide hot springs are analogs of early Earth geothermal systems where microbial metal(loid) resistance likely first evolved. Arsenic is a metalloid enriched in the acid-sulfide hot spring Champagne Pool (Waiotapu, New Zealand). Arsenic speciation in Champagne Pool follows reaction paths not yet fully understood with respect to biotic contributions and coupling to biogeochemical sulfur cycling. Here we present quantitative arsenic speciation from Champagne Pool, finding arsenite dominant in the pool, rim and outflow channel (55-75% total arsenic), and dithio- and trithioarsenates ubiquitously present as 18-25% total arsenic. In the outflow channel, dimethylmonothioarsenate comprised ≤9% total arsenic, while on the outflow terrace thioarsenates were present at 55% total arsenic. We also quantified sulfide, thiosulfate, sulfate and elemental sulfur, finding sulfide and sulfate as major species in the pool and outflow terrace, respectively. Elemental sulfur concentration reached a maximum at the terrace. Phylogenetic analysis of 16S rRNA genes from metagenomic sequencing revealed the dominance of Sulfurihydrogenibium at all sites and an increased archaeal population at the rim and outflow channel. Several phylotypes were found closely related to known sulfur- and sulfide-oxidizers, as well as sulfur- and sulfate-reducers. Bioinformatic analysis revealed genes underpinning sulfur redox transformations, consistent with sulfur speciation data, and illustrating a microbial role in sulfur-dependent transformation of arsenite to thioarsenate. Metagenomic analysis also revealed genes encoding for arsenate reductase at all sites, reflecting the ubiquity of thioarsenate and a need for microbial arsenate resistance despite anoxic conditions. Absence of the arsenite oxidase gene, aio, at all sites suggests prioritization of arsenite detoxification over coupling to energy conservation. Finally, detection of methyl arsenic in the outflow channel, in conjunction with increased sequences from Aquificaceae, supports a role for methyltransferase in thermophilic arsenic resistance. Our study highlights microbial contributions to coupled arsenic and sulfur cycling at Champagne Pool, with implications for understanding the evolution of microbial arsenic resistance in sulfidic geothermal systems.

Multi-trace element levels and arsenic speciation in urine of e-waste recycling workers from Agbogbloshie, Accra in Ghana.

PubMed

Asante, Kwadwo Ansong; Agusa, Tetsuro; Biney, Charles Augustus; Agyekum, William Atuobi; Bello, Mohammed; Otsuka, Masanari; Itai, Takaaki; Takahashi, Shin; Tanabe, Shinsuke

2012-05-01

To understand human contamination by multi-trace elements (TEs) in electrical and electronic waste (e-waste) recycling site at Agbogbloshie, Accra in Ghana, this study analyzed TEs and As speciation in urine of e-waste recycling workers. Concentrations of Fe, Sb, and Pb in urine of e-waste recycling workers were significantly higher than those of reference sites after consideration of interaction by age, indicating that the recycling workers are exposed to these TEs through the recycling activity. Urinary As concentration was relatively high, although the level in drinking water was quite low. Speciation analysis of As in human urine revealed that arsenobetaine and dimethylarsinic acid were the predominant As species and concentrations of both species were positively correlated with total As concentration as well as between each other. These results suggest that such compounds may be derived from the same source, probably fish and shellfish and greatly influence As exposure levels. To our knowledge, this is the first study on human contamination resulting from the primitive recycling of e-waste in Ghana. This study will contribute to the knowledge about human exposure to trace elements from an e-waste site in a less industrialized region so far scantly covered in the literature. Copyright © 2012 Elsevier B.V. All rights reserved.

Sequestration of arsenic in ombrotrophic peatlands

NASA Astrophysics Data System (ADS)

Rothwell, James; Hudson-Edwards, Karen; Taylor, Kevin; Polya, David; Evans, Martin; Allott, Tim

2014-05-01

Peatlands can be important stores of arsenic but we are lacking spectroscopic evidence of the sequestration pathways of this toxic metalloid in peatland environments. This study reports on the solid-phase speciation of anthropogenically-derived arsenic in atmospherically contaminated peat from the Peak District National Park (UK). Surface and sub-surface peat samples were analysed by synchrotron X-ray absorption spectroscopy on B18 beamline at Diamond Light Source (UK). The results suggest that there are contrasting arsenic sequestration mechanisms in the peat. The bulk arsenic speciation results, in combination with strong arsenic-iron correlations at the surface, suggest that iron (hydr)oxides are key phases for the immobilisation of arsenic at the peat surface. In contrast, the deeper peat samples are dominated by arsenic sulphides (arsenopyrite, realgar and orpiment). Given that these peats receive inputs solely from the atmosphere, the presence of these sulphide phases suggests an in-situ authigenic formation. Redox oscillations in the peat due to a fluctuating water table and an abundant store of legacy sulphur from historic acid rain inputs may favour the precipitation of arsenic sequestering sulphides in sub-surface horizons. Oxidation-induced loss of these arsenic sequestering sulphur species by water table drawdown has important implications for the mobility of arsenic and the quality of waters draining peatlands.

Speciation and Localization of Arsenic in White and Brown Rice Grains

DOE Office of Scientific and Technical Information (OSTI.GOV)

Meharg, Andrew A.; Lombi, Enzo; Williams, Paul N.

2008-06-30

Synchrotron-based X-ray fluorescence (S-XRF) was utilized to locate arsenic (As) in polished (white) and unpolished (brown) rice grains from the United States, China, and Bangladesh. In white rice As was generally dispersed throughout the grain, the bulk of which constitutes the endosperm. In brown rice As was found to be preferentially localized at the surface, in the region corresponding to the pericarp and aleurone layer. Copper, iron, manganese, and zinc localization followed that of arsenic in brown rice, while the location for cadmium and nickel was distinctly different, showing relatively even distribution throughout the endosperm. The localization of As inmore » the outer grain of brown rice was confirmed by laser ablation ICP?MS. Arsenic speciation of all grains using spatially resolved X-ray absorption near edge structure (?-XANES) and bulk extraction followed by anion exchange HPLC?ICP?MS revealed the presence of mainly inorganic As and dimethylarsinic acid (DMA). However, the two techniques indicated different proportions of inorganic:organic As species. A wider survey of whole grain speciation of white (n = 39) and brown (n = 45) rice samples from numerous sources (field collected, supermarket survey, and pot trials) showed that brown rice had a higher proportion of inorganic arsenic present than white rice. Furthermore, the percentage of DMA present in the grain increased along with total grain arsenic.« less

Quantitative analysis of arsenic speciation in guano and ornithogenic sediments using microwave-assisted extraction followed by high-performance liquid chromatography coupled to hydride generation atomic fluorescence spectrometry.

PubMed

Lou, Chuangneng; Liu, Wenqi; Liu, Xiaodong

2014-10-15

Seabird guano is one of the main sources of nutrient fertilizers in remote coastal island areas, but guano-derived contaminants such as arsenic may cause serious threats to local ecosystems and public health issues. In this study, a new method was developed to analyze arsenic speciation in guano and ornithogenic sediments. Good extraction efficiencies of As(III) (arsenite), DMA (dimethylarsinate), MMA (monomethylarsonate) and As(V) (arsenate) were obtained by using 1.0molL(-1) orthophosphoric acid and 0.1molL(-1) ascorbic acid, followed by microwave-assisted extraction and high-performance liquid chromatography coupled to hydride generation atomic fluorescence spectrometry (HPLC-HG-AFS) detection. Under the optimized conditions, the extraction efficiencies of four arsenic species were over 80%. The relative standard deviations (RSDs) were 9.60, 6.15, 6.34 and 2.93% (n=7), and the detection limits (μgL(-1)) were 0.82, 2.38, 1.45 and 2.31 for As(III), DMA, MMA and As(V), respectively. This method was successfully used to determine arsenic speciation in the guano samples collected from the Xisha Islands of the South China Sea, and the results indicated that As(III) and As(V) were the dominant arsenic species in modern and ancient guano, respectively. Copyright © 2014 Elsevier B.V. All rights reserved.

[Study on arsenic speciation changes in crude and processed traditional Chinese medicines by HPLC-ICP-MS].

PubMed

Jin, Peng-fei; Wu, Xue-jun; Zou, Ding; Kuang, Yong-mei; Hu, Xin; Jiang, Wen-qing; Sun, Chun-hua

2011-03-01

A HPLC-ICP-MS method for simultaneous determination of As(III), As(V), MMA and DMA in traditional Chinese medicines (TCMs) was established, and the contents of As(III), As(V), MMA and DMA in a TCM with high total arsenic content (Cordyceps) and 5 crude and processed TCMs (Radix Astragali, Radix et Rhizoma Rhei, Radix Scutellariae, Radix Polygoni Multiflori and Radix Rehmanniae) were determined and analyzed. The method validation indicated that the correlative coefficients (r) for all speciations were bigger than 0.9984; the limits of quantitation (LOQ) were from 0.8 to 1.0 microg x L(-1); the reproducibility and stability were satisfactory with all RSDs less than 10%; the spiked recoveries ranged from 82.40% to 119.5%. The results of samples analysis showed that the inorganic arsenic (As(III) and As(V)) was the dominating speciation in the tested TCMs; MMA and DMA were not found in all plant resourced TCMs, but MMA was found in Cordyceps; all the tested TCMs indicated a content increasing of inorganic arsenic after processing.

Effects of biological and behavioral factors on urinary arsenic metabolic profiles in a U.S. population

EPA Science Inventory

Abstract In older men and women who were long-term residents of Churchill County, Nevada, we examined the relation between arsenic exposure from home tap water and urinary levels of inorganic arsenic and its methylated metabolites. Over a wide exposure range (up to 1850 ug of a...

Arsenic Speciation of Waters from the Aegean Region, Turkey by Hydride Generation: Atomic Absorption Spectrometry.

PubMed

Çiftçi, Tülin Deniz; Henden, Emur

2016-08-01

Arsenic in drinking water is a serious problem for human health. Since the toxicity of arsenic species As(III) and As(V) is different, it is important to determine the concentrations separately. Therefore, it is necessary to develop an accurate and sensitive method for the speciation of arsenic. It was intended with this work to determine the concentrations of arsenic species in water samples collected from Izmir, Manisa and nearby areas. A batch type hydride generation atomic absorption spectrometer was used. As(V) gave no signal under the optimal measurement conditions of As(III). A certified reference drinking water was analyzed by the method and the results showed excellent agreement with the reported values. The procedure was applied to 34 water samples. Eleven tap water, two spring water, 19 artesian well water and two thermal water samples were analyzed under the optimal conditions.

Urinary arsenic species, toenail arsenic, and arsenic intake estimates in a Michigan population with low levels of arsenic in drinking water.

PubMed

Rivera-Núñez, Zorimar; Meliker, Jaymie R; Meeker, John D; Slotnick, Melissa J; Nriagu, Jerome O

2012-01-01

The large disparity between arsenic concentrations in drinking water and urine remains unexplained. This study aims to evaluate predictors of urinary arsenic in a population exposed to low concentrations (≤50 μg/l) of arsenic in drinking water. Urine and drinking water samples were collected from a subsample (n=343) of a population enrolled in a bladder cancer case-control study in southeastern Michigan. Total arsenic in water and arsenic species in urine were determined using ICP-MS: arsenobetaine (AsB), arsenite (As[III]), arsenate (As[V]), methylarsenic acid (MMA[V]), and dimethylarsenic acid (DMA[V]). The sum of As[III], As[V], MMA[V], and DMA[V] was denoted as SumAs. Dietary information was obtained through a self-reported food intake questionnaire. Log(10)-transformed drinking water arsenic concentration at home was a significant (P<0.0001) predictor of SumAs (R(2)=0.18). Associations improved (R(2)=0.29, P<0.0001) when individuals with less than 1 μg/l of arsenic in drinking water were removed and further improved when analyses were applied to individuals who consumed amounts of home drinking water above the median volume (R(2)=0.40, P<0.0001). A separate analysis indicated that AsB and DMA[V] were significantly correlated with fish and shellfish consumption, which may suggest that seafood intake influences DMA[V] excretion. The Spearman correlation between arsenic concentration in toenails and SumAs was 0.36 and between arsenic concentration in toenails and arsenic concentration in water was 0.42. Results show that arsenic exposure from drinking water consumption is an important determinant of urinary arsenic concentrations, even in a population exposed to relatively low levels of arsenic in drinking water, and suggest that seafood intake may influence urinary DMA[V] concentrations.

An investigation of the health effects caused by exposure to arsenic from drinking water and coal combustion: arsenic exposure and metabolism.

PubMed

Wei, Binggan; Yu, Jiangping; Kong, Chang; Li, Hairong; Yang, Linsheng; Guo, Zhiwei; Cui, Na; Xia, Yajuan; Wu, Kegong

2017-11-01

Few studies have been conducted to compare arsenic exposure, metabolism, and methylation in populations exposed to arsenic in drinking water and from coal combustion. Therefore, arsenic concentrations in the environment and arsenic speciation in the urine of subjects exposed to arsenic as a consequence of coal combustion in a rural area in Shaanxi province (CCA) and in drinking water in a rural area in Inner Mongolia (DWA) were investigated. The mean arsenic concentrations in drinking water, indoor air, and soil in CCA were 4.52 μg/L, 0.03 mg/m 3 , and 14.93 mg/kg, respectively. The mean arsenic concentrations in drinking water and soil in DWA were 144.71 μg/L and 10.19 mg/kg, respectively, while the level in indoor air was lower than the limit of detection. The total daily intakes of arsenic in DWA and CCA were 4.47 and 3.13 μg/day·kg, respectively. The mean urinary concentrations of inorganic arsenic (iAs), monomethylarsonic acid (MMA), dimethylarsenic acid (DMA), and total arsenic (TAs) for subjects with skin lesions in DWA were 50.41, 47.01, 202.66, and 300.08 μg/L. The concentrations for subjects without skin lesions were 49.76, 44.20, 195.60, and 289.56 μg/L, respectively. The %iAs, %MMA, and %DMA in the TAs in the urine of subjects from CCA were 12.24, 14.73, and 73.03%, while the corresponding values from DWA were 17.54, 15.57, and 66.89%, respectively. The subjects in DWA typically had a higher %iAs and %MMA, and a lower %DMA, and primary and secondary methylation index (PMI and SMI) than the subjects in CCA. It was concluded that the arsenic methylation efficiency of subjects in DWA and CCA was significantly influenced by chronic exposure to high levels of arsenic in the environment. The lower PMI and SMI values in DWA revealed lower arsenic methylation capacity due to ingestion of arsenic in drinking water. However, it remained unclear if the differences in arsenic metabolism between the two groups were due to differences in exposure levels or in exposure route.

SPECIATION OF ARSENIC IN DIETARY AND DIETARY COMPOSITE SAMPLES TO PROVIDE A MORE COMPLETE ASSESSMENT OF ARSENIC EXPOSURE FROM DIETARY SOURCES

EPA Science Inventory

The FDA's market basket study reports total arsenic concentrations from composite diet samples. The use of composite diets, based on market basket sampling, is the most cost effective means of obtaining a generic arsenic exposure estimate for a population. For example, the tota...

Speciation of the Bioaccessible Fraction of Arsenic in Rice using IC-ICP-MS

EPA Science Inventory

Dietary arsenic exposure occurs mainly through drinking water and food; therefore, both aspects should be incorporated into any aggregate exposure assessment. Drinking water exposures are predominantly inorganic arsenic (AsIng) while dietary exposures are made up of a diverse se...

SPECIATION OF ARSENIC IN TARGET FOODS AND COMPOSITE DIET SAMPLES

EPA Science Inventory

For the general population, food may surpass drinking water as the major source of ingestion of total elemental arsenic. Accurate assessments of inorganic arsenic intake via food are needed to understand the relative contributions of drinking water and foods to human exposures t...

Occurrence of inorganic arsenic in edible Shiitake (Lentinula edodes) products.

PubMed

Llorente-Mirandes, Toni; Barbero, Mercedes; Rubio, Roser; López-Sánchez, José Fermín

2014-09-01

The present study reports arsenic speciation analysis in edible Shiitake (Lentinula edodes) products. The study focused on the extraction, and accurate quantification of inorganic arsenic (iAs), the most toxic form of arsenic, which was selectively separated and determined using anion exchange LC-ICPMS. A wide variety of edible Shiitake products (fresh mushrooms, food supplements, canned and dehydrated) were purchased and analysed. A cultivated Shiitake grown under controlled conditions was also analysed. The extraction method showed satisfactory extraction efficiencies (>90%) and column recoveries (>85%) for all samples. Arsenic speciation revealed that iAs was the major As compound up to 1.38 mg As kg(-1) dm (with a mean percentage of 84% of the total arsenic) and other organoarsenicals were found as minor species. Shiitake products had high proportions of iAs and therefore should not be ignored as potential contributors to dietary iAs exposure in populations with a high intake of Shiitake products. Copyright © 2014 Elsevier Ltd. All rights reserved.

Bioaccumulation and biotransformation of arsenic compounds in Hediste diversicolor (Muller 1776) after exposure to spiked sediments.

PubMed

Gaion, Andrea; Sartori, Davide; Scuderi, Alice; Fattorini, Daniele

2014-05-01

This study focused on the exposure of the common ragworm Hediste diversicolor (Müller 1776) to sediments enriched with different arsenic compounds, namely arsenate, dimethyl-arsinate, and arsenobetaine. Speciation analysis was carried out on both the spiked sediments and the exposed polychaetes in order to investigate H. diversicolor capability of arsenic bioaccumulation and biotransformation. Two levels of contamination (acute and moderate dose) were chosen for enriched sediments to investigate possible differences in the arsenic bioaccumulation patterns. The highest value of arsenic in tissues was reached after 15 days of exposure to dimethyl-arsinate (acute dose) spiked sediment (1,172 ± 176 μg/g). A significant increase was also obtained in worms exposed both to arsenate and arsenobetaine. Speciation analysis showed that trimethyl-arsine oxide was the predominant chemical form in tissues of H. diversicolor exposed to all the spiked sediments, confirming the importance of this intermediate in biological transformation of arsenic.

Association of cadmium and arsenic exposure with salivary telomere length in adolescents in Terai, Nepal

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fillman, Toki, E-mail: tokif@humeco.m.u-tokyo.ac.jp; Shimizu-Furusawa, Hana, E-mail: hana-shimizu@umin.ac.jp; Ng, Chris Fook Sheng, E-mail: chrisng-tky@umin.ac.jp

Background: Cadmium and arsenic are ubiquitous metals commonly found in the environment which can harm human health. A growing body of research shows telomere length as a potential biomarker of future disease risk. Few studies have examined the effects of metals on telomere length and none have focused on adolescents. Objectives: In this study, the impact of cadmium and arsenic on salivary telomere length was studied in adolescents in Terai, Nepal. Methods: Adolescents aged 12–16 years old (n=351)were recruited where questionnaire interviews and both saliva and urine collection took place. Telomere length was determined by quantitative polymerase chain reaction usingmore » DNA extracted from saliva. Urinary cadmium and arsenic concentration were measured by inductively coupled plasma mass spectrometry. Multivariable linear regression was used to examine associations between urinary metals and salivary telomere length. Results: The geometric means and standard deviations of cadmium and arsenic were 0.33±0.33 μg/g creatinine and 196.0±301.1 μg/g creatinine, respectively. Urinary cadmium concentration was negatively associated with salivary telomere length after adjustment for confounders (β=−0.24, 95% CI −0.42,−0.07). Arsenic showed positive associations with telomere length but did not reach statistical significance. Conclusions: This is the first study to demonstrate that cadmium may shorten adolescent telomeres, even at exposure levels that may be considered low. These results agree with prior experimental and adult epidemiological studies, and also help identify the mechanism of DNA damage by cadmium. This study expanded current evidence on the harmful effects of cadmium exposure on telomere length even to adolescents. - Highlights: • This is the first study examining metal exposure on telomere length in adolescents. • Urinary cadmium levels were similar to non-industrially polluted levels in Asia. • Urinary arsenic levels were as high as groundwater arsenic polluted areas in Asia. • Urinary cadmium was negatively associated with salivary telomere length. • Urinary arsenic was not significantly associated with salivary telomere length.« less

A Population-based Case–Control Study of Urinary Arsenic Species and Squamous Cell Carcinoma in New Hampshire, USA

PubMed Central

Li, Zhigang; Perry, Ann E.; Spencer, Steven K.; Gandolfi, A. Jay; Karagas, Margaret R.

2013-01-01

Background: Chronic high arsenic exposure is associated with squamous cell carcinoma (SCC) of the skin, and inorganic arsenic (iAs) metabolites may play an important role in this association. However, little is known about the carcinogenicity of arsenic at levels commonly observed in the United States. Objective: We estimated associations between total urinary arsenic and arsenic species and SCC in a U.S. population. Methods: We conducted a population-based case–control SCC study (470 cases, 447 controls) in a U.S. region with moderate arsenic exposure through private well water and diet. We measured urinary iAs, monomethylarsonic acid (MMA), and dimethylarsinic acid (DMA), and summed these arsenic species (ΣAs). Because seafood contains arsenolipids and arsenosugars that metabolize into DMA through alternate pathways, participants who reported seafood consumption within 2 days before urine collection were excluded from the analyses. Results: In adjusted logistic regression analyses (323 cases, 319 controls), the SCC odds ratio (OR) was 1.37 for each ln-transformed microgram per liter increase in ln-transformed ΣAs concentration [ln(ΣAs)] (95% CI: 1.04, 1.80). Urinary ln(MMA) and ln(DMA) also were positively associated with SCC (OR = 1.34; 95% CI: 1.04, 1.71 and OR = 1.34; 95% CI: 1.03, 1.74, respectively). A similar trend was observed for ln(iAs) (OR = 1.20; 95% CI: 0.97, 1.49). Percent iAs, MMA, and DMA were not associated with SCC. Conclusions: These results suggest that arsenic exposure at levels common in the United States relates to SCC and that arsenic metabolism ability does not modify the association. Citation: Gilbert-Diamond D, Li Z, Perry AE, Spencer SK, Gandolfi AJ, Karagas MR. 2013. A population-based case–control study of urinary arsenic species and squamous cell carcinoma in New Hampshire, USA. Environ Health Perspect 121:1154–1160; http://dx.doi.org/10.1289/ehp.1206178 PMID:23872349

Fetal-sex dependent genomic responses in the circulating lymphocytes of arsenic-exposed pregnant women in New Hampshire.

PubMed

Bommarito, Paige A; Martin, Elizabeth; Smeester, Lisa; Palys, Thomas; Baker, Emily R; Karagas, Margaret R; Fry, Rebecca C

2017-10-01

Exposure to inorganic arsenic (iAs) during pregnancy is associated with adverse health outcomes present both at birth and later in life. A biological mechanism may include epigenetic and genomic alterations in fetal genes involved in immune functioning. To investigate the role of the maternal immune response to in utero iAs exposure, we conducted an analysis of the expression of immune-related genes in pregnant women from the New Hampshire Birth Cohort Study. A set of 31 genes was identified with altered expression in association with levels of urinary total arsenic, urinary iAs, urinary monomethylated arsenic and urinary dimethylated arsenic. Notably, maternal gene expression signatures differed when stratified on fetal sex, with a more robust inflammatory response observed in male pregnancies. Moreover, the differentially expressed genes were also related to birth outcomes. These findings highlight the sex-dependent nature of the maternal iAs-induced inflammatory response in relationship to fetal outcomes. Copyright © 2017. Published by Elsevier Inc.

A comparison of the determination and speciation of inorganic arsenic using general HPLC methodology with UV, MS and MS/MS detection.

PubMed

Gilmartin, Gregory; Gingrich, Diane

2018-04-15

The determination and speciation of arsenic in natural resources such as drinking water and agricultural soils has been a growing concern in recent years due to its many toxicological effects [1-3]. To speciate and quantitate concentrations of <1 ppm of arsenic, typically an ion chromatograph (IC) interfaced to an inductively coupled plasma mass spectrometer (ICP-MS) is employed [4-9]. This methodology may be very robust and sensitive, but it is expensive and not as ubiquitous as high performance liquid chromatography (HPLC) with ultraviolet (UV) absorbance detection or electrospray ionization mass spectrometry (ESI-MS). Anion exchange chromatography is a well-documented means of speciating arsenite (As(III), As 2 O 3 ) and arsenate (As(V), AsO 4 ) using UV [10], conductivity [11], or ESI-MS detection [12,13]. This paper demonstrates the utilization of common liquid chromatographic instrumentation to speciate and determines inorganic Arsenic compounds using UV or MS via selected ion recording (SIR) or multiple reaction monitoring (MRM) detection. This paper describes the analysis of arsenite and arsenate samples prepared using both deionized and ground water. The limit of quantitation for the techniques described in this paper for samples spiked in ground water were 454 ppb (As(III)) and 562 ppb (As(V)) for UV detection, 45.4 ppb (As(III)) and 56.2 ppb (As(V)) for SIR detection, and 4.54 ppb (As(III)) and 5.62 ppb (As(V)) for MRM detection. Copyright © 2018 Elsevier B.V. All rights reserved.

Severe systemic toxicity and urinary bladder cytotoxicity and regenerative hyperplasia induced by arsenite in arsenic (+3 oxidation state) methyltransferase knockout mice. A preliminary report

EPA Science Inventory

Arsenic (+3 oxidation state) methyltransferase (As3mt) catalyzes reactions which convert inorganic arsenic to methylated metabolites. This study determined whether the As3mt null genotype in the mouse modifies cytotoxic and proliferative effects seen in urinary bladders of wild t...

A review on environmental factors regulating arsenic methylation in humans.

PubMed

Tseng, Chin-Hsiao

2009-03-15

Subjects exposed to arsenic show significant inter-individual variation in urinary patterns of arsenic metabolites but insignificant day-to-day intra-individual variation. The inter-individual variation in arsenic methylation can be partly responsible for the variation in susceptibility to arsenic toxicity. Wide inter-ethnic variation and family correlation in urinary arsenic profile suggest a genetic effect on arsenic metabolism. In this paper the environmental factors affecting arsenic metabolism are reviewed. Methylation capacity might reduce with increasing dosage of arsenic exposure. Furthermore, women, especially at pregnancy, have better methylation capacity than their men counterparts, probably due to the effect of estrogen. Children might have better methylation capacity than adults and age shows inconsistent relevance in adults. Smoking and alcohol consumption might be associated with a poorer methylation capacity. Nutritional status is important in the methylation capacity and folate may facilitate the methylation and excretion of arsenic. Besides, general health conditions and medications might influence the arsenic methylation capacity; and technical problems can cause biased estimates. The consumption of seafood, seaweed, rice and other food with high arsenic contents and the extent of cooking and arsenic-containing water used in food preparation may also interfere with the presentation of the urinary arsenic profile. Future studies are necessary to clarify the effects of the various arsenic metabolites including the trivalent methylated forms on the development of arsenic-induced human diseases with the consideration of the effects of confounding factors and the interactions with other effect modifiers.

MINERALOGY AND CHARACTERIZATION OF ARSENIC, IRON, AND LEAD IN A MINE WASTE-DERIVED FERTILIZER

EPA Science Inventory

The solid-state speciation of arsenic (As), iron (Fe), and lead (Pb) was studied in the mine waste-derived fertilizer Ironite using X-ray absorption spectroscopy, Mössbauer spectroscopy, and aging studies. Arsenic was primarily associated with ferrihydrite (60-70%) with the rema...

Assessing the Selectivity of Extractant Solutions for Recovering Labile Arsenic Associated with Iron (Hydr)oxides and Sulfides in Sediments

EPA Science Inventory

Sequential extractions can provide analytical constraints on the identification of mineral phases that control arsenic speciation in sediments. Model solids were used in this study to evaluate different solutions designed to extract arsenic from relatively labile solid phases. ...

SPECIATION OF ARSENIC IN BIOLOGICAL MATRICES BY AUTOMATED HG-AAS WITH MULTIPLE MICROFLAME QUARTZ TUBE ATOMIZER (MULTIATOMIZER)

EPA Science Inventory

Analyses of arsenic (As) species in body fluids and tissues of individuals chronically exposed to inorganic arsenic (iAs) provide essential information about the exposure level and pattern of iAs metabolism. This information facilitates the risk assessment of disorders associated...

BIOGEOCHEMICAL PROCESSES CONTROLLING ARSENIC SPECIATION AND BIOTRANSFORMATION IN GRANULAR FERRIC HYDROXIDE COATED SAND

EPA Science Inventory

Arsenic mobilization from solid phase Fe (III) hydroxides is an issue of concern, as water-borne arsenic can migrate into pristine environments, endangering aquatic and human life. In general, metal oxide (hydroxides) exerts a dominating effect on the fate and transport of arseni...

COMPLEMENTARY APPROACHES TO THE DETERMINATION OF ARSENIC SPECIES RELEVANT TO CONCENTRATED ANIMAL FEEDING OPERATIONS

EPA Science Inventory

Ion-exchange chromatography is the most often used analytical approach for arsenic

speciation, due to the weak-acid nature of several of its species. However, no single

technique can determine all potentially occurring arsenic species, especially in complex

e...

SPATIAL AND TEMPORAL DYNAMICS IN ARSENIC SPECIATION ACROSS THE GROUND WATER-SURFACE WATER TRANSITION ZONE AT A CONTAMINATED SITE

EPA Science Inventory

Field investigations have been conducted to understand the fate of arsenic in contaminated ground water during discharge into a small lake. The ground-water plume contains elevated levels of arsenic and hydrocarbon contaminants derived from historical disposal of process wastes ...

ARSENIC SPECIATION IN PROBLEMATIC SEAFOOD MATRICES: THE IMPORTANCE OF A SPECIES SPECIFIC MASS BALANCE

EPA Science Inventory

Arsenic has two major exposure routes: dietary and drinking water ingestion. Dietary exposures can easily exceed those typically associated with drinking water but the risk associated with these exposures is strongly influenced by the toxicity of the arsenicals present in the s...

ARSENIC SPECIATION ANALYSIS IN GROUND WATER BY IC-HG-AFS

EPA Science Inventory

The determination of low levels of arsenic draws concern more than ever today, because of the possible legislative changes in the drinking water limit. The toxicity of arsenic depends upon its chemical form. Arsenite is the most toxic form, 25 to 50 times more toxic than arsena...

DETECTION OF ARSENOSUGARS FROM KELP EXTRACTS VIA IC-ELECTROSPRAY IONIZATION-MS-MS AND IC MEMBRANE HYDRIDE GENERATION ICP-MS

EPA Science Inventory

The selectivity and the ability to obtain structural information from detection schemes used in arsenic speciation research are growing analytical requirements driven by the growing number of arsenicalS extracted from natural products and the need to minimize misidentification in...

Speciated arsenic in air: measurement methodology and risk assessment considerations.

PubMed

Lewis, Ari S; Reid, Kim R; Pollock, Margaret C; Campleman, Sharan L

2012-01-01

Accurate measurement of arsenic (As) in air is critical to providing a more robust understanding of arsenic exposures and associated human health risks. Although there is extensive information available on total arsenic in air, less is known on the relative contribution of each arsenic species. To address this data gap, the authors conducted an in-depth review of available information on speciated arsenic in air. The evaluation included the type of species measured and the relative abundance, as well as an analysis of the limitations of current analytical methods. Despite inherent differences in the procedures, most techniques effectively separated arsenic species in the air samples. Common analytical techniques such as inductively coupled plasma mass spectrometry (ICP-MS) and/or hydride generation (HG)- or quartz furnace (GF)-atomic absorption spectrometry (AAS) were used for arsenic measurement in the extracts, and provided some of the most sensitive detection limits. The current analysis demonstrated that, despite limited comparability among studies due to differences in seasonal factors, study duration, sample collection methods, and analytical methods, research conducted to date is adequate to show that arsenic in air is mainly in the inorganic form. Reported average concentrations of As(III) and As(V) ranged up to 7.4 and 10.4 ng/m3, respectively, with As(V) being more prevalent than As(III) in most studies. Concentrations of the organic methylated arsenic compounds are negligible (in the pg/m3 range). However because of the variability in study methods and measurement methodology, the authors were unable to determine the variation in arsenic composition as a function of source or particulate matter (PM) fraction. In this work, the authors include the implications of arsenic speciation in air on potential exposure and risks. The authors conclude that it is important to synchronize sample collection, preparation, and analytical techniques in order to generate data more useful for arsenic inhalation risk assessment, and a more robust documentation of quality assurance/quality control (QA/QC) protocols is necessary to ensure accuracy, precision, representativeness, and comparability.

Arsenic Exposure in Relation to Ischemic Stroke: The Reasons for Geographic and Racial Differences in Stroke Study.

PubMed

Tsinovoi, Cari L; Xun, Pengcheng; McClure, Leslie A; Carioni, Vivian M O; Brockman, John D; Cai, Jianwen; Guallar, Eliseo; Cushman, Mary; Unverzagt, Frederick W; Howard, Virginia J; He, Ka

2018-01-01

The purpose of this case-cohort study was to examine urinary arsenic levels in relation to incident ischemic stroke in the United States. We performed a case-cohort study nested within the REGARDS (REasons for Geographic and Racial Differences in Stroke) cohort. A subcohort (n=2486) of controls was randomly sampled within region-race-sex strata while all incident ischemic stroke cases from the full REGARDS cohort (n=671) were included. Baseline urinary arsenic was measured by inductively coupled plasma-mass spectrometry. Arsenic species, including urinary inorganic arsenic and its metabolites monomethylarsonic acid and dimethylarsinic acid, were measured in a random subset (n=199). Weighted Cox's proportional hazards models were used to calculate hazard ratios and 95% confidence intervals of ischemic stroke by arsenic and its species. The average follow-up was 6.7 years. Although incident ischemic stroke showed no association with total arsenic or total inorganic arsenic, for each unit higher level of urinary monomethylarsonic acid on a log-scale, after adjustment for potential confounders, ischemic stroke risk increased ≈2-fold (hazard ratio=1.98; 95% confidence interval: 1.12-3.50). Effect modification by age, race, sex, or geographic region was not evident. A metabolite of arsenic was positively associated with incident ischemic stroke in this case-cohort study of the US general population, a low-to-moderate exposure area. Overall, these findings suggest a potential role for arsenic methylation in the pathogenesis of stroke, having important implications for future cerebrovascular research. © 2017 American Heart Association, Inc.

Arsenate and dimethylarsinic acid in drinking water did not affect DNA damage repair in urinary bladder transitional cells or micronuclei in bone marrow

EPA Science Inventory

Arsenic is a recognized human skin, lung, and urinary bladder carcinogen, and may act as a cocarcinogen in the urinary bladder (with cigarette smoking) and skin (with UV light exposure). Possible modes of action of arsenic carcinogenesis/cocarcinogenesis include induction of DNA ...

Sample preparation for arsenic speciation analysis in baby food by generation of substituted arsines with atomic absorption spectrometry detection.

PubMed

Huber, Charles S; Vale, Maria Goreti R; Dessuy, Morgana B; Svoboda, Milan; Musil, Stanislav; Dědina, Jiři

2017-12-01

A slurry sampling procedure for arsenic speciation analysis in baby food by arsane generation, cryogenic trapping and detection with atomic absorption spectrometry is presented. Several procedures were tested for slurry preparation, including different reagents (HNO 3 , HCl and tetramethylammonium hydroxide - TMAH) and their concentrations, water bath heating and ultrasound-assisted agitation. The best results for inorganic arsenic (iAs) and dimethylarsinate (DMA) were reached when using 3molL -1 HCl under heating and ultrasound-assisted agitation. The developed method was applied for the analysis of five porridge powder and six baby meal samples. The trueness of the method was checked with a certified reference material (CRM) of total arsenic (tAs), iAs and DMA in rice (ERM-BC211). Arsenic recoveries (mass balance) for all samples and CRM were performed by the determination of the tAs by inductively coupled plasma mass spectrometry (ICP-MS) after microwave-assisted digestion and its comparison against the sum of the results from the speciation analysis. The relative limits of detection were 0.44, 0.24 and 0.16µgkg -1 for iAs, methylarsonate and DMA, respectively. The concentrations of the most toxic arsenic species (iAs) in the analyzed baby food samples ranged between 4.2 and 99µgkg -1 which were below the limits of 300, 200 and 100µgkg -1 set by the Brazilian, Chinese and European legislation, respectively. Copyright © 2017 Elsevier B.V. All rights reserved.

Application of Hyphenated Techniques in Speciation Analysis of Arsenic, Antimony, and Thallium

PubMed Central

Michalski, Rajmund; Szopa, Sebastian; Jabłońska, Magdalena; Łyko, Aleksandra

2012-01-01

Due to the fact that metals and metalloids have a strong impact on the environment, the methods of their determination and speciation have received special attention in recent years. Arsenic, antimony, and thallium are important examples of such toxic elements. Their speciation is especially important in the environmental and biomedical fields because of their toxicity, bioavailability, and reactivity. Recently, speciation analytics has been playing a unique role in the studies of biogeochemical cycles of chemical compounds, determination of toxicity and ecotoxicity of selected elements, quality control of food products, control of medicines and pharmaceutical products, technological process control, research on the impact of technological installation on the environment, examination of occupational exposure, and clinical analysis. Conventional methods are usually labor intensive, time consuming, and susceptible to interferences. The hyphenated techniques, in which separation method is coupled with multidimensional detectors, have become useful alternatives. The main advantages of those techniques consist in extremely low detection and quantification limits, insignificant interference, influence as well as high precision and repeatability of the determinations. In view of their importance, the present work overviews and discusses different hyphenated techniques used for arsenic, antimony, and thallium species analysis, in different clinical, environmental and food matrices. PMID:22654649

Speciation of arsenic in marine food (Anemonia sulcata) by liquid chromatography coupled to inductively coupled plasma mass spectrometry and organic mass spectrometry.

PubMed

Contreras-Acuña, M; García-Barrera, T; García-Sevillano, M A; Gómez-Ariza, J L

2013-03-22

Arsenic species have been investigated in Anemonia sulcata, which is frequently consumed food staple in Spain battered in wheat flour and fried with olive oil. Speciation in tissue extracts was carried out by anion/cation exchange chromatography with inductively coupled plasma mass spectrometry (HPLC-(AEC/CEC)-ICP-MS). Three methods for the extraction of arsenic species were investigated (ultrasonic bath, ultrasonic probe and focused microwave) and the optimal one was applied. Arsenic speciation was carried out in raw and cooked anemone and the dominant species are dimethylarsinic acid (DMA(V)) followed by arsenobetaine (AB), As(V), monomethylarsonic acid (MA(V)), tetramethylarsonium ion (TETRA) and trimethylarsine oxide (TMAO). In addition, arsenocholine (AsC), glyceryl phosphorylarsenocholine (GPAsC) and dimethylarsinothioic acid (DMAS) were identified by liquid chromatography coupled to triple quadrupole mass spectrometry (HPLC-MS). These results are interesting since GPAsC has been previously reported in marine organisms after experimental exposure to AsC, but not in natural samples. In addition, this paper reports for the first time the identification of DMAS in marine food. Copyright © 2013 Elsevier B.V. All rights reserved.

Concentrations of urinary arsenic species in relation to rice and seafood consumption among children living in Spain.

PubMed

Signes-Pastor, Antonio J; Vioque, Jesus; Navarrete-Muñoz, Eva M; Carey, Manus; García de la Hera, Manoli; Sunyer, Jordi; Casas, Maribel; Riaño-Galán, Isolina; Tardón, Adonina; Llop, Sabrina; Amorós, Rubén; Amiano, Pilar; Bilbao, José R; Karagas, Margaret R; Meharg, Andrew A

2017-11-01

Inorganic arsenic (i-As) has been related to wide-ranging health effects in children, leading to lifelong concerns. Proportionally, dietary i-As exposure dominates in regions with low arsenic drinking water. This study aims to investigate the relation between rice and seafood consumption and urinary arsenic species during childhood and to assess the proportion of urinary i-As metabolites. Urinary arsenic species concentration in 400 4-year-old children living in four geographical areas of Spain, in addition to repeated measures from 100 children at 7 years of age are included in this study. Rice and seafood products intake was collected from children's parents using a validated food frequency questionnaire (FFQ). At 4 years of age, children's urine i-As and monomethylarsonic acid (MMA) concentrations increased with rice product consumption (p-value = 0.010 and 0.018, respectively), and urinary arsenobetaine (AsB) with seafood consumption (p = 0.002). Four-year-old children had a higher consumption of both rice and seafood per body weight and a higher urinary %MMA (p-value = 0.001) and lower % dimethylarsinic acid (DMA) (p-value = 0.017). This study suggests increased dietary i-As exposure related to rice product consumption among children living in Spain, and the younger ones may be especially vulnerable to the health impacts of this exposure also considering that they might have a lower i-As methylation capacity than older children. In contrast, seafood consumption did not appear to influence the presence of potentially toxic arsenic species in this population of children. Copyright © 2017 Elsevier Inc. All rights reserved.

Arsenic exposure and oral cavity lesions in Bangladesh.

PubMed

Syed, Emdadul H; Melkonian, Stephanie; Poudel, Krishna C; Yasuoka, Junko; Otsuka, Keiko; Ahmed, Alauddin; Islam, Tariqul; Parvez, Faruque; Slavkovich, Vesna; Graziano, Joseph H; Ahsan, Habibul; Jimba, Masamine

2013-01-01

To evaluate the relationship between arsenic exposure and oral cavity lesions among an arsenic-exposed population in Bangladesh. We carried out an analysis utilizing the baseline data of the Health Effects of Arsenic Exposure Longitudinal Study, which is an ongoing population-based cohort study to investigate health outcomes associated with arsenic exposure via drinking water in Araihazar, Bangladesh. We used multinomial regression models to estimate the risk of oral cavity lesions. Participants with high urinary arsenic levels (286.1 to 5000.0 μg/g) were more likely to develop arsenical lesions of the gums (multinomial odds ratio = 2.90; 95% confidence interval, 1.11 to 7.54), and tongue (multinomial odds ratio = 2.79; 95% confidence interval, 1.51 to 5.15), compared with those with urinary arsenic levels of 7.0 to 134.0 μg/g. Higher level of arsenic exposure was positively associated with increased arsenical lesions of the gums and tongue.

FY06 ORD PILOT STUDY: DETERMINE BIOAVAILABILITY AND BIOACCESSIBILITY OF ARSENIC IN SOIL AND DEVELOP ARSENIC SPECIATION METHODS

EPA Science Inventory

The product is a presentation requested by the organizers of the 2005 US EPA Bioavailability Technical Review Workgroup. It presents an overview, approaches (in-vivo & in-vitro), and logistics of the ORD pilot study on bioavailability of arsenic in soil. The overall project was ...

Total Arsenic Determination and Speciation in Infant Food Products by Ion Chromatography Inductively Coupled Plasma Mass Spectrometry

EPA Science Inventory

Health risk associated with dietary arsenic intake may be different for infants and adults. Seafood is the main contributor to arsenic intake for adults while terrestrial-based food is the primary source for infants. Processed infant food products such as rice-based cereals, mi...

THE IMPORTANCE OF ARSENIC SPECIES SPECIFIC MASS BALANCE ON THE EVALUATION OF ARSENIC SPECIATION RESULTS IN SEAFOOD MATRICES

EPA Science Inventory

The two predominant pathways to arsenic exposure are drinking water and dietary ingestion. A large percentage of the dietary exposure component is associated with a few food groups. For example, seafood alone represents over 50% of the total dietary exposure. From a daily dose...

Arsenic drinking water exposure and urinary excretion among adults in the Yaqui Valley, Sonora, Mexico.

PubMed

Meza, Maria Mercedes; Kopplin, Michael J; Burgess, Jefferey L; Gandolfi, A Jay

2004-10-01

The objective of this study was to determine arsenic exposure via drinking water and to characterize urinary arsenic excretion among adults in the Yaqui Valley, Sonora, Mexico. A cross-sectional study was conducted from July 2001 to May 2002. Study subjects were from the Yaqui Valley, Sonora, Mexico, residents of four towns with different arsenic concentrations in their drinking water. Arsenic exposure was estimated through water intake over 24 h. Arsenic excretion was assessed in the first morning void urine. Total arsenic concentrations and their species arsenate (As V), arsenite (As III), monomethyl arsenic (MMA), and dimethyl arsenic (DMA) were determined by HPLC/ICP-MS. The town of Esperanza with the highest arsenic concentration in water had the highest daily mean intake of arsenic through drinking water, the mean value was 65.5 microg/day. Positive correlation between total arsenic intake by drinking water/day and the total arsenic concentration in urine (r = 0.50, P < 0.001) was found. Arsenic excreted in urine ranged from 18.9 to 93.8 microg/L. The people from Esperanza had the highest geometric mean value of arsenic in urine, 65.1 microg/L, and it was statistically significantly different from those of the other towns (P < 0.005). DMA was the major arsenic species in urine (47.7-67.1%), followed by inorganic arsenic (16.4-25.4%), and MMA (7.5-15%). In comparison with other reports the DMA and MMA distribution was low, 47.7-55.6% and 7.5-9.7%, respectively, in the urine from the Yaqui Valley population (except the town of Cocorit). The difference in the proportion of urinary arsenic metabolites in those towns may be due to genetic polymorphisms in the As methylating enzymes of these populations.

Combined effects of DNA methyltransferase 1 and 3A polymorphisms and urinary total arsenic levels on the risk for clear cell renal cell carcinoma

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Shu-Mei

Our previous study showed that high urinary total arsenic levels were associated with higher odds ratio (OR) for renal cell carcinoma (RCC). Single nucleotide polymorphisms (SNPs) of DNA methyltransferases (DNMTs) might influence DNMT enzyme activity associated with tumorigenesis. In this study, we investigated the association of five SNPs from DNMT1 (rs8101626 and rs2228611), DNMT3A (rs34048824 and rs1550117), and DNMT3B (rs1569686) with the risk of clear cell renal cell carcinoma (ccRCC). We also examined the combined effects of DNMT genotypes and urinary arsenic levels on ccRCC risk. We conducted a hospital-based case-control study, which included 293 subjects with ccRCC and 293more » age- and gender-matched controls. The urinary arsenic species were determined by a high performance liquid chromatography-linked hydride generator and atomic absorption spectrometry. Genotypes were investigated using polymerase chain reaction and restriction fragment length polymorphism analyses. We observed that the DNMT1 rs8101626 G/G genotype was significantly associated with reduced odds ratio (OR) of ccRCC [OR = 0.38, 95% confidence interval (CI) 0.14–0.99]. Subjects with concurrent DNMT1 rs8101626 A/A + A/G and DNMT3A rs34048824 T/T + T/C genotypes had significantly higher OR for ccRCC [OR = 2.88, 95% CI 1.44–5.77]. Participants with the high-risk genotype of DNMT1 rs8101626 and DNMT3A rs34048824 with concurrently high urinary total arsenic levels had even higher OR of ccRCC in a dose-response manner. This is the first study to evaluate variant DNMT1 rs8101626 and DNMT3A rs34048824 genotypes that modify the arsenic-related ccRCC risk in a geographic area without significant arsenic exposure in Taiwan. - Highlights: • High urinary total arsenic level or polymorphism of DNMT1 increased the OR of ccRCC. • High risk genotypes of combination of DNMT1 and DNMT3A increased the OR of ccRCC. • A joint effect of urinary total arsenic level and DNMTs genotypes may affect ccRCC.« less

Maternal arsenic exposure, arsenic methylation efficiency, and birth outcomes in the Biomarkers of Exposure to ARsenic (BEAR) pregnancy cohort in Mexico.

PubMed

Laine, Jessica E; Bailey, Kathryn A; Rubio-Andrade, Marisela; Olshan, Andrew F; Smeester, Lisa; Drobná, Zuzana; Herring, Amy H; Stýblo, Miroslav; García-Vargas, Gonzalo G; Fry, Rebecca C

2015-02-01

Exposure to inorganic arsenic (iAs) from drinking water is a global public health problem, yet much remains unknown about the extent of exposure in susceptible populations. We aimed to establish the Biomarkers of Exposure to ARsenic (BEAR) prospective pregnancy cohort in Gómez Palacio, Mexico, to better understand the effects of iAs exposure on pregnant women and their children. Two hundred pregnant women were recruited for this study. Concentrations of iAs in drinking water (DW-iAs) and maternal urinary concentrations of iAs and its monomethylated and dimethylated metabolites (MMAs and DMAs, respectively) were determined. Birth outcomes were analyzed for their relationship to DW-iAs and to the concentrations and proportions of maternal urinary arsenicals. DW-iAs for the study subjects ranged from < 0.5 to 236 μg As/L. More than half of the women (53%) had DW-iAs that exceeded the World Health Organization's recommended guideline of 10 μg As/L. DW-iAs was significantly associated with the sum of the urinary arsenicals (U-tAs). Maternal urinary concentrations of MMAs were negatively associated with newborn birth weight and gestational age. Maternal urinary concentrations of iAs were associated with lower mean gestational age and newborn length. Biomonitoring results demonstrate that pregnant women in Gómez Palacio are exposed to potentially harmful levels of DW-iAs. The data support a relationship between iAs metabolism in pregnant women and adverse birth outcomes. The results underscore the risks associated with iAs exposure in vulnerable populations.

Polymorphism of inflammatory genes and arsenic methylation capacity are associated with urothelial carcinoma

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wu, Chia-Chang; Department of Urology, Taipei Medical University—Shuang Ho Hospital, Taipei, Taiwan; Huang, Yung-Kai

2013-10-01

Chronic exposure to arsenic can generate reactive oxidative species, which can induce certain proinflammatory cytokines such as tumor necrosis factor-alpha (TNF-α), interleukin-6 (IL-6) and interleukin-8 (IL-8). TNF-α, IL-6 and IL-8 have been shown to be involved in the development and progression of various cancers, including bladder cancer. This study aimed to investigate the joint effect of the polymorphism of TNF-α − 308 G/A, IL-6 − 174 G/C, IL-8 − 251 T/A and urinary arsenic profiles on urothelial carcinoma (UC) risk. This study evaluated 300 pathologically-confirmed cases of UC and 594 cancer-free controls. Urinary arsenic species were detected using high-performance liquidmore » chromatography-linked hydride generator and atomic absorption spectrometry. The polymorphism of TNF-α − 308 G/A, IL-6 − 174 G/C and IL-8 − 251 T/A was determined using polymerase chain reaction-restriction fragment length polymorphism. The joint effects on UC risk were estimated by odds ratios and 95% confidence intervals using unconditional logistic regression. We found that the TNF-α − 308 A/A and IL-8 − 251 T/T polymorphisms were significantly associated with UC. Moreover, significant dose–response joint effect of TNF-α − 308 A/A or IL-8 − 251 T/T genotypes and arsenic methylation indices were seen to affect UC risk. The present results also showed a significant increase in UC risk in subjects with the IL-8 − 251 T/T genotype for each SD increase in urinary total arsenic and MMA%. In contrast, a significant decrease in UC risk was found in subjects who carried the IL-8 − 251 T/T genotype for each SD increase in DMA%. - Highlights: • Joint effect of the TNF-α -308 A/A genotype and urinary total arsenic affected UC. • Joint effect of the IL-8 -251 T/T genotype and urinary total arsenic affected UC. • Urinary total arsenic level, TNF-α -308 A/A and IL-8 -251 T/T genotype affected UC.« less

Direct comparison of XAFS spectroscopy and sequential extraction for arsenic speciation in coal

USGS Publications Warehouse

Huggins, Frank E.; Huffman, G.P.; Kolker, A.; Mroczkowski, S.; Palmer, C.A.; Finkelman, R.B.

2000-01-01

The speciation of arsenic in an Ohio bituminous coal and a North Dakota lignite has been examined by the complementary methods of arsenic XAFS spectroscopy and sequential extraction by aqueous solutions of ammonium acetate, HCl, HF, and HNO3. In order to facilitate a more direct comparison of the two methods, the arsenic XAFS spectra were obtained from aliquots of the coal prepared after each stage of the leaching procedure. For the aliquots, approximately linear correlations (r2 > 0.98 for the Ohio coal, > 0.90 for the ND lignite) were observed between the height of the edge-step in the XAFS analysis and the concentration of arsenic measured by instrumental neutron activation analysis. Results from the leaching sequence indicate that there are two major arsenic forms present in both coals; one is removed by leaching with HCl and the other by HNO3. Whereas the XAFS spectral signatures of the arsenic leached by HCl are compatible with arsenate for both coals, the arsenic leached by HNO3 is identified as arsenic associated with pyrite for the Ohio coal and as an As3+ species for the North Dakota lignite. Minor arsenate forms persist in both coals after the final leaching with nitric acid. The arsenate forms extracted in HCl are believed to be oxidation products derived from the other major arsenic forms upon exposure of the pulverized coals to air.

A study of method robustness for arsenic speciation in drinking water samples by anion exchange HPLC-ICP-MS.

PubMed

Day, Jason A; Montes-Bayón, María; Vonderheide, Anne P; Caruso, Joseph A

2002-08-01

Regulating arsenic species in drinking waters is a reasonable objective, since the various species have different toxicological impacts. However, developing robust and sensitive speciation methods is mandatory prior to any such regulations. Numerous arsenic speciation publications exist, but the question of robustness or ruggedness for a regulatory method has not been fully explored. The present work illustrates the use of anion exchange chromatography coupled to ICP-MS with a commercially available "speciation kit" option. The mobile phase containing 2 mM NaH(2)PO(4) and 0.2 mM EDTA at pH 6 allowed adequate separation of four As species (As(III), As(V), MMAA, DMAA) in less than 10 min. The analytical performance characteristics studied, including method detection limits (lower than 100 ng L(-1) for all the species evaluated), proved the suitability of the method to fulfill the current regulation. Other parameters evaluated such as laboratory fortified blanks, spiked recoveries, and reproducibility over a certain period of time produced adequate results. The samples analyzed were taken from water utilities in different areas of the United States and were provided by the U.S. EPA. The data suggests the speciation setup performs to U.S. EPA specifications but sample treatment and chemistry are also important factors for achieving good recoveries for samples spiked with As(III) as arsenite and As(V) as arsenate.

Environmental microbes can speciate and cycle arsenic.

PubMed

Rhine, E Danielle; Garcia-Dominguez, Elizabeth; Phelps, Craig D; Young, L Y

2005-12-15

Naturally occurring arsenic is found predominantly as arsenate [As(V)] or arsenite [As(III)], and can be readily oxidized or reduced by microorganisms. Given the health risks associated with arsenic in groundwater and the interest in arsenic-active microorganisms, we hypothesized that environmental microorganisms could mediate a redox cycling of arsenic that is linked to their metabolism. This hypothesis was tested using an As(V) respiring reducer (strain Y5) and an aerobic chemoautotrophic As(II) oxidizer (strain OL1 ) both isolated from a Superfund site, Onondaga Lake, in Syracuse, NY. Strains were grown separately and together in sealed serum bottles, and the oxic/anoxic condition was the only parameter changed. Initially, under anoxic conditions when both isolates were grown together, 2 mM As(V) was stoichiometrically reduced to As(III) within 14 days. Following complete reduction, sterile ambient air was added and within 24 h As(III) was completely oxidized to As(V). The anoxic-oxic cycle was repeated, and sterile controls showed no abiotic transformation within the 28-day incubation period. These results demonstrate that microorganisms can cycle arsenic in response to dynamic environmental conditions, thereby affecting the speciation, and hence mobility and toxicity of arsenic in the environment.

Changes in iron, sulfur, and arsenic speciation associated with bacterial sulfate reduction in ferrihydrite-rich systems.

PubMed

Saalfield, Samantha L; Bostick, Benjamin C

2009-12-01

Biologically mediated redox processes have been shown to affect the mobility of iron oxide-bound arsenic in reducing aquifers. This work investigates how dissimilatory sulfate reduction and secondary iron reduction affect sulfur, iron, and arsenic speciation. Incubation experiments were conducted with As(III/V)-bearing ferrihydrite in carbonate-buffered artificial groundwater enriched with lactate (10 mM) and sulfate (0.08-10 mM) and inoculated with Desulfovibrio vulgaris (ATCC 7757, formerly D. desulfuricans), which reduces sulfate but not iron or arsenic. Sulfidization of ferrihydrite led to formation of magnetite, elemental sulfur, and trace iron sulfides. Observed reaction rates imply that the majority of sulfide is recycled to sulfate, promoting microbial sulfate reduction in low-sulfate systems. Despite dramatic changes in Fe and S speciation, and minimal formation of Fe or As sulfides, most As remained in the solid phase. Arsenic was not solubilized in As(V)-loaded incubations, which experienced slow As reduction by sulfide, whereas As(III)-loaded incubations showed limited and transient As release associated with iron remineralization. This suggests that As(III) production is critical to As release under reducing conditions, with sulfate reduction alone unlikely to release As. These data also suggest that bacterial reduction of As(V) is necessary for As sequestration in sulfides, even where sulfate reduction is active.

Arsenic Speciation in Plankton Organisms from Contaminated Lakes: Transformations at the Base of the Freshwater Food Chain

DOE Office of Scientific and Technical Information (OSTI.GOV)

Caumette, Guilhem; Koch, Iris; Estrada, Esteban

2012-02-06

The two complementary techniques high performance liquid chromatography-inductively coupled plasma-mass spectrometry (HPLC-ICP-MS) and X-ray absorption near edge structure (XANES) analysis were used to assess arsenic speciation in freshwater phytoplankton and zooplankton collected from arsenic-contaminated lakes in Yellowknife (Northwest Territories, Canada). Arsenic concentrations in lake water ranged from 7 {micro}g L{sup -1} in a noncontaminated lake to 250 {micro}g L{sup -1} in mine-contaminated lakes, which resulted in arsenic concentrations ranging from 7 to 340 mg kg{sup -1} d.w. in zooplankton organisms (Cyclops sp.) and from 154 to 894 mg kg{sup -1} d.w. in phytoplankton. The main arsenic compounds identified by HPLC-ICP-MSmore » in all plankton were inorganic arsenic (from 38% to 98% of total arsenic). No other arsenic compounds were found in phytoplankton, but zooplankton organisms showed the presence of organoarsenic compounds, the most common being the sulfate arsenosugar, up to 47% of total arsenic, with traces of phosphate sugar, glycerol sugar, methylarsonate (MMA), and dimethylarsinate (DMA). In the uncontaminated Grace Lake, zooplankton also contained arsenobetaine (AB). XANES characterization of arsenic in the whole plankton samples showed AsV-O as the only arsenic compound in phytoplankton, and AsIII-S and AsV-O compounds as the two major inorganic arsenic species in zooplankton. The proportion of organoarsenicals and inorganic arsenic in zooplankton depends upon the arsenic concentration in lakes and shows the impact of arsenic contamination: zooplankton from uncontaminated lake has higher proportions of organoarsenic compounds and contains arsenobetaine, while zooplankton from contaminated area contains mostly inorganic arsenic.« less

Arsenic Transport and Transformation Associated with MSMA Application on a Golf Course Green

PubMed Central

Feng, Min; Schrlau, Jill E.; Snyder, Raymond; Snyder, George H.; Chen, Ming; Cisar, John L.; Cai, Yong

2008-01-01

The impact of extensively used arsenic-containing herbicides on groundwater beneath golf courses has become a topic of interest. Although currently used organoarsenicals are less toxic, their application into the environment may produce the more toxic inorganic arsenicals. The objective of this work was to understand the behavior of arsenic species in percolate water from monosodium methanearsonate (MSMA) applied golf course greens, as well as to determine the influences of root-zone media for United State Golf Association (USGA) putting green construction on arsenic retention and species conversion. The field test was established at the Fort Lauderdale Research and Education Center (FLREC), University of Florida. Percolate water was collected after MSMA application for speciation and total arsenic analyses. The results showed that the substrate composition significantly influenced arsenic mobility and arsenic species transformation in the percolate water. In comparison to uncoated sands (S) and uncoated sands and peat (S + P), naturally coated sands and peat (NS + P) showed a higher capacity of preventing arsenic from leaching into percolate water, implying that the coatings of sands with clay reduce arsenic leaching. Arsenic species transformation occurred in soil, resulting in co-occurrence of four arsenic species, arsenite (AsIII), arsenate (AsV), monomethylarsonic acid (MMA), and dimethylarsinic acid (DMA) in percolate water. The results indicated that substrate composition can significantly affect both arsenic retention in soil and arsenic speciation in percolate water. The clay coatings on the soil particles and the addition of peat in the soil changed the arsenic bioavailability, which in turn controlled the microorganism-mediated arsenic transformation. To better explain and understand arsenic transformation and transport after applying MSMA in golf green, a conceptual model was proposed. PMID:15853401

Field Deployable Method for Arsenic Speciation in Water.

PubMed

Voice, Thomas C; Flores Del Pino, Lisveth V; Havezov, Ivan; Long, David T

2011-01-01

Contamination of drinking water supplies by arsenic is a world-wide problem. Total arsenic measurements are commonly used to investigate and regulate arsenic in water, but it is well understood that arsenic occurs in several chemical forms, and these exhibit different toxicities. It is problematic to use laboratory-based speciation techniques to assess exposure as it has been suggested that the distribution of species is not stable during transport in some types of samples. A method was developed in this study for the on-site speciation of the most toxic dissolved arsenic species: As (III), As (V), monomethylarsonic acid (MMA) and dimethylarsenic acid (DMA). Development criteria included ease of use under field conditions, applicable at levels of concern for drinking water, and analytical performance.The approach is based on selective retention of arsenic species on specific ion-exchange chromatography cartridges followed by selective elution and quantification using graphite furnace atomic absorption spectroscopy. Water samples can be delivered to a set of three cartridges using either syringes or peristaltic pumps. Species distribution is stable at this point, and the cartridges can be transported to the laboratory for elution and quantitative analysis. A set of ten replicate spiked samples of each compound, having concentrations between 1 and 60 µg/L, were analyzed. Arsenic recoveries ranged from 78-112 % and relative standard deviations were generally below 10%. Resolution between species was shown to be outstanding, with the only limitation being that the capacity for As (V) was limited to approximately 50 µg/L. This could be easily remedied by changes in either cartridge design, or the extraction procedure. Recoveries were similar for two spiked hard groundwater samples indicating that dissolved minerals are not likely to be problematic. These results suggest that this methodology can be use for analysis of the four primary arsenic species of concern in drinking water supplies.

Arsenic Speciation of Solvent-Extracted Leachate from New and Weathered CCA-Treated Wood

PubMed Central

KHAN, BERNINE I.; SOLO - GABRIELE, HELENA M.; DUBEY, BRAJESH K.; TOWNSEND, TIMOTHY G.; CAI, YONG

2009-01-01

For the past 60 yr, chromate-copper-arsenate (CCA) has been used to pressure-treat millions of cubic meters of wood in the United States for the construction of many outdoor structures. Leaching of arsenic from these structures is a possible health concern as there exists the potential for soil and groundwater contamination. While previous studies have focused on total arsenic concentrations leaching from CCA-treated wood, information pertaining to the speciation of arsenic leached is limited. Since arsenic toxicity is dependent upon speciation, the objective of this study was to identify and quantify arsenic species leaching from new and weathered CCA-treated wood and CCA-treated wood ash. Solvent-extraction experiments were carried out by subjecting the treated wood and the ash to solvents of varying pH values, solvents defined in the EPA’s Synthetic Precipitation Leaching Procedure (SPLP) and Toxicity Characteristic Leaching Procedure (TCLP), rainwater, deionized water, and seawater. The generated leachates were analyzed for inorganic As(III) and As(V) and the organoarsenic species, monomethylarsonic acid (MMAA) and dimethylarsinic acid (DMAA), using high-performance liquid chromatography followed by hydride generation and atomic fluorescence spectrometry (HPLC–HG-AFS). Only the inorganic species were detected in any of the wood leachates; no organoarsenic species were found. Inorganic As(V) was the major detectable species leaching from both new and weathered wood. The weathered wood leached relatively more overall arsenic and was attributed to increased inorganic As(III) leaching. The greater presence of As(III) in the weathered wood samples as compared to the new wood samples may be due to natural chemical and biological transformations during the weathering process. CCA-treated wood ash leached more arsenic than unburned wood using the SPLP and TCLP, and ash samples leached more inorganic As(III) than the unburned counterparts. Increased leaching was due to higher concentrations of arsenic within the ash and to the conversion of some As(V) to As(III) during combustion. PMID:15461159

Field Deployable Method for Arsenic Speciation in Water

PubMed Central

Voice, Thomas C.; Flores del Pino, Lisveth V.; Havezov, Ivan; Long, David T.

2010-01-01

Contamination of drinking water supplies by arsenic is a world-wide problem. Total arsenic measurements are commonly used to investigate and regulate arsenic in water, but it is well understood that arsenic occurs in several chemical forms, and these exhibit different toxicities. It is problematic to use laboratory-based speciation techniques to assess exposure as it has been suggested that the distribution of species is not stable during transport in some types of samples. A method was developed in this study for the on-site speciation of the most toxic dissolved arsenic species: As (III), As (V), monomethylarsonic acid (MMA) and dimethylarsenic acid (DMA). Development criteria included ease of use under field conditions, applicable at levels of concern for drinking water, and analytical performance. The approach is based on selective retention of arsenic species on specific ion-exchange chromatography cartridges followed by selective elution and quantification using graphite furnace atomic absorption spectroscopy. Water samples can be delivered to a set of three cartridges using either syringes or peristaltic pumps. Species distribution is stable at this point, and the cartridges can be transported to the laboratory for elution and quantitative analysis. A set of ten replicate spiked samples of each compound, having concentrations between 1 and 60 µg/L, were analyzed. Arsenic recoveries ranged from 78–112 % and relative standard deviations were generally below 10%. Resolution between species was shown to be outstanding, with the only limitation being that the capacity for As (V) was limited to approximately 50 µg/L. This could be easily remedied by changes in either cartridge design, or the extraction procedure. Recoveries were similar for two spiked hard groundwater samples indicating that dissolved minerals are not likely to be problematic. These results suggest that this methodology can be use for analysis of the four primary arsenic species of concern in drinking water supplies. PMID:21822400

A population-based case-control study of urinary arsenic species and squamous cell carcinoma in New Hampshire, USA.

PubMed

Gilbert-Diamond, Diane; Li, Zhigang; Perry, Ann E; Spencer, Steven K; Gandolfi, A Jay; Karagas, Margaret R

2013-10-01

Chronic high arsenic exposure is associated with squamous cell carcinoma (SCC) of the skin, and inorganic arsenic (iAs) metabolites may play an important role in this association. However, little is known about the carcinogenicity of arsenic at levels commonly observed in the United States. We estimated associations between total urinary arsenic and arsenic species and SCC in a U.S. population. We conducted a population-based case-control SCC study (470 cases, 447 controls) in a U.S. region with moderate arsenic exposure through private well water and diet. We measured urinary iAs, monomethylarsonic acid (MMA), and dimethylarsinic acid (DMA), and summed these arsenic species (ΣAs). Because seafood contains arsenolipids and arsenosugars that metabolize into DMA through alternate pathways, participants who reported seafood consumption within 2 days before urine collection were excluded from the analyses. In adjusted logistic regression analyses (323 cases, 319 controls), the SCC odds ratio (OR) was 1.37 for each ln-transformed microgram per liter increase in ln-transformed ΣAs concentration [ln(ΣAs)] (95% CI: 1.04, 1.80). Urinary ln(MMA) and ln(DMA) also were positively associated with SCC (OR = 1.34; 95% CI: 1.04, 1.71 and OR = 1.34; 95% CI: 1.03, 1.74, respectively). A similar trend was observed for ln(iAs) (OR = 1.20; 95% CI: 0.97, 1.49). Percent iAs, MMA, and DMA were not associated with SCC. These results suggest that arsenic exposure at levels common in the United States relates to SCC and that arsenic metabolism ability does not modify the association.

Arsenic Exposure From Drinking Water and the Incidence of CKD in Low to Moderate Exposed Areas of Taiwan: A 14-Year Prospective Study.

PubMed

Hsu, Ling-I; Hsieh, Fang-I; Wang, Yuan-Hung; Lai, Tai-Shuan; Wu, Meei-Maan; Chen, Chien-Jen; Chiou, Hung-Yi; Hsu, Kuang-Hung

2017-12-01

Arsenic exposure is associated with decreased kidney function. The association between low to moderate arsenic exposure and kidney disease has not been fully clarified. The association between arsenic exposure from drinking water and chronic kidney disease (CKD) was examined in a long-term prospective observational study. 6,093 participants 40 years and older were recruited from arseniasis-endemic areas in northeastern Taiwan. Arsenic levels were 28.0, 92.8, and 295.7μg/L at the 50th, 75th, and 90th percentiles, respectively. Well-water arsenic and urinary total arsenic (inorganic plus methylated arsenic species) concentrations, adjusted for urinary creatinine concentration. Kidney diseases (ICD-9 codes: 250.4, 274.1, 283.11, 403.*1, 404.*2, 404.*3, 440.1, 442.1, 447.3, or 580-589) and CKD (ICD-9 code: 585) ascertained using Taiwan's National Health Insurance database 1998 to 2011. HRs contrasting CKD risk across arsenic exposure levels were estimated using Cox regression. Prevalence ORs for proteinuria (protein excretion ≥ 200mg/g) comparing quartiles of total urinary arsenic concentrations were estimated using logistic regression. We identified 1,104 incident kidney disease cases, including 447 CKD cases (incidence rates, 166.5 and 67.4 per 10 4 person-years, respectively). A dose-dependent association between well-water arsenic concentrations and kidney diseases was observed after adjusting for age, sex, education, body mass index, cigarette smoking, alcohol consumption, and analgesic use. Using arsenic concentration ≤ 10.0μg/L as reference, multivariable-adjusted HRs for incident CKD were 1.12 (95% CI, 0.88-1.42), 1.33 (95% CI, 1.03-1.72), and 1.33 (95% CI, 1.00-1.77) for arsenic concentrations of 10.1 to 49.9, 50.0 to 149.9, and ≥150.0μg/L, respectively (P for trend=0.02). The association between arsenic concentration and kidney diseases was stronger for women (P for interaction=0.06). Arsenic values in the range of 50th to 75th and 75th to 100th percentiles of total urinary arsenic concentrations were associated with 50% and 67% higher prevalences, respectively, of proteinuria. Kidney diseases and CKD outcomes were based on diagnostic codes. Glomerular filtration rates were not available. Other heavy metals were not measured. This study describes the temporal relationship between arsenic concentrations ≥ 10μg/L in drinking water and CKD. A dose-dependent association between well-water arsenic concentration and kidney diseases was observed. Higher creatinine-adjusted urinary total arsenic concentrations were associated with a higher prevalence of proteinuria. Copyright © 2017 National Kidney Foundation, Inc. Published by Elsevier Inc. All rights reserved.

Total arsenic concentrations in Chinese children's urine by different geographic locations, ages, and genders.

PubMed

Zhang, Xuan; Wang, Beibei; Cui, Xiaoyong; Lin, Chunye; Liu, Xitao; Ma, Jin

2018-06-01

Little is known about the variation of Chinese children's exposure to arsenic by geography, age, gender, and other potential factors. The main objective of this study was to investigate the total arsenic concentration in Chinese children's urine by geographic locations, ages, and genders. In total, 259 24-h urine samples were collected from 210 2- to 12-year-old children in China and analyzed for total arsenic and creatinine concentrations. The results showed that the upper limit (upper limit of the 90% confidence interval for the 97.5 fractile) was 27.51 µg/L or 55.88 µg/g creatinine for Chinese children. The total urinary arsenic levels were significantly different for children in Guangdong, Hubei, and Gansu provinces (P < 0.05), where the upper limits were 24.29, 58.70, and 44.29 µg/g creatinine, respectively. In addition, the total urinary arsenic levels were higher for 2- to 7-year-old children than for 7- to 12-year-old children (P < 0.05; the upper limits were 59.06 and 44.29 µg/g creatinine, respectively) and higher for rural children than for urban children (P < 0.05; the upper limits were 59.06 and 50.44 µg/g creatinine, respectively). The total urinary arsenic levels for boys were not significantly different from those for girls (P > 0.05), although the level for boys (the upper limit was 59.30 µg/g) was slightly higher than that for girls (the upper limit was 58.64 µg/g creatinine). Because the total urinary arsenic concentrations are significantly different for general populations of children in different locations and age groups, the reference level of total urinary arsenic might be dependent on the geographic site and the child's age.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shen, Jun; Wanibuchi, Hideki; Waalkes, Michael P.

Epidemiological studies indicated that human arsenic exposure can induce urinary bladder cancer. Methylation of inorganic arsenic can generate more reactive and toxic organic arsenical species. In this regard, it was recently reported that the methylated arsenical metabolite, dimethylarsinic acid [DMA(V)], induced urinary bladder tumors in rats. However, other methylated metabolites, like monomethylarsonic acid [MMA(V)] and trimethylarsine oxide (TMAO) were not carcinogenic to the urinary bladder. In order to compare the early effects of DMA(V), MMA(V), and TMAO on the urinary bladder transitional cell epithelium at the scanning electron microscope (SEM) level, we investigated the sub-chronic (13 weeks) toxicological effects ofmore » MMA(V) (187 ppm), DMA(V) (184 ppm), TMAO (182 ppm) given in the drinking water to male and female F344 rats with a focus on the urinary bladder in this study. Obvious pathological changes, including ropy microridges, pitting, increased separation of epithelial cells, exfoliation, and necrosis, were found in the urinary bladders of both sexes, but particularly in females receiving carcinogenic doses of DMA(V). Urine arsenical metabolic differences were found between males and females, with levels of MMA(III), a potential genotoxic form, higher in females treated with DMA(V) than in males. Thus, this study provides clear evidence that DMA(V) is more toxic to the female urinary bladder, in accord with sensitivity to carcinogenesis. Important gender-related metabolic differences including enhanced presentation of MMA(III) to the urothelial cells might possibly account for heightened sensitivity in females. However, the potential carcinogenic effects of MMA(III) need to be further elucidated.« less

Association between maternal urinary arsenic species and infant cord blood leptin levels in a New Hampshire Pregnancy Cohort.

PubMed

Gossai, Anala; Lesseur, Corina; Farzan, Shohreh; Marsit, Carmen; Karagas, Margaret R; Gilbert-Diamond, Diane

2015-01-01

Leptin is an important pleiotropic hormone involved in the regulation of nutrient intake and energy expenditure, and is known to influence body weight in infants and adults. High maternal levels of arsenic have been associated with reduced infant birth weight, but the mechanism of action is not yet understood. This study aimed to investigate the association between in utero arsenic exposure and infant cord blood leptin concentrations within 156 mother-infant pairs from the New Hampshire Birth Cohort Study (NHBCS) who were exposed to low to moderate levels of arsenic through well water and diet. In utero arsenic exposure was obtained from maternal second trimester urinary arsenic concentration, and plasma leptin levels were assessed through immunoassay. Results indicate that urinary arsenic species concentrations were predictive of infant cord blood leptin levels following adjustment for creatinine, infant birth weight for gestational age percentile, infant sex, maternal pregnancy-related weight gain, and maternal education level amongst 149 white mother-infant pairs in multivariate linear regression models. A doubling or 100% increase in total urinary arsenic concentration (iAs+MMA+DMA) was associated with a 10.3% (95% CI: 0.8-20.7%) increase in cord blood leptin levels. A 100% increase in either monomethylarsonic acid (MMA) or dimethylarsinic acid (DMA) was also associated with an 8.3% (95% CI: -1.0-18.6%) and 10.3% (95% CI: 1.2-20.2%) increase in cord blood leptin levels, respectively. The association between inorganic arsenic (iAs) and cord blood leptin was of similar magnitude and direction as other arsenic species (a 100% increase in iAs was associated with a 6.5% (95% CI: -3.4-17.5%) increase in cord blood leptin levels), albeit not significant. These results suggest in utero exposure to low levels of arsenic influences cord blood leptin concentration and presents a potential mechanism by which arsenic may impact early childhood growth. Copyright © 2014 Elsevier Inc. All rights reserved.

Oxidative DNA damage and repair in children exposed to low levels of arsenic in utero and during early childhood: Application of salivary and urinary biomarkers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hinhumpatch, Pantip; Navasumrit, Panida; Chulabhorn Graduate Institute, Laksi, Bangkok

The present study aimed to assess arsenic exposure and its effect on oxidative DNA damage and repair in young children exposed in utero and continued to live in arsenic-contaminated areas. To address the need for biological specimens that can be acquired with minimal discomfort to children, we used non-invasive urinary and salivary-based assays for assessing arsenic exposure and early biological effects that have potentially serious health implications. Levels of arsenic in nails showed the greatest magnitude of difference between exposed and control groups, followed by arsenic concentrations in saliva and urine. Arsenic levels in saliva showed significant positive correlations withmore » other biomarkers of arsenic exposure, including arsenic accumulation in nails (r = 0.56, P < 0.001) and arsenic concentration in urine (r = 0.50, P < 0.05). Exposed children had a significant reduction in arsenic methylation capacity indicated by decreased primary methylation index and secondary methylation index in both urine and saliva samples. Levels of salivary 8-OHdG in exposed children were significantly higher (∼ 4-fold, P < 0.01), whereas levels of urinary 8-OHdG excretion and salivary hOGG1 expression were significantly lower in exposed children (∼ 3-fold, P < 0.05), suggesting a defect in hOGG1 that resulted in ineffective cleavage of 8-OHdG. Multiple regression analysis results showed that levels of inorganic arsenic (iAs) in saliva and urine had a significant positive association with salivary 8-OHdG and a significant negative association with salivary hOGG1 expression. - Highlights: • The effects of arsenic exposure in utero and through early childhood were studied. • Arsenic-exposed children had a reduction in arsenic methylation capacity. • Exposed children had more DNA damage, observed as elevated salivary 8-OHdG. • Lower salivary hOGG1 in exposed children indicated impairment of 8-OHdG repair. • Salivary and urinary 8-OHdG levels were discordant.« less

Arsenic Exposure through Drinking Water Is Associated with Longer Telomeres in Peripheral Blood

PubMed Central

2012-01-01

Inorganic arsenic is a strong carcinogen, possibly by interaction with the telomere length. The aim of the study was to evaluate how chronic arsenic exposure from drinking water as well as the arsenic metabolism efficiency affect the individual telomere length and the expression of telomere-related genes. Two hundred two women with a wide range in exposure to arsenic via drinking water (3.5–200 μg/L) were recruited. Concentrations of arsenic metabolites in urine [inorganic arsenic (iAs), methylarsonic acid (MMA), and dimethylarsinic acid (DMA)] were measured. The relative telomere length in blood was measured by quantitative real-time polymerase chain reaction. Genotyping (N = 172) for eight SNPs in AS3MT and gene expression of telomere-related genes (in blood; N = 90) were performed. Urinary arsenic (sum of metabolites) was positively associated with telomere length (β = 0.65 × 10–4, 95% CI = 0.031 × 10–4–1.3 × 10–4, adjusted for age and BMI). Individuals with above median fractions of iAs and MMA showed significantly longer telomeres by increasing urinary arsenic (β = 1.0 × 10–4, 95% CI = 0.21 × 10–4–1.8 × 10–4 at high % iAs; β = 0.88 × 10–4 95% CI = 0.12 × 10–4–1.6 × 10–4 at high % MMA) than those below the median (p = 0.80 and 0.44, respectively). Similarly, carriers of the slow and more toxic metabolizing AS3MT haplotype showed stronger positive associations between arsenic exposure and telomere length, as compared to noncarriers (interaction urinary arsenic and haplotype p = 0.025). Urinary arsenic was positively correlated with the expression of telomerase reverse transcriptase (TERT, Spearman r = 0.22, p = 0.037), but no association was found between TERT expression and telomere length. Arsenic in drinking water influences the telomere length, and this may be a mechanism for its carcinogenicity. A faster and less toxic arsenic metabolism diminishes arsenic-related telomere elongation. PMID:22917110

Measurements of Arsenic in the Urine and Nails of Individuals Exposed to Low Concentrations of Arsenic in Drinking Water From Private Wells in a Rural Region of Québec, Canada.

PubMed

Gagnon, Fabien; Lampron-Goulet, Eric; Normandin, Louise; Langlois, Marie-France

2016-01-01

Chronic exposure to inorganic arsenic leads to an increased risk of cancer. A biological measurement was conducted in 153 private well owners and their families consuming water contaminated by inorganic arsenic at concentrations that straddle 10 μg/L. The relationship between the external dose indicators (concentration of inorganic arsenic in wells and daily well water inorganic arsenic intake) and the internal doses (urinary arsenic--sum of As(III), DMA, and MMA, adjusted for creatinine--and total arsenic in toenails) was evaluated using multiple linear regressions, controlling for age, gender, dietary sources of arsenic, and number of cigarettes smoked. It showed that urinary arsenic was associated with concentration of inorganic arsenic in wells (p < .001) and daily well water inorganic arsenic intake (p < .001) in adults, and with daily well water inorganic arsenic intake (p = .017) and rice consumption (p = .022) in children (n = 43). The authors' study reinforces the drinking-water quality guidelines for inorganic arsenic.

SPECIATION ANALYSIS OF ARSENIC IN BIOLOGICAL MATRICES BY AUTOMATED HYDRIDE GENERATION-CRYOTRAPPING-ATOMIC ABSORPTION SPECTROMETRY WITH MULTIPLE MICROFLAME QUARTZ TUBE ATOMIZER (MULTIATOMIZER)

EPA Science Inventory

Abstract Analyses of arsenic (As) species in tissues and body fluids of individuals chronically exposed to inorganic arsenic (iAs) provide essential information about the exposure level and pattern of iAs metabolism. We have previously described an oxidation state-specifi...

The ecology of arsenic

USGS Publications Warehouse

Oremland, Ronald S.; Stolz, John F.

2003-01-01

Arsenic is a metalloid whose name conjures up images of murder. Nonetheless, certain prokaryotes use arsenic oxyanions for energy generation, either by oxidizing arsenite or by respiring arsenate. These microbes are phylogenetically diverse and occur in a wide range of habitats. Arsenic cycling may take place in the absence of oxygen and can contribute to organic matter oxidation. In aquifers, these microbial reactions may mobilize arsenic from the solid to the aqueous phase, resulting in contaminated drinking water. Here we review what is known about arsenic-metabolizing bacteria and their potential impact on speciation and mobilization of arsenic in nature.

Relative Bioavailability and Bioaccessability and Speciation of Arsenic in Contaminated Soils

EPA Science Inventory

Background: Assessment of soil arsenic (As) bioavailability may profoundly affect the extent of remediation required at contaminated sites by improving human exposure estimates. Because small adjustments in soil As bioavailability estimates can significantly alter risk assessment...

DIMETHYLITHIOARSINIC ANHYDRIDE: A STANDARD FOR ARSENIC SPECIATION

EPA Science Inventory

Recently, sulfar analogs of well know arsenicals have been identfied in biolgical, dietary and environmental matrices. These discoveries have generated a need for stable species-specific standards. This presentation will forcus on the isolation and characterization of a standar...

DIMETHYLTHIOARSINIC ANHYDRIDE: A STANDARD FOR ARSENIC SPECIATION

EPA Science Inventory

Dimethylthioarsinic acid (DMTAV) has recently been identified in biological, dietary and environmental matrices. The relevance of this compound to the toxicity of arsenic in humans is unknown and further exposure assessment and metabolic studies are difficult to conduct because ...

Strong positive associations between seafood, vegetables, and alcohol with blood mercury and urinary arsenic levels in the Korean adult population.

PubMed

Park, Sunmin; Lee, Byung-Kook

2013-01-01

Blood mercury and urinary arsenic levels are more than fivefold greater in the Korean population compared with those of the United States. This may be related to the foods people consumed. Therefore, we examined the associations between food categories and mercury and arsenic exposure in the Korean adult population. Data regarding nutritional, biochemical, and health-related parameters were obtained from a cross-sectional study, the 2008-2009 Korean National Health and Nutrition Examination Survey (3,404 men and women age ≥ 20 years). The log-transformed blood mercury and urinary arsenic levels were regressed against the frequency tertiles of each food group after covariate adjustment for sex, age, residence area, education level, smoking status, and drinking status using food-frequency data. Blood mercury levels in the high consumption groups compared to the low consumption groups were elevated by about 20 percents with salted fish, shellfish, whitefish, bluefish, and alcohol, and by about 9-14 percents with seaweeds, green vegetables, fruits and tea, whereas rice did not affect blood mercury levels. Urinary arsenic levels were markedly increased with consumption of rice, bluefish, salted fish, shellfish, whitefish, and seaweed, whereas they were moderately increased with consumption of grains, green and white vegetables, fruits, coffee, and alcohol. The remaining food categories tended to lower these levels only minimally. In conclusion, the typical Asian diet, which is high in rice, salted fish, shellfish, vegetables, alcoholic beverages, and tea, may be associated with greater blood mercury and urinary arsenic levels. This study suggests that mercury and arsenic contents should be monitored and controlled in soil and water used for agriculture to decrease health risks from heavy-metal contamination.

Maternal Arsenic Exposure, Arsenic Methylation Efficiency, and Birth Outcomes in the Biomarkers of Exposure to ARsenic (BEAR) Pregnancy Cohort in Mexico

PubMed Central

Laine, Jessica E.; Bailey, Kathryn A.; Rubio-Andrade, Marisela; Olshan, Andrew F.; Smeester, Lisa; Drobná, Zuzana; Herring, Amy H.; Stýblo, Miroslav; García-Vargas, Gonzalo G.

2014-01-01

Background: Exposure to inorganic arsenic (iAs) from drinking water is a global public health problem, yet much remains unknown about the extent of exposure in susceptible populations. Objectives: We aimed to establish the Biomarkers of Exposure to ARsenic (BEAR) prospective pregnancy cohort in Gómez Palacio, Mexico, to better understand the effects of iAs exposure on pregnant women and their children. Methods: Two hundred pregnant women were recruited for this study. Concentrations of iAs in drinking water (DW-iAs) and maternal urinary concentrations of iAs and its monomethylated and dimethylated metabolites (MMAs and DMAs, respectively) were determined. Birth outcomes were analyzed for their relationship to DW-iAs and to the concentrations and proportions of maternal urinary arsenicals. Results: DW-iAs for the study subjects ranged from < 0.5 to 236 μg As/L. More than half of the women (53%) had DW-iAs that exceeded the World Health Organization’s recommended guideline of 10 μg As/L. DW-iAs was significantly associated with the sum of the urinary arsenicals (U-tAs). Maternal urinary concentrations of MMAs were negatively associated with newborn birth weight and gestational age. Maternal urinary concentrations of iAs were associated with lower mean gestational age and newborn length. Conclusions: Biomonitoring results demonstrate that pregnant women in Gómez Palacio are exposed to potentially harmful levels of DW-iAs. The data support a relationship between iAs metabolism in pregnant women and adverse birth outcomes. The results underscore the risks associated with iAs exposure in vulnerable populations. Citation: Laine JE, Bailey KA, Rubio-Andrade M, Olshan AF, Smeester L, Drobná Z, Herring AH, Stýblo M, García-Vargas GG, Fry RC. 2015. Maternal arsenic exposure, arsenic methylation efficiency, and birth outcomes in the Biomarkers of Exposure to ARsenic (BEAR) pregnancy cohort in Mexico. Environ Health Perspect 123:186–192; http://dx.doi.org/10.1289/ehp.1307476 PMID:25325819

Solid-Phase Speciation of Arsenic As the Primary Control on Dissolved As Concentrations in a Glacial Aquifer System: Quantifying Speciation of Arsenic in Glacial Aquifer Solids with μXAS Mapping.

NASA Astrophysics Data System (ADS)

Nicholas, S. L.; Gowan, A. S.; Knaeble, A. R.; Erickson, M. L.; Woodruff, L. G.; Marcus, M.; Toner, B. M.

2014-12-01

Western Minnesota, USA, is a regional locus of drinking-water wells with high arsenic (As) (As>10µgL-1). Arsenic concentrations vary widely among neighboring wells with otherwise similar water chemistry [1,2]. As(III) should be the most mobile As species in Minnesota well waters (median Eh in As affected wells is -50mV). This As is geogenic, sourced from glacial deposits derived from Cretaceous sedimentary bedrock (dolostone, limestone, shale). Our hypothesis is that As speciation in the solid phase is the important factor controlling the introduction of As to groundwater—more significant in this region than absolute As concentrations or landscape variability. Our previous research used micro-X-ray absorption spectroscopy (µXAS) speciation mapping [3] on archived glacial tills (stored dry at room temperature in air). µXAS results from this material showed that As in a reduced chemical state within the till aquitard is spatially correlated with iron sulfide at the micron scale. Conversley, As in aquifer sediments was mainly oxidized As(V). At the aquifer-aquitard contact As was observed as a mixture of both reduced and oxidized forms. This suggests that the aquifer-aquitard contact is a geochemically active zone in which reduced As species present within glacial till are converted to As(V) through complex redox processes, and subsequently release into aquifer sediments. Our current research applies the same methods to describe As speciation in samples collected from fresh cores of glacial sediment and frozen under argon in the field. Preliminary results are similar to our previous work in that As is, in general, more reduced in aquitard sediments, and more oxidized at the contact and in aquifer sediments. Arsenic(III) was preserved as a minor consitutent in ambient archived cores but is a more significant constituent in fresh, anaerobically preserved cores. Results will be presented comparing anaerobic samples with ambient-air aliquots of the same sample to document changes in the relative abundance of As species depending on sample preservation. This work was supported by LBNL-ALS, ANL-APS, USGS-MNWSC, MGS, and CURA. [1]Berndt & Soule (1999) Minnesota Arsenic Research Study: Report on Geochemistry. [2] Erickson & Barnes (2005) Water Research 39 4029-4039. [3] Toner et al. (2014) Env. Chem. 11 4-9.

Urinary arsenic levels in the French adult population: the French National Nutrition and Health Study, 2006-2007.

PubMed

Saoudi, Abdessattar; Zeghnoun, Abdelkrim; Bidondo, Marie-Laure; Garnier, Robert; Cirimele, Vincent; Persoons, Renaud; Fréry, Nadine

2012-09-01

The French Nutrition and Health Survey (ENNS) was conducted to describe dietary intakes, nutritional status, physical activity, and levels of various biomarkers for environmental chemicals (heavy metals and pesticides) in the French population (adults aged 18-74 years and children aged 3-17 years living in continental France in 2006-2007). The aim of this paper was to describe the distributions of total arsenic and the sum of iAs+MMA+DMA in the general adult population, and to present their main risk factors. In the arsenic study, 1500 and 1515 adults (requested to avoid seafood intake in the previous 3 days preceding urine collection) were included respectively for the analysis of the sum of inorganic arsenic (iAs) and its two metabolites, monomethylarsonic acid (MMA) and dimethylarsinic acid (DMA), and for the total arsenic. Results were presented as geometric means and selected percentiles of urinary arsenic concentrations (μg/L) and creatinine-adjusted urinary arsenic (μg/g of creatinine) for total arsenic, and the sum of inorganic arsenic and metabolites (iAs+MMA+DMA). The geometric mean concentration of the sum of iAs+MMA+DMA in the adult population living in France was 3.34 μg/g of creatinine [3.23-3.45] (3.75 μg/L [3.61-3.90]) with a 95th percentile of 8.9 μg/g of creatinine (10.68 μg/L). The geometric mean concentration of total arsenic was 11.96 μg/g of creatinine [11.41-12.53] (13.42 μg/L [12.77-14.09]) with a 95th percentile of 61.29 μg/g of creatinine (72.75 μg/L). Urinary concentrations of total arsenic and iAS+MMA+DMA were influenced by sociodemographic and economic factors, and by risk factors such as consumption of seafood products and of wine. In our study, covariate-adjusted geometric means demonstrated several slight differences, due to consumption of fish, shellfish/crustaceans or wine. This study provides the first reference value for arsenic in a representative sample of the French population not particularly exposed to high levels of arsenic (10 μg/g of creatinine). It shows that urinary arsenic concentrations in the French adult population (in particular concentrations of iAs+MMA+DMA) were relatively low compared with foreign data. Copyright © 2012 Elsevier B.V. All rights reserved.

Effect of Dietary Treatment with Dimethylarsinous Acid (DMAIII) on the Urinary Bladder Epithelium of Arsenic (+3 Oxidation State) Methyltransferase (As3mt) Knockout and C57BL/6 Wild Type Female Mice

EPA Science Inventory

Abstract Chronic exposure to inorganic arsenic (iAs) is carcinogenic to the human urinary bladder. It produces urothelial cytotoxicity and proliferation in rats and mice. DMAv, a major methylated urinary metabolite of iAs, is a rat bladder carcinogen, but without effects on the...

[Transformation and mobility of arsenic in the rhizosphere and non-rhizosphere soils at different growth stages of rice].

PubMed

Yang, Wen-Tao; Wang, Ying-Jie; Zhou, Hang; Yi, Kai-Xin; Zeng, Min; Peng, Pei-Qin; Liao, Bo-Han

2015-02-01

Speciation and bioavailability of arsenic in the rhizosphere and non-rhizosphere soils at different growth stages (tillering stage, jointing stage, booting stage, filling stage and maturing stage) of rice (Oryza sativa L.) were studied using toxicity characteristic leaching procedure (TCLP) and arsenic speciation analysis. Pot experiments were conducted and the soil samples were taken from a certain paddy soil in Hunan Province contaminated by mining industry. The results showed that: (1) With the extension of rice growth period, pH values and TCLP extractable arsenic levels in the rhizosphere and non-rhizosphere soils increased gradually. Soil pH and TCLP extractable arsenic levels in non-rhizosphere soils were higher than those in the rhizosphere soils at the same growth stage. (2) At the different growth stages of rice, contents of exchangeable arsenic (AE-As) in rhizosphere and non-rhizosphere soils were lower than those before the rice planting, and increased gradually with the extension of the rice growing period. Contents of Al-bound arsenic (Al-As), Fe-bound arsenic (Fe-As) and Ca-bound arsenic (Ca-As) increased gradually after rice planting, but not significantly. Residual arsenic (O-As) and total arsenic (T-As) decreased gradually after rice planting, by 37.30% and 14.69% in the rhizosphere soils and by 31.38% and 8.67% in the non-rhizosphere soils, respectively. (3) At the different growth stages of rice, contents of various forms of arsenic in the soils were in the following order: residual arsenic (O-As) > Fe-bound arsenic ( Fe-As) > Al-bound arsenic (Al-As) > Ca-bound arsenic (Ca-As) > exchangeable arsenic (AE-As). In the pH range of 5.0- 5.8, significant positive linear correlations were found between most forms of arsenic or TCLP extractable arsenic levels and pH values, while the Ca-bound arsenic was poorly correlated with pH values in the rhizosphere soils.

EXAMINATION OF CHANGES IN AS SPECIATION IN SULFIDIC SOLUTIONS

EPA Science Inventory

The fate of arsenic (As) in the environment, its bioavailability and toxicity is fundamentally linked to its speciation. As in aerobic environments is predominantly arsenate (As(V)), however under reducing conditions arsenite (As(III)) species dominate. In sulfidic environments t...

Oxidative DNA damage and repair in children exposed to low levels of arsenic in utero and during early childhood: application of salivary and urinary biomarkers.

PubMed

Hinhumpatch, Pantip; Navasumrit, Panida; Chaisatra, Krittinee; Promvijit, Jeerawan; Mahidol, Chulabhorn; Ruchirawat, Mathuros

2013-12-15

The present study aimed to assess arsenic exposure and its effect on oxidative DNA damage and repair in young children exposed in utero and continued to live in arsenic-contaminated areas. To address the need for biological specimens that can be acquired with minimal discomfort to children, we used non-invasive urinary and salivary-based assays for assessing arsenic exposure and early biological effects that have potentially serious health implications. Levels of arsenic in nails showed the greatest magnitude of difference between exposed and control groups, followed by arsenic concentrations in saliva and urine. Arsenic levels in saliva showed significant positive correlations with other biomarkers of arsenic exposure, including arsenic accumulation in nails (r=0.56, P<0.001) and arsenic concentration in urine (r=0.50, P<0.05). Exposed children had a significant reduction in arsenic methylation capacity indicated by decreased primary methylation index and secondary methylation index in both urine and saliva samples. Levels of salivary 8-OHdG in exposed children were significantly higher (~4-fold, P<0.01), whereas levels of urinary 8-OHdG excretion and salivary hOGG1 expression were significantly lower in exposed children (~3-fold, P<0.05), suggesting a defect in hOGG1 that resulted in ineffective cleavage of 8-OHdG. Multiple regression analysis results showed that levels of inorganic arsenic (iAs) in saliva and urine had a significant positive association with salivary 8-OHdG and a significant negative association with salivary hOGG1 expression. © 2013.

Speciation of arsenic in biological samples.

PubMed

Mandal, Badal Kumar; Ogra, Yasumitsu; Anzai, Kazunori; Suzuki, Kazuo T

2004-08-01

Speciation of arsenicals in biological samples is an essential tool to gain insight into its distribution in tissues and its species-specific toxicity to target organs. Biological samples (urine, hair, fingernail) examined in the present study were collected from 41 people of West Bengal, India, who were drinking arsenic (As)-contaminated water, whereas 25 blood and urine samples were collected from a population who stopped drinking As contaminated water 2 years before the blood collection. Speciation of arsenicals in urine, water-methanol extract of freeze-dried red blood cells (RBCs), trichloroacetic acid treated plasma, and water extract of hair and fingernail was carried out by high-performance liquid chromatography (HPLC)-inductively coupled argon plasma mass spectrometry (ICP MS). Urine contained arsenobetaine (AsB, 1.0%), arsenite (iAs(III), 11.3), arsenate (iAs(V), 10.1), monomethylarsonous acid (MMA(III), 6.6), monomethylarsonic acid (MMA(V), 10.5), dimethylarsinous acid (DMA(III), 13.0), and dimethylarsinic acid (DMA(V), 47.5); fingernail contained iAs(III) (62.4%), iAs(V) (20.2), MMA(V) (5.7), DMA(III) (8.9), and DMA(V) (2.8); hair contained iAs(III) (58.9%), iAs(V) (34.8), MMA(V) (2.9), and DMA(V) (3.4); RBCs contained AsB (22.5%) and DMA(V) (77.5); and blood plasma contained AsB (16.7%), iAs(III) (21.1), MMA(V) (27.1), and DMA(V) (35.1). MMA(III), DMA(III), and iAs(V) were not found in any plasma and RBCs samples, but urine contained all of them. Arsenic in urine, fingernails, and hair are positively correlated with water As, suggesting that any of these measurements could be considered as a biomarker to As exposure. Status of urine and exogenous contamination of hair urgently need speciation of As in these samples, but speciation of As in nail is related to its total As (tAs) concentration. Therefore, total As concentrations of nails could be considered as biomarker to As exposure in the endemic areas.

Magnetic ferrite particles combined with electrothermal atomic absorption spectrometry for the speciation of low concentrations of arsenic.

PubMed

López-García, Ignacio; Marín-Hernández, Juan José; Hernández-Córdoba, Manuel

2018-05-01

Freshly in situ prepared ferrite particles were used for the micro-solid phase extraction of arsenic species. When the separation was carried out at pH 8, inorganic arsenic (As(III) + As(V)) and monomethylarsonic acid (MMA) were retained in the magnetic material. A second aliquot was treated with 2,3 dimercapto propanol, leading to the retention of As(V)+MMA, while a third aliquot was first treated with sodium thiosulphate, in which case only inorganic arsenic passed to the solid phase. In all cases, the solid residue collected by a magnet was suspended in a dilute nitric acid solution containing Triton X-100 and introduced into the electrothermal atomizer to obtain the analytical signal of arsenic. The use of palladium as a chemical modifier allowed calibration to be carried out with aqueous standards. The detection limit was 0.02µgL -1 arsenic for a 10mL sample volume. The procedure was applied to waters and herbal infusions, and its reliability was evaluated by analyzing eleven certified reference materials for which speciation data are provided. Copyright © 2017 Elsevier B.V. All rights reserved.

PEPTIDE BINDING AS A MODE OF ACTION FOR THE CARCINOGENICITY AND TOXICITY OF ARSENIC

EPA Science Inventory

Arsenic exposure leads to tumors in human skin, lung, urinary bladder, kidney and liver. Three likely initial stages of arsenical-macromolecular interaction are (1) binding of trivalent arsenicals to the sulfhydryl groups of peptides and proteins, (2) arsenical-induced generation...

Preserving the distribution of inorganic arsenic species in groundwater and acid mine drainage samples

USGS Publications Warehouse

Bednar, A.J.; Garbarino, J.R.; Ranville, J.F.; Wildeman, T.R.

2002-01-01

The distribution of inorganic arsenic species must be preserved in the field to eliminate changes caused by metal oxyhydroxide precipitation, photochemical oxidation, and redox reactions. Arsenic species sorb to iron and manganese oxyhydroxide precipitates, and arsenite can be oxidized to arsenate by photolytically produced free radicals in many sample matrices. Several preservatives were evaluated to minimize metal oxyhydroxide precipitation, such as inorganic acids and ethylenediaminetetraacetic acid (EDTA). EDTA was found to work best for all sample matrices tested. Storing samples in opaque polyethylene bottles eliminated the effects of photochemical reactions. The preservation technique was tested on 71 groundwater and six acid mine drainage samples. Concentrations in groundwater samples reached 720 ??g-As/L for arsenite and 1080 ??g-As/L for arsenate, and acid mine drainage samples reached 13 000 ??g-As/L for arsenite and 3700 ??g-As/L for arsenate. The arsenic species distribution in the samples ranged from 0 to 90% arsenite. The stability of the preservation technique was established by comparing laboratory arsenic speciation results for samples preserved in the field to results for subsamples speciated onsite. Statistical analyses indicated that the difference between arsenite and arsenate concentrations for samples preserved with EDTA in opaque bottles and field speciation results were analytically insignificant. The percentage change in arsenite:arsenate ratios for a preserved acid mine drainage sample and groundwater sample during a 3-month period was -5 and +3%, respectively.

PROPOSED CARCINOGENIC MECHANISMS FOR ARSENIC

EPA Science Inventory

PROPOSED CARCINOGENIC MECHANISMS FOR ARSENIC.

Arsenic is a human carcinogen in skin, lung, liver, urinary bladder and kidney. In contrast,
there is no accepted experimental animal model of inorganic arsenic carcinogenesis.
Proposed mechanisms/modes of action for a...

Understanding arsenic metabolism through a comparative study of arsenic levels in the urine, hair and fingernails of healthy volunteers from three unexposed ethnic groups in the United Kingdom

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brima, Eid I.; Haris, Parvez I.; Jenkins, Richard O.

2006-10-01

Very little is known about arsenic (As) metabolism in healthy populations that are not exposed to high concentrations of As in their food or water. Here we present a study with healthy volunteers from three different ethnic groups, residing in Leicester, UK, which reveals statistically significant differences in the levels of total As in urine and fingernail samples. Urine (n = 63), hair (n = 36) and fingernail (n = 36) samples from Asians, Somali Black-Africans and Whites were analysed using inductively coupled plasma mass spectrometry (ICP-MS) and graphite furnace atomic absorption spectroscopy (GF-AAS). The results clearly show that themore » total concentrations of As in urine and fingernail samples of a Somali Black-African population (urine 7.2 {mu}g/g creatinine; fingernails 723.1 {mu}g/kg) are significantly (P < 0.05) different from the Asian (urine 24.5 {mu}g/g creatinine; fingernails 153.9 {mu}g/kg) and White groups (urine 20.9 {mu}g/g creatinine; fingernails 177.0 {mu}g/kg). The chemical speciation of As in the urine of the three groups was also measured using high performance liquid chromatography coupled to ICP-MS. This showed that the proportion of the total urinary As present as dimethylarsenate (DMA) was higher for the Somali Black-African group (50%) compared to the Asians (16%) and Whites (22%). However, there was no significant difference (P > 0.05) in the level of As in the hair samples from these three groups; Somali Black-Africans (116.0 {mu}g/kg), Asians (117.4 {mu}g/kg) and Whites (141.2 {mu}g/kg). Significantly different levels of total As in fingernail and urine and a higher percentage of urinary DMA in the Somali Black-Africans are suggestive of a different pattern of As metabolism in this ethnic group.« less

Speciation and Attenuation of Arsenic and Selenium at Coal Combustion By-Product Management Facilities

DOE Office of Scientific and Technical Information (OSTI.GOV)

K. Ladwig

2005-12-31

The overall objective of this project was to evaluate the impact of key constituents captured from power plant air streams (principally arsenic and selenium) on the disposal and utilization of coal combustion products (CCPs). Specific objectives of the project were: (1) to develop a comprehensive database of field leachate concentrations at a wide range of CCP management sites, including speciation of arsenic and selenium, and low-detection limit analyses for mercury; (2) to perform detailed evaluations of the release and attenuation of arsenic species at three CCP sites; and (3) to perform detailed evaluations of the release and attenuation of seleniummore » species at three CCP sites. Each of these objectives was accomplished using a combination of field sampling and laboratory analysis and experimentation. All of the methods used and results obtained are contained in this report. For ease of use, the report is subdivided into three parts. Volume 1 contains methods and results for the field leachate characterization. Volume 2 contains methods and results for arsenic adsorption. Volume 3 contains methods and results for selenium adsorption.« less

Arsenic speciation for the phytoremediation by the Chinese brake fern, Pteris vittata.

PubMed

Shoji, R; Yajima, R; Yano, Y

2008-01-01

Arsenic (As) speciation for the phytoremediation by the Chinese brake fern was studied. In particular, the mechanism of how plants induce compounds containing thiol (SH) and proteins by As exposure in terms of the relationship between As and phosphate uptaken into plant cells was examined. Pteris vittata callus could efficiently reduce As(V) to As(III) by the rapid introduction of reductase and synthesize thiols leading to phytochelatins production. Furthermore, Pteris vittata could control phosphate concentration in the cells corresponding to the concentration of arsenite and arsenate. To our best knowledge, this is the first report to show the mechanisms of such high As tolerance of Pteris vittata using their callus in terms of in vitro approach for the analysis of As speciation and metabolism route.

Differences in Urinary Arsenic Metabolites between Diabetic and Non-Diabetic Subjects in Bangladesh

PubMed Central

Nizam, Saika; Kato, Masashi; Yatsuya, Hiroshi; Khalequzzaman, Md.; Ohnuma, Shoko; Naito, Hisao; Nakajima, Tamie

2013-01-01

Ingestion of inorganic arsenic (iAs) is considered to be related to the development of diabetes mellitus. In order to clarify the possible differences in the metabolism in diabetics, we measured urinary iAs metabolites in diabetic cases and non-diabetic control subjects in Faridpur, an arsenic-contaminated area in Bangladesh. Physician-diagnosed type 2 diabetic cases (140 persons) and non-diabetic controls (180 persons) were recruited. Drinking water and spot urine samples were collected. Mean concentrations of total arsenic in drinking water did not differ between cases (85.1 μg/L) and controls (85.8 μg/L). The percentage of urinary iAs (iAs%) was significantly lower in cases (8.6%) than in controls (10.4%), while that of dimethylarsinic acid (DMA%) was higher in cases (82.6%) than in controls (79.9%). This may have been due to the higher secondary methylation index (SMI) in the former (11.6) rather than the latter (10.0). Adjusting for matching factors (sex and unions), and the additional other covariates (age and water arsenic) significantly attenuated the differences in iAs%, SMI, and DMA%, respectively, though the difference in monomethylarsonic acid% was newly significant in the latter adjustment. Our study did not suggest any significant differences in urinary arsenic metabolites between diabetic and non-diabetic subjects. PMID:23481591

Geochemical processes controlling fate and transport of arsenic in acid mine drainage (AMD) and natural systems.

PubMed

Cheng, Hefa; Hu, Yuanan; Luo, Jian; Xu, Bin; Zhao, Jianfu

2009-06-15

Acid mine drainage (AMD) is often accompanied with elevated concentrations of arsenic, in the forms of arsenite, As(III), and/or arsenate, As(V), due to the high affinity of arsenic for sulfide mineral ores. This review summarizes the major geochemical processes controlling the release, speciation, fate, and distribution of inorganic arsenic in mine drainage and natural systems. Arsenic speciation depends highly on redox potential and pH of the solution, and arsenite can be oxidized to the less toxic arsenate form. Homogeneous oxidation of arsenite occurs rather slowly while its heterogeneous oxidation on mineral surfaces can greatly enhance the reaction rates. Little evidence suggests that precipitation reaction limits the concentrations of arsenic in natural water, while co-precipitation may lead to rapid arsenic removal when large amount of iron hydroxides precipitate out of the aqueous phase upon neutralization of the mine drainage. Both arsenate and arsenite adsorb on common metal oxides and clay minerals through formation of inner-sphere and/or outer-sphere complexes, controlling arsenic concentration in natural water bodies. Arsenite adsorbs less strongly than arsenate in the typical pH range of natural water and is more mobile. Part of the adsorbed arsenic species can be exchanged by common anions (e.g., PO(4)(3-) and SO(4)(2-)), especially phosphate, which leads to their re-mobilization. Understanding the geochemistry of arsenic is helpful for predicting its mobility and fate in AMD and natural systems, and for designing of cost-effective remediation/treatment strategies to reduce the occurrence and risk of arsenic contamination.

ELEMENTAL SPECIATION IN ENVIRONMENTAL EXPOSURE ASSESSMENT MATRICES

EPA Science Inventory

Arsenic and tin are two trace metals where exposure assessments have moved towards a speciation based approach because the toxicity is very chemical form dependent. This toxicity difference can be one of many factors which influence the formulation of certain regulations. For a...

Application Of Synchrotron Techniques To Investigate In-Situ Arsenic Speciation

EPA Science Inventory

The speciation, or chemical form of elements governs their fate, toxicity, mobility, and bioavailability in contaminated soils, sediments and water as well as food chain transfer mechanisms. To assess these chemical properties and to accurately gauge contaminant impact on human h...

Determination of arsenite, arsenate, monomethylarsonic acid and dimethylarsinic acid in cereals by hydride generation atomic fluorescence spectrometry

NASA Astrophysics Data System (ADS)

Matos Reyes, M. N.; Cervera, M. L.; Campos, R. C.; de la Guardia, M.

2007-09-01

A fast, sensitive and simple non-chromatographic analytical method was developed for the speciation analysis of toxic arsenic species in cereal samples, namely rice and wheat semolina. An ultrasound-assisted extraction of the toxic arsenic species was performed with 1 mol L - 1 H 3PO 4 and 0.1% (m/v) Triton XT-114. After extraction, As(III), As(V), dimethylarsinic acid (DMA) and monomethylarsonic acid (MMA) concentrations were determined by hydride generation atomic fluorescence spectrometry using a series of proportional equations corresponding to four different experimental reduction conditions. The detection limits of the method were 1.3, 0.9, 1.5 and 0.6 ng g - 1 for As(III), As(V), DMA and MMA, respectively, expressed in terms of sample dry weight. Recoveries were always greater than 90%, and no species interconversion occurred. The speciation analysis of a rice flour reference material certified for total arsenic led to coherent results, which were also in agreement with other speciation studies made on the same certified reference material.

MODES OF ACTION FOR THE CARCINOGENICITY AND TOXICITY OF ARSENIC - MOVING TOWARDS A MORE QUANTITATIVE RISK ASSESSMENT

EPA Science Inventory

Arsenic exposures can lead to human tumors in skin, lung, urinary bladder, kidney and liver. Three likely initial stages of arsenical¬macromolecular interaction are (1) binding of trivalent arsenicals to sulfhydryl groups of peptides and proteins, (2) arsenical-induced generation...

Association between body mass index and arsenic methylation efficiency in adult women from southwest U.S. and northwest Mexico

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gomez-Rubio, Paulina; Roberge, Jason; Arendell, Leslie

2011-04-15

Human arsenic methylation efficiency has been consistently associated with arsenic-induced disease risk. Interindividual variation in arsenic methylation profiles is commonly observed in exposed populations, and great effort has been put into the study of potential determinants of this variability. Among the factors that have been evaluated, body mass index (BMI) has not been consistently associated with arsenic methylation efficiency; however, an underrepresentation of the upper BMI distribution was commonly observed in these studies. This study investigated potential factors contributing to variations in the metabolism of arsenic, with specific interest in the effect of BMI where more than half of themore » population was overweight or obese. We studied 624 adult women exposed to arsenic in drinking water from three independent populations. Multivariate regression models showed that higher BMI, arsenic (+ 3 oxidation state) methyltransferase (AS3MT) genetic variant 7388, and higher total urinary arsenic were significantly associated with low percentage of urinary arsenic excreted as monomethylarsonic acid (%uMMA) or high ratio between urinary dimethylarsinic acid and uMMA (uDMA/uMMA), while AS3MT genetic variant M287T was associated with high %uMMA and low uDMA/uMMA. The association between BMI and arsenic methylation efficiency was also evident in each of the three populations when studied separately. This strong association observed between high BMI and low %uMMA and high uDMA/uMMA underscores the importance of BMI as a potential arsenic-associated disease risk factor, and should be carefully considered in future studies associating human arsenic metabolism and toxicity.« less

SPECIATION OF SELENIUM AND ARSENIC COMPOUNDS BY CAPILLARY...

EPA Science Inventory

Capillary electrophoresis (CE) with hydride generation inductively coupled plasma mass spectrometry was used to determine four arsenicals and two selenium species. Selenate (SeVI) was reduced on-line to selenite (SeIV) by mixing the CE effluent with concentrated HCl. A microporou...

Chronic arsenic exposure increases TGFalpha concentration in bladder urothelial cells of Mexican populations environmentally exposed to inorganic arsenic

DOE Office of Scientific and Technical Information (OSTI.GOV)

Valenzuela, Olga L.; Germolec, Dori R.; Borja-Aburto, Victor H.

Inorganic arsenic (iAs) is a well-established carcinogen and human exposure has been associated with a variety of cancers including those of skin, lung, and bladder. High expression of transforming growth factor alpha (TGF-{alpha}) has associated with local relapses in early stages of urinary bladder cancer. iAs exposures are at least in part determined by the rate of formation and composition of iAs metabolites (MAs{sup III}, MAs{sup V}, DMAs{sup III}, DMAs{sup V}). This study examines the relationship between TGF-{alpha} concentration in exfoliated bladder urothelial cells (BUC) separated from urine and urinary arsenic species in 72 resident women (18-51 years old) frommore » areas exposed to different concentrations of iAs in drinking water (2-378 ppb) in central Mexico. Urinary arsenic species, including trivalent methylated metabolites were measured by hydride generation atomic absorption spectrometry method. The concentration of TGF-{alpha} in BUC was measured using an ELISA assay. Results show a statistically significant positive correlation between TGF-{alpha} concentration in BUC and each of the six arsenic species present in urine. The multivariate linear regression analyses show that the increment of TGF-{alpha} levels in BUC was importantly associated with the presence of arsenic species after adjusting by age, and presence of urinary infection. People from areas with high arsenic exposure had a significantly higher TGF-{alpha} concentration in BUC than people from areas of low arsenic exposure (128.8 vs. 64.4 pg/mg protein; p < 0.05). Notably, exfoliated cells isolated from individuals with skin lesions contained significantly greater amount of TGF-{alpha} than cells from individuals without skin lesions: 157.7 vs. 64.9 pg/mg protein (p = 0.003). These results suggest that TGF-{alpha} in exfoliated BUC may serve as a susceptibility marker of adverse health effects on epithelial tissue in arsenic-endemic areas.« less

Arsenic speciation and uranium concentrations in drinking water supply wells in Northern Greece: correlations with redox indicative parameters and implications for groundwater treatment.

PubMed

Katsoyiannis, Ioannis A; Hug, Stephan J; Ammann, Adrian; Zikoudi, Antonia; Hatziliontos, Christodoulos

2007-09-20

The cities in the Aksios and Kalikratia areas in Northern Greece rely on arsenic contaminated groundwater for their municipal water supply. As remedial action strongly depends on arsenic speciation, the presence of other possible contaminants, and on the general water composition, a detailed study with samples from 21 representative locations was undertaken. Arsenic concentrations were typically 10-70 microg/L. In the groundwaters of the Aksios area with lower Eh values (87-172 mV), pH 7.5-8.2 and 4-6 mM HCO(3) alkalinity, As(III) predominated. Manganese concentrations were mostly above the EC standard of 0.05 mg/L (0.1-0.7 mg/L). In groundwaters of the Kalikratia area with higher Eh values (272-352 mV), pH 6.7-7.5 and 6-12 mM HCO(3) alkalinity, As(V) was the main species. Uranium in the groundwaters was also investigated and correlations with total arsenic concentrations and speciation were examined to understand more of the redox chemistry of the examined groundwaters. Uranium concentrations were in the range 0.01-10 microg/L, with the higher concentrations to occur in the oxidizing groundwaters of the Kalikratia area. Uranium and total arsenic concentrations showed no correlation, whereas uranium concentrations correlated strongly with As(III)/As(tot) ratios, depicting their use as a possible indicator of groundwater redox conditions. Finally, boron was found to exceed the EC drinking water standard of 1 mg/L in some wells in the Kalikratia area and its removal should also be considered in the design of a remedial action.

Total and inorganic arsenic in Mid-Atlantic marine fish and shellfish and implications for fish advisories.

PubMed

Greene, Richard; Crecelius, Eric

2006-10-01

Sampling was conducted in 2002 to determine the total concentration and chemical speciation of arsenic in several marine fish and shellfish species collected from the Delaware Inland Bays and the Delaware Estuary, both of which are important estuarine waterbodies in the US Mid-Atlantic region that support recreational and commercial fishing. Edible meats from summer flounder (Paralicthys dentatus), striped bass (Marone saxatilis), Atlantic croaker (Micropogonias undulates), and hard clam (Mercenaria mercenaria) were tested. Total arsenic was highest in summer flounder, followed by hard clam, then striped bass, and finally, Atlantic croaker. Total arsenic was higher in summer flounder collected during the spring, as these fish migrated into the Inland Bays from the continental shelf, compared with levels in summer flounder collected during the fall, after these fish had spent the summer in the Inland Bays. Similarly, striped bass collected in the early spring close to the ocean had higher total arsenic levels compared with levels detected in striped bass collected later during the year in waters with lower salinity. Speciation of arsenic revealed low concentrations (0.00048-0.02 microg/g wet wt) of toxic inorganic arsenic. Dimethylarsinic acid was more than an order of magnitude greater in hard clam meats than in the other species tested, a finding that was attributed to arsenic uptake by phytoplankton and subsequent dietary uptake by the clam. Risk assessment using the inorganic arsenic concentrations was used to conclude that a fish consumption advisory is not warranted.

Evaluation of epigenetic alterations (mir-126 and mir-155 expression levels) in Mexican children exposed to inorganic arsenic via drinking water.

PubMed

Pérez-Vázquez, Mónica S; Ochoa-Martínez, Ángeles C; RuÍz-Vera, Tania; Araiza-Gamboa, Yesenia; Pérez-Maldonado, Iván N

2017-12-01

Recently, a great number of epidemiological studies have shown evidence that exposure to inorganic arsenic could have harmful effects on the cardiovascular system of humans. However, the underlying mechanisms through which arsenic induces cardiovascular toxic effects remain unclear. In this regard, epigenetic mechanisms have emerged as a probable connection between environment and disease phenotypes, including cardiovascular diseases. Therefore, this study aimed to evaluate epigenetic changes related to cardiotoxicity (miR-126 and miR-155 expression levels) in children from San Luis Potosi, Mexico exposed to inorganic arsenic. From 2014 to 2015, in a cross-sectional study, children (aged 6-12 years; n = 73) attending public schools at the studied sites were enrolled to take part in this study. Urinary arsenic was used as an exposure biomarker and analyzed by an atomic absorption spectrophotometry technique. On the other hand, miR-126 and miR-155 expression levels were evaluated by qRT-PCR. A mean urinary arsenic level of 30.5 ± 25.5 μg/g of creatinine was found. Moreover, the data showed a significant negative association (p < 0.05) between urinary arsenic concentrations and plasma miR-126 levels. However, an association between urinary arsenic concentrations and plasma miR-155 levels was not found (p > 0.05). In this regard, some investigations have shown an association between diminished plasma miR-126 levels and cardiovascular illnesses. The results found in this study are of concern. However, more similar studies including a larger sample size are necessary in order to clarify the real significance of the data.

A Prospective Study of Arsenic Exposure, Arsenic Methylation Capacity, and Risk of Cardiovascular Disease in Bangladesh

PubMed Central

Wu, Fen; Liu, Mengling; Parvez, Faruque; Slavkovich, Vesna; Eunus, Mahbub; Ahmed, Alauddin; Argos, Maria; Islam, Tariqul; Rakibuz-Zaman, Muhammad; Hasan, Rabiul; Sarwar, Golam; Levy, Diane; Graziano, Joseph

2013-01-01

Background: Few prospective studies have evaluated the influence of arsenic methylation capacity on cardiovascular disease (CVD) risk. Objective: We evaluated the association of arsenic exposure from drinking water and arsenic methylation capacity with CVD risk. Method: We conducted a case–cohort study of 369 incident fatal and nonfatal cases of CVD, including 211 cases of heart disease and 148 cases of stroke, and a subcohort of 1,109 subjects randomly selected from the 11,224 participants in the Health Effects of Arsenic Longitudinal Study (HEALS). Results: The adjusted hazard ratios (aHRs) for all CVD, heart disease, and stroke in association with a 1-SD increase in baseline well-water arsenic (112 µg/L) were 1.15 (95% CI: 1.01, 1.30), 1.20 (95% CI: 1.04, 1.38), and 1.08 (95% CI: 0.90, 1.30), respectively. aHRs for the second and third tertiles of percentage urinary monomethylarsonic acid (MMA%) relative to the lowest tertile, respectively, were 1.27 (95% CI: 0.85, 1.90) and 1.55 (95% CI: 1.08, 2.23) for all CVD, and 1.65 (95% CI: 1.05, 2.60) and 1.61 (95% CI: 1.04, 2.49) for heart disease specifically. The highest versus lowest ratio of urinary dimethylarsinic acid (DMA) to MMA was associated with a significantly decreased risk of CVD (aHR = 0.54; 95% CI: 0.34, 0.85) and heart disease (aHR = 0.54; 95% CI: 0.33, 0.88). There was no significant association between arsenic metabolite indices and stroke risk. The effects of incomplete arsenic methylation capacity—indicated by higher urinary MMA% or lower urinary DMA%—with higher levels of well-water arsenic on heart disease risk were additive. There was some evidence of a synergy of incomplete methylation capacity with older age and cigarette smoking. Conclusions: Arsenic exposure from drinking water and the incomplete methylation capacity of arsenic were adversely associated with heart disease risk. PMID:23665672

Relation of dietary inorganic arsenic exposure and urinary inorganic arsenic metabolites excretion in Japanese subjects.

PubMed

Oguri, Tomoko; Yoshinaga, Jun; Suzuki, Yayoi; Tao, Hiroaki; Nakazato, Tetsuya

2017-06-03

Inorganic arsenic (InAs) is a ubiquitous metalloid that has been shown to exert multiple adverse health outcomes. Urinary InAs and its metabolite concentration has been used as a biomarker of arsenic (As) exposure in some epidemiological studies, however, quantitative relationship between daily InAs exposure and urinary InAs metabolites concentration has not been well characterized. We collected a set of 24-h duplicated diet and spot urine sample of the next morning of diet sampling from 20 male and 19 female subjects in Japan from August 2011 to October 2012. Concentrations of As species in duplicated diet and urine samples were determined by using liquid chromatography-ICP mass spectrometry with a hydride generation system. Sum of the concentrations of urinary InAs and methylarsonic acid (MMA) was used as a measure of InAs exposure. Daily dietary InAs exposure was estimated to be 0.087 µg kg -1 day -1 (Geometric mean, GM), and GM of urinary InAs+MMA concentrations was 3.5 ng mL -1 . Analysis of covariance did not find gender-difference in regression coefficients as significant (P > 0.05). Regression equation Log 10 [urinary InAs+MMA concentration] = 0.570× Log 10 [dietary InAs exposure level per body weight] + 1.15 was obtained for whole data set. This equation would be valuable in converting urinary InAs concentration to daily InAs exposure, which will be important information in risk assessment.

DEVELOPMENT OF ULTRATRACE LASER SPECTROMETRY TECHNIQUES FOR MEASUREMENTS OF ARSENIC

EPA Science Inventory

Development of Arsenic Speciation Techniques Based on High Performance Liquid Chromatography and Atomic Fluorescence Spectrometry

J.B. Simeonsson, H.D. Beach and D.J. Thomas
US EPA, Office of Research and Development, National Health and Environmental Effects Resear...

Assessment of arsenic speciation and bioaccessibility in mine-impacted materials

EPA Science Inventory

Mine-impacted materials were collected from Victoria, Australia and categorized into three source materials; tailings (n = 35), calcinated (n = 10) and grey slimes (n = 5). Arsenic (As) concentrations in these materials varied over several orders of magnitude (30-47,000 mg kg

ARSENIC PARTITIONING TO IRON OXIDES AND SULFIDES: LOCAL ENVIRONMENT AND OXIDATION STATE

EPA Science Inventory

his document summarizes research activities conducted at the Advanced Photon Source at Argonne National Laboratory, Argonne, IL during FY2003. The analytical data collected using X-ray absorption spectroscopy was used to evaluated the chemical speciation of arsenic associated wi...

Arsenic Metabolism by Human Gut Microbiota upon in Vitro Digestion of Contaminated Soils

EPA Science Inventory

Speciation analysis is essential when evaluating risks from, arsenic (As) exposure. In an oral exposure scenario, the importance of presystemic metabolism by gut microorganisms has been evidenced with in vivo animal models and in vitro experiments with animal microbiota. Howeve...

Estimation of Inorganic Arsenic Exposure in Populations With Frequent Seafood Intake: Evidence From MESA and NHANES

PubMed Central

Jones, Miranda R.; Tellez-Plaza, Maria; Vaidya, Dhananjay; Grau, Maria; Francesconi, Kevin A.; Goessler, Walter; Guallar, Eliseo; Post, Wendy S.; Kaufman, Joel D.; Navas-Acien, Ana

2016-01-01

The sum of urinary inorganic arsenic (iAs) and methylated arsenic (monomethylarsonate and dimethylarsinate (DMA)) species is the main biomarker of iAs exposure. Assessing iAs exposure, however, is difficult in populations with moderate-to-high seafood intakes. In the present study, we used subsamples from the Multi-Ethnic Study of Atherosclerosis (2000–2002) (n = 310) and the 2003–2006 National Health and Nutrition Examination Survey (n = 1,175). We calibrated urinary concentrations of non–seafood-derived iAs, DMA, and methylarsonate, as well as the sum of inorganic and methylated arsenic species, in the Multi-Ethnic Study of Atherosclerosis and of DMA in the National Health and Nutrition Examination Survey by regressing their original concentrations by arsenobetaine and extracting model residuals. To confirm that calibrated biomarkers reflected iAs exposure but not seafood intake, we compared urinary arsenic concentrations by levels of seafood and rice intakes. Self-reported seafood intakes, estimated n-3 polyunsaturated fatty acid levels, and measured n-3 polyunsaturated fatty acid levels were positively associated with the original urinary arsenic biomarkers. Using the calibrated arsenic biomarkers, we found a marked attenuation of the associations with self-reported seafood intake and estimated or measured n-3 fatty acids, whereas associations with self-reported rice intake remained similar. Our residual-based method provides estimates of iAs exposure and metabolism for each participant that no longer reflect seafood intake and can facilitate research about low-to-moderate levels of iAs exposure in populations with high seafood intakes. PMID:27702745

COMPARISON OF GENE EXPRESSION IN KIDNEY AND URINARY BLADDER FROM RATS TREATED WITH DIMETHYLARSINIC ACID

EPA Science Inventory

Arsenic is widespread in the environment and a human carcinogen. A major metabolite of inorganic arsenic (iAs) in most species, including humans, is dimethylarsinic acid (DMA), which is also used as a pesticide. Unlike iAs, DMA induces urinary bladder tumors in rats. DMA is belie...

Arsenic Concentrations and Speciation in Shellfishes from Korea

NASA Astrophysics Data System (ADS)

Yoon, C.; Yoon, H.

2005-12-01

Speciation of arsenic has received significant attention over the past 20 years in both mechanistic and exposure assessment research. Because the toxicity of arsenic is related to its oxidation state and its chemical forms, the determination of the total arsenic contents in a sample is not adequate to allow its impact on living organisms to be estimated. The inorganic arsenic species, arsenite (As3+) and arsenate (As5+), have been classified as carcinogenic and the methylated forms, monomethyl arsonic acid (MMA) and dimethyl arsinic acid (DMA) have recently been identified as cancer promoters. The highly methylated compounds like as arsenobetaine (AsB) and arsenocholine (AsC) are considered to be nontoxic. Although organisms in marine environment contain high amounts of total arsenic (ppm level), it is not usually present as inorganic arsenic or simple methylated forms well known as one of the toxic species. Arsenobetaine is the dominant species in marine animals and arsenosugars are most abundant in marine algae. This study aims to clarify those arsenic species present in the whole body of eleven different shellfishes from Korea. And those arsenic species were separated and measured by characterization using high performance liquid chromatography-inductively coupled plasma-mass spectrometry (HPLC-ICP-MS) coupled system. The separation of arsenic species was achieved on anion exchange column and cation exchange column using phosphate and pyridine eluent, respectively. The ultrasonic extraction was employed for extraction of arsenic from whole body of shellfishes. The method was validated by analyzing three certified reference materials (DORM-2, TORT-2, 1566b). Total arsenic concentrations ranged from 0.1 mg/kg dry mass to 21.7 mg/kg dry mass. Most marine shellfishes contained higher arsenobetaine and arsenocholine with the exception of two shellfishes living in river. The lower amounts of inorganic arsenic species were also found in the some sample extracts. Detection of inorganic arsenic can be explained by the conversion of inorganic arsenic to organic arsenic compounds in digestion system in the body may be occurring.

On the fate of arsenic in the Menez Gwen hydrothermal system, Mid-Atlantic Ridge

NASA Astrophysics Data System (ADS)

Breuer, C.; Ruiz Chancho, M.; Pichler, T.

2011-12-01

Samples of hydrothermal fluids and on-site associated mussels (Bathymodiolus azoricus) were collected during the M 82/3 cruise of RV Meteor at the Menez Gwen hydrothermal field (37° 50' N, MAR) and analyzed for total and arsenic species (arsenite, arsenate and organorarsenicals) with ICP-(HR)MS and HPLC-ICP-(HR)MS respectively. Fluids emitting with temperatures of up to 280 °C and at 840 - 865 m depth contained total endmember As concentrations between 9.5 and 19.23 μg L-1 while local seawater concentrations varied around 1.5 μg L-1. The most important factors controlling the amount of As in these fluids are the E-MORB host rock composition and temperature of the fluids leading to phase separation or not. Regarding arsenic speciation in the fluids, there is discrepancy about the best method of preservation for water samples when speciation analysis of arsenic species must be carried out and a lack of information is especially relevant when marine hydrothermal vent samples have to be preserved. For this, one of the objectives of the present study was the comparison of different preservation methods of fluid samples collected at the Menez Gwen hydrothermal field. The methods used in the present study were: freezing at -20 °C, acidification with HCl and addition of EDTA. Most of these have been used by different authors for the preservation of inorganic arsenic species but organic arsenic species have not been taken into account and particularly hydrothermal fluids were not investigated. The results show very different proportions of arsenite and arsenate depending on the preservation procedure but the presence of methylated arsenic species or arsenosugars was not detected. The highest proportions of arsenite were found in the samples preserved with HCl. The presence of thio-arsenic species was tested with the addition of hydrogen peroxide. Moreover, mass balance calculations showed the presence of one or more species, which could not be detected with the chromatographic separation used in the present study. It was also observed that there was a strong T and pH dependence with arsenite, especially in the flash frozen samples. From this study it can be clearly stated that sample preservation is a critical point and further studies related with preservation of marine hydrothermal vent fluids for arsenic speciation must be carried out. Although arsenic has been extensively investigated in marine organisms, there is still little information about the metabolism of this element in organisms habiting the deep see, with only one publication so far. Bathymodiolus azoricus has never been studied regarding arsenic speciation and the fact that it is exposed to arsenic concentrations higher than other marine organisms makes it very interesting from the metabolism point of view. The mussels collected near the vents were dissected in gill, muscle and digestive gland and analyzed for total and arsenic species. Results are discussed taking into account the exposure and possible metabolism paths taking place in deep-sea hydrothermal systems.

THE REACTIVE OXYGEN SPECIES (ROS) THEORY OF ARSENIC CARCINOGENESIS

EPA Science Inventory

Arsenic is a human carcinogen in skin, lung, liver, urinary bladder
and kidney. At this time, there is not a scientific consensus on the
mechanisms/modes of action for arsenic carcinogenesis. Proposed
mechanisms/modes of action for arsenic carcinogenesi...

What is the best biomarker to assess arsenic exposure via drinking water?

PubMed

Marchiset-Ferlay, Nathalie; Savanovitch, Chantal; Sauvant-Rochat, Marie-Pierre

2012-02-01

Arsenic (As) is a ubiquitous element. The current WHO guideline for As in drinking water is 10 μg/L. Furthermore, about 130 million people have only access to drinking water containing more than 10 g As/L. Although numerous studies have shown the related adverse effects of As, sensitive appropriate biomarkers are still required for studies of environmental epidemiology. A review of the literature has shown that various biomarkers are used for such research. Their limits and advantages are highlighted in this paper: (i) the detection of As or its derivatives in the blood is an indication of the dose ingested but it is not evidence of chronic intoxication. (ii) The detection of As in urine is an indispensible procedure because it is a good marker for internal dose. It has been demonstrated to correlate well for a number of chronic effects related to As levels in drinking water. However confounding factors must be taken into account to avoid misinterpretation and this may require As speciation. (iii) As in the hair and nails reflects the level of long term exposure but it is difficult to relate the level with the dose ingested. (iv) Some studies showed a correlation between urinary As and urinary and blood porphyrins. However, it is difficult to use only porphyrins as a biomarker in a population survey carried out without doing further studies. (v) Genotoxic effects are based on the characterization of these potential effects. Most studies have detected increases in DNA damage, sister chromatid exchange, micronuclei or chromosomal aberrations in populations exposed to As in drinking water. Micronuclei assay is the technique of choice to follow these populations, because it is sensitive and easy to use. To conclude, whatever epidemiological studies are, the urinary and toenail biomarkers are useful to provide indications of internal dose. Moreover, micronuclei assay can be complementary use as biomarker of early effects. Copyright © 2011 Elsevier Ltd. All rights reserved.

ASSESSING SPECIATION AND RELEASE OF HEAVY METALS FROM COAL COMBUSTION PRODUCTS

EPA Science Inventory

In this study, the speciation of heavy metals such as arsenic, selenium, lead, zinc and mercury in coal combustion products (CCPs) was evaluated using sequential extraction procedures. Coal fly ash, bottom ash and flue gas desulphurization (FGD) sludge samples were used in the ex...

CHARACTERIZATION OF ARSENOSUGARS AND ASSOCIATED DEGRADATION PRODUCTS FOLLOWING AN AGGRESSIVE ACID/BASE EXTRACTION PROCEDURE

EPA Science Inventory

The speciation of arsenic in seafood products is important for the determination of an improved toxicity based relative source (water vs. diet) contribution estimate. The two major sources of arsenic are drinking water and seafood ingestion. Drinking water contains predominatel...

Speciation And Localization Of Arsenic In White And Brown Rice Grains

EPA Science Inventory

Synchrotron-based X-ray fluorescence (S-XRF) was utilized to locate arsenic (As) in polished (white) and unpolished (brown) rice grains from the United States, China, and Bangladesh. In white rice As was generally dispersed throughout the grain, the bulk of which constitutes the...

Arsenic Metabolism by Human Gut Microbiota upon In Vitro Digestion of Contaminated Soils

EPA Science Inventory

Background: Speciation analysis is essential when evaluating risks from arsenic (As) exposure. In an oral exposure scenario, the importance of presystemic metabolism by gut microorganisms has been evidenced with in vivo animal models and in vitro experiments with ...

Speciation of arsenic in different types of nuts by ion chromatography-inductively coupled plasma mass spectrometry.

PubMed

Kannamkumarath, Sasi S; Wróbel, Kazimierz; Wróbel, Katarzyna; Caruso, Joseph A

2004-03-24

In this work the quantitative determination and analytical speciation of arsenic were undertaken in different types of nuts, randomly purchased from local markets. The hardness of the whole nuts and high lipid content made the preparation of this material difficult for analysis. The lack of sample homogeneity caused irreproducible results. To improve the precision of analysis, arsenic was determined separately in nut oil and in the defatted sample. The lipids were extracted from the ground sample with the two portions of a mixture of chloroform and methanol (2:1). The defatted material was dried and ground again, yielding a fine powder. The nut oil was obtained by combining the two organic extracts and by evaporating the solvents. The two nut fractions were microwave digested, and total arsenic was determined by inductively coupled plasma mass spectrometry (ICP-MS). The results obtained for oils from different types of nuts showed element concentration in the range 2.9-16.9 ng g(-)(1). Lower levels of arsenic were found in defatted material (<0.1 ng g(-)(1) with the exception of Brazil nuts purchased with and without shells, 3.0 and 2.8 ng g(-)(1) respectively). For speciation analysis of arsenic in nut oils, elemental species were extracted from 2 g of oil with 12 mL of chloroform/methanol (2:1) and 8 mL of deionized water. The aqueous layer, containing polar arsenic species, was evaporated and the residue dissolved and analyzed by ion chromatography-ICP-MS. The anion exchange chromatography enabled separation of As(III), dimethylarsinic acid (DMAs(V)), monomethylarsonic acid (MMAs(V)), and As(V) within 8 min. Several types of nuts were analyzed, including walnuts, Brazil nuts, almonds, cashews, pine nuts, peanuts, pistachio nuts, and sunflower seeds. The recovery for the speciation procedure was in the range 72.7-90.6%. The primary species found in the oil extracts were As(III) and As(V). The arsenic concentration levels in these two species were 0.7-12.7 and 0.5-4.3 ng g(-)(1), respectively. The contribution of As in DMAs(V) ranged from 0.1 +/- 0.1 ng g(-)(1) in walnuts to 1.3 +/- 0.3 ng g(-)(1) in pine nuts. MMAs(V) was not detected in almonds, peanuts, pine nuts, sunflower seeds, or walnuts, and the highest concentration was found in pistachio nuts (0.5 +/- 0.2 ng g(-)(1)).

Associations between Methylated Metabolites of Arsenic and Selenium in Urine of Pregnant Bangladeshi Women and Interactions between the Main Genes Involved.

PubMed

Skröder, Helena; Engström, Karin; Kuehnelt, Doris; Kippler, Maria; Francesconi, Kevin; Nermell, Barbro; Tofail, Fahmida; Broberg, Karin; Vahter, Marie

2018-02-01

It has been proposed that interactions between selenium and arsenic in the body may affect their kinetics and toxicity. However, it is unknown how the elements influence each other in humans. We aimed to investigate potential interactions in the methylation of selenium and arsenic. Urinary selenium (U-Se) and arsenic (U-As) were measured using inductively coupled plasma mass spectrometry (ICPMS) in samples collected from pregnant women ( n =226) in rural Bangladesh at gestational weeks (GW) 8, 14, 19, and 30. Urinary concentrations of trimethyl selenonium ion (TMSe) were measured by HPLC-vapor generation-ICPMS, as were inorganic arsenic (iAs), methylarsonic acid (MMA), and dimethylarsinic acid (DMA). Methylation efficiency was assessed based on relative amounts (%) of arsenic and selenium metabolites in urine. Genotyping for the main arsenite and selenium methyltransferases, AS3MT and INMT, was performed using TaqMan probes or Sequenom. Multivariable-adjusted linear regression analyses indicated that %TMSe (at GW8) was positively associated with %MMA (β=1.3, 95% CI: 0.56, 2.0) and U-As, and inversely associated with %DMA and U-Se in producers of TMSe ( INMT rs6970396 AG+AA, n =74), who had a wide range of urinary TMSe (12-42%). Also, %TMSe decreased in parallel to %MMA during pregnancy, especially in the first trimester (-0.58 %TMSe per gestational week). We found a gene-gene interaction for %MMA ( p -interaction=0.076 for haplotype 1). In analysis stratified by INMT genotype, the association between %MMA and both AS3MT haplotypes 1 and 3 was stronger in women with the INMT GG (TMSe nonproducers, 5th-95th percentile: 0.2-2%TMSe) vs. AG+AA genotype. Our findings for Bangladeshi women suggest a positive association between urinary %MMA and %TMSe. Genes involved in the methylation of selenium and arsenic may interact on associations with urinary %MMA. https://doi.org/10.1289/EHP1912.

Renal, hepatic, pulmonary and adrenal tumors induced by prenatal inorganic arsenic followed by dimethylarsinic acid in adulthood in CD1 mice

PubMed Central

Tokar, Erik J.; Diwan, Bhalchandra A.; Waalkes, Michael P.

2012-01-01

Inorganic arsenic, an early life carcinogen in humans and mice, can initiate lesions promotable by other agents in later life. The biomethylation product of arsenic, dimethylarsinic acid (DMA), is a multi-site tumor promoter. Thus, pregnant CD1 mice were given drinking water (0 or 85 ppm arsenic) from gestation day 8 to 18 and after weaning male offspring received DMA (0 or 200 ppm; drinking water) for up to 2 years. No renal tumors occurred in controls or DMA alone treated mice while gestational arsenic exposure plus later DMA induced a significant renal tumor incidence of 17% (primarily renal cell carcinoma). Arsenic plus DMA or arsenic alone also increased renal hyperplasia over control but DMA alone did not. Arsenic alone, DMA alone and arsenic plus DMA all induced urinary bladder hyperplasia (33–35%) versus control (2%). Compared to control (6%), arsenic alone tripled hepatocellular carcinoma (20%), and arsenic plus DMA doubled this rate again (43%), but DMA alone had no effect. DMA alone, arsenic alone, and arsenic plus DMA increased lung adenocarcinomas and adrenal adenomas versus control. Overall, DMA in adulthood promoted tumors/lesions initiated by prenatal arsenic in the kidney and liver, but acted independently in the urinary bladder, lung and adrenal. PMID:22230260

Oxidation State Specific Generation of Arsines from Methylated Arsenicals Based on L- Cysteine Treatment in Buffered Media for Speciation Analysis by Hydride Generation - Automated Cryotrapping - Gas Chromatography-Atomic Absorption Spectrometry with the Multiatomizer

PubMed Central

Matoušek, Tomáš; Hernández-Zavala, Araceli; Svoboda, Milan; Langrová, Lenka; Adair, Blakely M.; Drobná, Zuzana; Thomas, David J.; Stýblo, Miroslav; Dědina, Jiří

2008-01-01

An automated system for hydride generation - cryotrapping- gas chromatography - atomic absorption spectrometry with the multiatomizer is described. Arsines are preconcentrated and separated in a Chromosorb filled U-tube. An automated cryotrapping unit, employing nitrogen gas formed upon heating in the detection phase for the displacement of the cooling liquid nitrogen, has been developed. The conditions for separation of arsines in a Chromosorb filled U-tube have been optimized. A complete separation of signals from arsine, methylarsine, dimethylarsine, and trimethylarsine has been achieved within a 60 s reading window. The limits of detection for methylated arsenicals tested were 4 ng l−1. Selective hydride generation is applied for the oxidation state specific speciation analysis of inorganic and methylated arsenicals. The arsines are generated either exclusively from trivalent or from both tri- and pentavalent inorganic and methylated arsenicals depending on the presence of L-cysteine as a prereductant and/or reaction modifier. A TRIS buffer reaction medium is proposed to overcome narrow optimum concentration range observed for the L-cysteine modified reaction in HCl medium. The system provides uniform peak area sensitivity for all As species. Consequently, the calibration with a single form of As is possible. This method permits a high-throughput speciation analysis of metabolites of inorganic arsenic in relatively complex biological matrices such as cell culture systems without sample pretreatment, thus preserving the distribution of tri- and pentavalent species. PMID:18521190

Chronic arsenic exposure increases TGFalpha concentration in bladder urothelial cells of Mexican populations environmentally exposed to inorganic arsenic☆

PubMed Central

Valenzuela, Olga L.; Germolec, Dori R.; Borja-Aburto, Víctor H.; Contreras-Ruiz, José; García-Vargas, Gonzalo G.; Del Razo, Luz M.

2009-01-01

Inorganic arsenic (iAs) is a well-established carcinogen and human exposure has been associated with a variety of cancers including those of skin, lung, and bladder. High expression of transforming growth factor alpha (TGF-α) has associated with local relapses in early stages of urinary bladder cancer. iAs exposures are at least in part determined by the rate of formation and composition of iAs metabolites (MAsIII, MAsV, DMAsIII, DMAsV). This study examines the relationship between TGF-α concentration in exfoliated bladder urothelial cells (BUC) separated from urine and urinary arsenic species in 72 resident women (18-51 years old) from areas exposed to different concentrations of iAs in drinking water (2-378 ppb) in central Mexico. Urinary arsenic species, including trivalent methylated metabolites were measured by hydride generation atomic absorption spectrometry method. The concentration of TGF-α in BUC was measured using an ELISA assay. Results show a statistically significant positive correlation between TGF-α concentration in BUC and each of the six arsenic species present in urine. The multivariate linear regression analyses show that the increment of TGF-α levels in BUC was importantly associated with the presence of arsenic species after adjusting by age, and presence of urinary infection. People from areas with high arsenic exposure had a significantly higher TGF-α concentration in BUC than people from areas of low arsenic exposure (128.8 vs. 64.4 pg/mg protein; p<0.05). Notably, exfoliated cells isolated from individuals with skin lesions contained significantly greater amount of TGF-α than cells from individuals without skin lesions: 157.7 vs. 64.9 pg/mg protein (p=0.003). These results suggest that TGF-α in exfoliated BUC may serve as a susceptibility marker of adverse health effects on epithelial tissue in arsenic-endemic areas. PMID:17267001

COMPARISON OF IN VITRO AND IN VIVO RESPONSES TO ARSENIC: GENE EXPRESSION PROFILING IN NORMAL HUMAN EPIDERMAL KERATINOCYTES AND HYPERKERATOSES FROM ARSENIC-EXPOSED HUMANS

EPA Science Inventory

Chronic exposure to arsenic is positively associated with skin, urinary bladder, lung, liver and kidney cancer development in humans. Elucidating the mode of action of arsenic carcinogenesis is a complicated issue as target cells are exposed to different toxic species of arsenic....

Arsenate Impact on the Metabolite Profile, Production, and Arsenic Loading of Xylem Sap in Cucumbers (Cucumis sativus L.)

PubMed Central

Uroic, M. Kalle; Salaün, Pascal; Raab, Andrea; Feldmann, Jörg

2012-01-01

Arsenic uptake and translocation studies on xylem sap focus generally on the concentration and speciation of arsenic in the xylem. Arsenic impact on the xylem sap metabolite profile and its production during short term exposure has not been reported in detail. To investigate this, cucumbers were grown hydroponically and arsenate (AsV) and DMA were used for plant treatment for 24 h. Total arsenic and arsenic speciation in xylem sap was analyzed including a metabolite profiling under AsV stress. Produced xylem sap was quantified and absolute arsenic transported was determined. AsV exposure had a significant impact on the metabolite profile of xylem sap. Four m/z values corresponding to four compounds were up-regulated, one compound down-regulated by AsV exposure. The compound down-regulated was identified to be isoleucine. Furthermore, AsV exposure had a significant influence on sap production, leading to a reduction of up to 96% sap production when plants were exposed to 1000 μg kg−1 AsV. No difference to control plants was observed when plants were exposed to 1000 μg kg−1 DMA. Absolute arsenic amount in xylem sap was the lowest at high AsV exposure. These results show that AsV has a significant impact on the production and metabolite profile of xylem sap. The physiological importance of isoleucine needs further attention. PMID:22536187

Ground water arsenic contamination in West Bengal, India: a risk of sub-clinical toxicity in cattle as evident by correlation between arsenic exposure, excretion and deposition.

PubMed

Bera, Asit Kumar; Rana, Tanmoy; Das, Subhshree; Bhattacharya, Debasis; Bandyopadhyay, Subhasish; Pan, Diganta; De, Sumanta; Samanta, Srikanta; Chowdhury, Atalanta Narayan; Mondal, Tapan Kumar; Das, Subrata Kumar

2010-11-01

Arsenic contamination of ground water in West Bengal, India, is a great concern for both human and livestock populations. Our study investigated and correlated the arsenic concentration in the drinking water, urinary excretion and deposition of total arsenic in hair of cattle at an arsenic contaminated zone in West Bengal. The results of our study indicated that the average concentration of arsenic in tube well water in contaminated villages ranged from 0.042 to 0.251 ppm and a statistical significant (p < 0.01) difference was seen when compared to samples from a non-contaminated zone. The arsenic concentration in urine and hair of cattle ranged between 0.245-0.691 ppm and 0.461-0.984 ppm, respectively. A close relationship was found between the total arsenic in drinking water urinary excretion (r² = 0.03664, p < 0.05) and the arsenic concentration in hair (r² = 0.03668, p < 0.05). Our findings indicate that quantification of arsenic concentration in cattle urine and hair can serve as biomarkers for both present and past exposure in cattle population.

DIFFERENTIAL MODULATION OF CANCER-RELATED MOLECULAR NETWORKS IN HUMAN AND RAT URINARY BLADDER CELLS EXPOSED TO TRIVALENT ARSENICALS

EPA Science Inventory

Arsenic (As) is classified as a known human carcinogen with primary targets of urinary bladder (UB), skin and lung. The most prevalent source of As exposure in humans is drinking water contaminated with inorganic As (iAs), and millions of people worldwide are exposed to drinking ...

Investigation of Health Effects According to the Exposure of Low Concentration Arsenic Contaminated Ground Water

PubMed Central

Hong, Young-seoub; Ye, Byeong-jin; Kim, Yu-mi; Kim, Byoung-gwon; Kang, Gyeong-hui; Kim, Jeong-jin; Song, Ki-hoon; Kim, Young-hun

2017-01-01

Recent epidemiological studies have reported adverse health effects, including skin cancer, due to low concentrations of arsenic via drinking water. We conducted a study to assess whether low arsenic contaminated ground water affected health of the residents who consumed it. For precise biomonitoring results, the inorganic (trivalent arsenite (As III) and pentavalent arsenate (As V)) and organic forms (monomethylarsonate (MMA) and dimethylarsinate (DMA)) of arsenic were separately quantified by combining high-performance liquid chromatography and inductively coupled plasma mass spectroscopy from urine samples. In conclusion, urinary As III, As V, MMA, and hair arsenic concentrations were significantly higher in residents who consumed arsenic contaminated ground water than control participants who consumed tap water. But, most health screening results did not show a statistically significant difference between exposed and control subjects. We presume that the elevated arsenic concentrations may not be sufficient to cause detectable health effects. Consumption of arsenic contaminated ground water could result in elevated urinary organic and inorganic arsenic concentrations. We recommend immediate discontinuation of ground water supply in this area for the safety of the residents. PMID:29186890

THE DISTRIBUTION, SOLID-PHASE SPECIATION, AND DESORPTION/DISSOLUTION OF AS IN IRON-BASED DRINKING WATER TREATMENT MEDIA 1

EPA Science Inventory

Arsenic concentrations (Total Recoverable As by EPA Method 3051, soluble, Toxicity Characteristic Leaching Procedure extractable) and solid-phase speciation (by X-ray Absorption Near-Edge Spectroscopy-XANES) were assessed as a function of depth through Fe-media beds for two comme...

THE DISTRIBUTION, SOLID-PHASE SPECIATION, AND DESORPTION/DISSOLUTION OF AS IN IRON-BASED TREATMENT MEDIA

EPA Science Inventory

Arsenic concentrations (Total Recoverable As by EPA Method 3051) and solid-phase speciation (by X-ray Absorption Near-Edge Spectroscopy-XANES) were assessed as a function of depth through Fe-media beds for two commercially available products from pilot-scale field tests. These re...

THE DISTRIBUTION, SOLID-PHASE SPECIATION, AND DESORPTION/DISSOLUTION OF AS IN IRON-BASED DRINKING WATER TREATMENT MEDIA - JOURNAL

EPA Science Inventory

Arsenic concentrations (Total Recoverable As by EPA Method 3051, soluble, Toxicity Characteristic Leaching Procedure extractable) and solid-phase speciation (by X-ray Absorption Near-Edge Spectroscopy-XANES) were assessed as a function of depth through Fe-media beds for two comme...

THE DISTRIBUTION AND SOLID-PHASE SPECIATION OF AS IN IRON-BASED TREATMENT MEDIA

EPA Science Inventory

Arsenic concentrations (Total Recoverable As by EPA Method 3051) and solid-phase speciation (by X-ray Absorption Near-Edge Spectroscopy-XANES) were assessed as a function of depth through Fe-media beds for two commercially available products from pilot-scale field tests. These r...

Inductively coupled plasma mass spectrometry study of the retention behavior of arsenic species on various solid phase extraction cartridges and its application in arsenic speciation

NASA Astrophysics Data System (ADS)

Yu, Chunhai; Cai, Qiantao; Guo, Zhong-Xian; Yang, Zhaoguang; Khoo, Soo Beng

2003-07-01

Inductively coupled plasma mass spectrometry (ICP-MS) was used to investigate the retention behavior of arsenite, arsenate, monomethylarsonic acid (MMA), dimethylarsinic acid (DMA), arsenobetaine (AsB), arsenocholine (AsC), trimethylarsine oxide (TMAO) and tetramethylarsonium ion (TMAI) on various silica-based solid phase extraction (SPE) cartridges. A method for arsenic speciation is then developed on the basis of selective SPE separation of arsenic species and highly sensitive ICP-MS detection. Factors affecting the retention and elution of arsenic species were examined. Results showed that the retention of arsenic species depended on the chemical characteristics of arsenic species and the types of sorbent materials. Change of pH in the range of 2.0-9.0 did not show significant effects on the retention of DMA, AsB, AsC, TMAI and TMAO on an ethylbenzene sulfonic acid-based strong cation exchange (SCX-3) cartridge. pH also did not influence the retention of AsB, AsC, TMAI and TMAO on a mixed-mode (M-M) cartridge containing non-polar, strong cation exchange and strong anion exchange (SAX) functional groups. However, the retentions of As(V) and MMA on the SAX and the M-M cartridge changed with pH. As(V) and MMA were completely retained on the SAX cartridge and sequentially selectively eluted with 1.0 mol l -1 acetic acid (for MMA). DMA, AsB, AsC, TMAI and TMAO were completely retained on the SCX-3 cartridge and sequentially selectively eluted with 1.0 mol l -1 HNO 3 (for DMA). As(V), MMA, AsB, AsC, TMAI and TMAO were completely retained on the M-M cartridge. As(III) was not retained on either cartridge and remained in solution. Arsenic species in solution and those eluted from the cartridges were subsequently determined by ICP-MS. A detection limit of 8 ng l -1 arsenic in water sample was obtained. This method was successfully applied to arsenic speciation in various sources of water samples (drinking water, waste water, raw water, etc.) and US National Institute of Standards and Technology standard reference materials with good precision and accuracy.

Tissue-specific distributions of inorganic arsenic and its methylated metabolites, especially in cerebral cortex, cerebellum and hippocampus of mice after a single oral administration of arsenite.

PubMed

Li, Jinlong; Duan, Xiaoxu; Dong, Dandan; Zhang, Yang; Zhao, Lu; Li, Wei; Chen, Jinli; Sun, Guifan; Li, Bing

2017-09-01

Groundwater contaminated with inorganic arsenic (iAs) is the main source of human exposure to arsenic and generates a global health issue. In this study, the urinary excretion, as well as the time-course distributions of various arsenic species in murine tissues, especially in different brain regions were determined after a single oral administration of 2.5, 5, 10 and 20mg/kg sodium arsenite (NaAsO 2 ). Our data showed that the peak times of urinary, hepatic and nephritic total arsenic (TAs) were happened at about 1h, then TAs levels decreased gradually and almost could not be observed after 72h. On contrast, the time course of TAs in lung, urinary bladder and different brain regions exhibited an obvious process of accumulation and elimination,and the peak times were nearly at 6h to 9h. TAs levels of 10 and 20mg/kg NaAsO 2 groups were significantly higher than 2.5 and 5mg/kg groups, and the amounts of TAs in 5mg/kg groups were in the order of liver>lung>kidney>urinary bladder>hippocampus>cerebral cortex>cerebellum. In addition, iAs was the most abundant species in liver and kidney, while lung and urinary bladder accumulated the highest concentrations of dimethylated arsenicals (DMA). What's more, the distributions of arsenic species were not homogeneous among different brain regions, as DMA was the sole species in cerebral cortex and cerebellum, while extremely high concentrations and percentages of monomethylated arsenicals (MMA) were found in hippocampus. These results demonstrated that distributions of iAs and its methylated metabolites were tissue-specific and even not homogeneous among different brain regions, which must be considered as to the tissue- and region-specific toxicity of iAs exposure. Our results thus provide useful information for clarifying and reducing the uncertainty in the risk assessment for this metalloid. Copyright © 2016 Elsevier GmbH. All rights reserved.

EXTRACTION AND SPECIATION OF ARSENIC CONTAINING DRINKING WATER TREATMENT SOLIDS BY IC-ICP-MS

EPA Science Inventory

In 2001, the U.S. Environmental Protection Agency (EPA) passed the Arsenic Rule, which established a maximum contaminant level of 105g/L. Compliance with this regulation has caused a number of drinking water utilities to investigate potential treatment options. The adsorption o...

Elemental Speciation as an Essential Part of Formulating Exposure Assessments that Support Risk Estimates

EPA Science Inventory

The chemical form specific toxicity of arsenic has caused scientists to move toward species specific assessments with an emphasis on biological relevance of an exposure. For example, numerous studies on the occurrence of arsenic in rice have documented the exposure potential fro...

EPA STUDIES OF ARSENIC SPECIATION IN SEAFOOD MATRICES WITH AN EMPHASIS ON EXTRACTABILITY AND ARSENOSUGAR INTEGRITY

EPA Science Inventory

The anthropogenic and geological occurrence of arsenic (As) results in human exposure to a potentially carcinogenic element. The two predominant pathways to As exposure are drinking water (DW) and dietary ingestion (DI). DW exposures are almost exclusively toxic inorganic As. ...

IDENTIFICATION OF INTERSPECIES CONCORDANCE OF MECHANISMS OF ARSENIC INDUCED BLADDER CANCER BY GENE EXPRESSION.

EPA Science Inventory

Arsenic is a human carcinogen that induces urinary bladder cancer. Several mechanisms have been proposed for arsenic-induced cancer. Although inorganic arsenic (iAs) does not induce tumors in adult rodents, dimethylarsinic acid (DMA), a major metabolite of iAs, is a rat bladder c...

PLASMID DNA DAMAGE CAUSED BY METHYLATED ARSENICALS, ASCORBIC ACID AND HUMAN LIVER FERRITIN

EPA Science Inventory

Plasmid DNA damage caused by methylated arsenicals, ascorbic acid and human liver ferritin.

Arsenic causes cancer in human skin, urinary bladder, lung, liver and kidney and is a significant world-wide public health problem. Although the metabolism of inorganic arsenic is ...

MEETING AT CAMBRIDGE, MA: GENE EXPRESSION IN NORMAL HUMAN KERATINOCYTES MODULATED BY TRIVALENT ARSENICALS

EPA Science Inventory

Arsenic exposure has been correlated with the development of several human cancers including those found in the skin, lung, liver, kidney and urinary bladder. Humans are generally exposed to inorganic forms of arsenic, which may be inhaled or ingested. Arsenic forms mono- and d...

MEETING AT SAN DIEGO, CA: GENE EXPRESSION IN NORMAL HUMAN KERATINOCYTES MODULATED BY TRIVALENT ARSENICALS

EPA Science Inventory

Arsenic exposure has been correlated with the development of several human cancers including those found in the skin, lung, liver, kidney and urinary bladder. Humans are generally exposed to inorganic forms of arsenic, which may be inhaled or ingested. Arsenic forms mono- and di-...

Beam-induced redox transformation of arsenic during As K-edge XAS measurements: availability of reducing or oxidizing agents and As speciation.

PubMed

Han, Young Soo; Jeong, Hoon Young; Hyun, Sung Pil; Hayes, Kim F; Chon, Chul Min

2018-05-01

During X-ray absorption spectroscopy (XAS) measurements of arsenic (As), beam-induced redox transformation is often observed. In this study, the As species immobilized by poorly crystallized mackinawite (FeS) was assessed for the susceptibility to beam-induced redox reactions as a function of sample properties including the redox state of FeS and the solid-phase As speciation. The beam-induced oxidation of reduced As species was found to be mediated by the atmospheric O 2 and the oxidation products of FeS [e.g. Fe(III) (oxyhydr)oxides and intermediate sulfurs]. Regardless of the redox state of FeS, both arsenic sulfide and surface-complexed As(III) readily underwent the photo-oxidation upon exposure to the atmospheric O 2 during XAS measurements. With strict O 2 exclusion, however, both As(0) and arsenic sulfide were less prone to the photo-oxidation by Fe(III) (oxyhydr)oxides than NaAsO 2 and/or surface-complexed As(III). In case of unaerated As(V)-reacted FeS samples, surface-complexed As(V) was photocatalytically reduced during XAS measurements, but arsenic sulfide did not undergo the photo-reduction.

Raman spectra of thiolated arsenicals with biological importance.

PubMed

Yang, Mingwei; Sun, Yuzhen; Zhang, Xiaobin; McCord, Bruce; McGoron, Anthony J; Mebel, Alexander; Cai, Yong

2018-03-01

Surface enhanced Raman scattering (SERS) has great potential as an alternative tool for arsenic speciation in biological matrices. SERS measurements have advantages over other techniques due to its ability to maintain the integrity of arsenic species and its minimal requirements for sample preparation. Up to now, very few Raman spectra of arsenic compounds have been reported. This is particularly true for thiolated arsenicals, which have recently been found to be widely present in humans. The lack of data for Raman spectra in arsenic speciation hampers the development of new tools using SERS. Herein, we report the results of a study combining the analysis of experimental Raman spectra with that obtained from density functional calculations for some important arsenic metabolites. The results were obtained with a hybrid functional B3LYP approach using different basis sets to calculate Raman spectra of the selected arsenicals. By comparing experimental and calculated spectra of dimethylarsinic acid (DMA V ), the basis set 6-311++G** was found to provide computational efficiency and precision in vibrational frequency prediction. The Raman frequencies for the rest of organoarsenicals were studied using this basis set, including monomethylarsonous acid (MMA III ), dimethylarsinous acid (DMA III ), dimethylmonothioarinic acid (DMMTA V ), dimethyldithioarsinic acid (DMDTA V ), S-(Dimethylarsenic) cysteine (DMA III (Cys)) and dimethylarsinous glutathione (DMA III GS). The results were compared with fingerprint Raman frequencies from As─O, As─C, and As─S obtained under different chemical environments. These fingerprint vibrational frequencies should prove useful in future measurements of different species of arsenic using SERS. Copyright © 2017 Elsevier B.V. All rights reserved.

Carotid Intima-Media Thickness and Plasma Asymmetric Dimethylarginine in Mexican Children Exposed to Inorganic Arsenic

PubMed Central

Osorio-Yáñez, Citlalli; Ayllon-Vergara, Julio C.; Aguilar-Madrid, Guadalupe; Arreola-Mendoza, Laura; Hernández-Castellanos, Erika; Barrera-Hernández, Angel; De Vizcaya-Ruiz, Andrea

2013-01-01

Background: Arsenic exposure is a risk factor for atherosclerosis in adults, but there is little information on arsenic and early risk biomarkers for atherosclerosis in children. Carotid intima-media thickness (cIMT) is an indicator of subclinical atherosclerotic burden that has been associated with plasma asymmetric dimethylarginine (ADMA), a predictor of cardiovascular disease risk. Objectives: The aim of this study was to investigate associations of arsenic exposure with cIMT, ADMA, and endothelial adhesion molecules [soluble intercellular cell adhesion molecule-1 (sICAM-1); soluble vascular cell adhesion molecule-1 (sVCAM-1)] in children who had been exposed to environmental inorganic arsenic (iAs). Methods: We conducted a cross-sectional study in 199 children 3–14 years of age who were residents of Zimapan, México. We evaluated cIMT using ultrasonography, and plasma lipid profiles by standard methods. We analyzed ADMA, sICAM-1, and sVCAM-1 by ELISA, and measured the concentrations of total speciated arsenic (tAs) in urine using hydride generation cryotrapping atomic absorption spectrometry. Results: In the multiple linear regression model for cIMT, tAs categories were positively associated with cIMT increase. The estimated cIMT diameter was greater in 35- to 70-ng/mL and > 70-ng/mL groups (0.035 mm and 0.058 mm per 1-ng/mL increase in urinary tAs, respectively), compared with the < 35-ng/mL group. In addition to tAs level, plasma ADMA was a significant predictor of cIMT. In the adjusted regression model, cIMT, percent iAs, and plasma sVCAM-1 were significant predictors of ADMA levels (e.g., 0.419-μmol/L increase in ADMA per 1-mm increase in cIMT). Conclusions: Arsenic exposure and plasma ADMA levels were positively associated with cIMT in a population of Mexican children with environmental arsenic exposure through drinking water. Citation: Osorio-Yáñez C, Ayllon-Vergara JC, Aguilar-Madrid G, Arreola-Mendoza L, Hernández-Castellanos E, Barrera-Hernández A, De Vizcaya-Ruíz A, Del Razo LM. 2013. Carotid intima-media thickness and plasma asymmetric dimethylarginine in Mexican children exposed to inorganic arsenic. Environ Health Perspect 121:1090–1096; http://dx.doi.org/10.1289/ehp.1205994 PMID:23757599

Relative Bioavailability and Bioaccessability and Speciation of ...

EPA Pesticide Factsheets

Background: Assessment of soil arsenic (As) bioavailability may profoundly affect the extent of remediation required at contaminated sites by improving human exposure estimates. Because small adjustments in soil As bioavailability estimates can significantly alter risk assessments and remediation goals, convenient, rapid, reliable, and inexpensive tools are needed to determine soil As bioavailability. Objectives: We evaluated inexpensive methods for assessing As bioavailability in soil as a means to improve human exposure estimates and potentially reduce remediation costs. Methods: Nine soils from residential sites affected by mining or smelting activity and two National Institute of Standards and Technology standard reference materials were evaluated for As bioavailability, bioaccessibility, and speciation. Arsenic bioavailability was determined using an in vivo mouse model, and As bioaccessibility was determined using the Solubility/Bioavailability Research Consortium in vitro assay. Arsenic speciation in soil and selected soil physicochemical properties were also evaluated to determine whether these parameters could be used as predictors of As bio¬availability and bioaccessibility. Results: In the mouse assay, we compared bioavailabilities of As in soils with that for sodium arsenate. Relative bioavailabilities (RBAs) of soil As ranged from 11% to 53% (mean, 33%). In vitro soil As bioaccessibility values were strongly correlated with soil As RBAs (R

Arsenic accumulation and speciation in rice are affected by root aeration and variation of genotypes.

PubMed

Wu, Chuan; Ye, Zhihong; Shu, Wensheng; Zhu, Yongguan; Wong, Minghung

2011-05-01

Root aeration, arsenic (As) accumulation, and speciation in rice of 20 different genotypes with regular irrigation of water containing 0.4 mg As l(-1) were investigated. Different genotypes had different root anatomy demonstrated by entire root porosity (ranging from 12.43% to 33.21%), which was significantly correlated with radial oxygen loss (ROL) (R=0.64, P<0.01). Arsenic accumulation differed between genotypes, but there were no significant differences between Indica and Japonica subspecies, as well as paddy and upland rice. Total ROL from entire roots was correlated with metal tolerance (expressed as percentage mean of control straw biomass, R=0.69, P<0.01) among the 20 genotypes; total As concentration (R=-0.67, P<0.01) and inorganic As concentration (R=-0.47, P<0.05) in rice grains of different genotypes were negatively correlated with ROL. There were also significant genotype effects in percentage inorganic As (F=15.8, P<0.001) and percentage cacodylic acid (F=22.1, P<0.001), respectively. Root aeration of different genotypes and variation of genotypes on As accumulation and speciation would be useful for selecting genotypes to grow in areas contaminated by As.

Release of Arsenic to the Environment from CCA-Treated Wood: Part II – Leaching and Speciation during Disposal

PubMed Central

KHAN, BERNINE I.; JAMBECK, JENNA; SOLO-GABRIELE, HELENA M.; TOWNSEND, TIMOTHY G.; CAI, YONG

2008-01-01

Wood treated with chromated copper arsenate (CCA) is primarily disposed within construction and demolition (C&D) debris landfills, with wood monofills and municipal solid waste (MSW) landfills as alternative disposal options. This study evaluated the extent and speciation of arsenic leaching from landfills containing CCA-treated wood. In control lysimeters where untreated wood was used, DMAA represented the major arsenic species. The dominant arsenic species differed in the lysimeters containing CCA-treated wood, with As(V) greatest in the monofill and C&D lysimeters and As(III) greatest in the MSW lysimeters. In CCA-containing lysimeters, the organoarsenic species MMAA and DMAA were virtually absent in the monofill lysimeter and observed in the C&D and MSW lysimeters. Overall arsenic leaching rate varied for the wood monofill (0.69% per meter of water added), C&D (0.36% per m), and MSW (0.84% per m) lysimeters. Utilizing these rates with annual disposal data, a mathematical model was developed to quantify arsenic leaching from CCA-treated wood disposed to Florida landfills. Model findings showed between 20 to 50 metric tons of arsenic (depending on lysimeter type) had leached prior to 2000 with an expected increase between 350 to 830 metric tons by 2040. Groundwater analysis from 21 Florida C&D landfills suspected of accepting CCA-treated wood showed that groundwater at 3 landfills were characterized by elevated arsenic concentrations with only 1 showing impacts from the C&D waste. The slow release of arsenic from disposed treated wood may account for the lack of significant impact to groundwater near most C&D facilities at this time. However, greater impacts are anticipated in the future given that the maximum releases of arsenic are expected by the year 2100. PMID:16509348

Hypomethylation of inflammatory genes (COX2, EGR1, and SOCS3) and increased urinary 8-nitroguanine in arsenic-exposed newborns and children

DOE Office of Scientific and Technical Information (OSTI.GOV)

Phookphan, Preeyaphan; Navasumrit, Panida

Early-life exposure to arsenic increases risk of developing a variety of non-malignant and malignant diseases. Arsenic-induced carcinogenesis may be mediated through epigenetic mechanisms and pathways leading to inflammation. Our previous study reported that prenatal arsenic exposure leads to increased mRNA expression of several genes related to inflammation, including COX2, EGR1, and SOCS3. This study aimed to investigate the effects of arsenic exposure on promoter DNA methylation and mRNA expression of these inflammatory genes (COX2, EGR1, and SOCS3), as well as the generation of 8-nitroguanine, which is a mutagenic DNA lesion involved in inflammation-related carcinogenesis. Prenatally arsenic-exposed newborns had promoter hypomethylationmore » of COX2, EGR1, and SOCS3 in cord blood lymphocytes (p < 0.01). A follow-up study in these prenatally arsenic-exposed children showed a significant hypomethylation of these genes in salivary DNA (p < 0.01). In vitro experiments confirmed that arsenite treatment at short-term high doses (10–100 μM) and long-term low doses (0.5–1 μM) in human lymphoblasts (RPMI 1788) caused promoter hypomethylation of these genes, which was in concordance with an increase in their mRNA expression. Additionally, the level of urinary 8-nitroguanine was significantly higher (p < 0.01) in exposed newborns and children, by 1.4- and 1.8-fold, respectively. Arsenic accumulation in toenails was negatively correlated with hypomethylation of these genes and positively correlated with levels of 8-nitroguanine. These results indicated that early-life exposure to arsenic causes hypomethylation of COX2, EGR1, and SOCS3, increases mRNA expression of these genes, and increases 8-nitroguanine formation. These effects may be linked to mechanisms of arsenic-induced inflammation and cancer development later in life. - Highlight: • Early-life arsenic exposure caused promoter hypomethylation of COX2, EGR1 and SOCS3. • Hypomethylation of these genes is associated with increased mRNA expression. • Arsenite treatment in vitro showed hypomethylation and increased mRNA expression. • Arsenic-exposed newborns and children had higher levels of urinary 8-nitroguanine. • Urinary 8-nitroguanine correlated with hypomethylation and mRNA expression.« less

Arsenic methylation and skin lesions in migrant and native adult women with chronic exposure to arsenic from drinking groundwater.

PubMed

Wei, Binggan; Yu, Jiangping; Yang, Linsheng; Li, Hairong; Chai, Yuanqing; Xia, Yajuan; Wu, Kegong; Gao, Jianwei; Guo, Zhiwei; Cui, Na

2017-02-01

In order to figure out the prevalence of skin lesions and methylation capacity for migrant and native adult women in an endemic area for arsenic poisoning in Inner Mongolia, China, 207 adult women were selected for study subjects. The results showed that the prevalence of skin lesions for the external group, provincial group and native group was 36.54, 26.15 and 35.56 %, respectively. The nail content of arsenic and urinary concentrations of dimethylarsenic (DMA), monomethylarsenic (MMA) and inorganic arsenic (iAs) were significantly higher in women with skin lesions than in those without skin lesions. The highest urinary concentrations of DMA, MMA and iAs were 213.93, 45.72 and 45.01 μg/L in the native group. The arsenic methylation capacity index revealed that the external group had the greatest capacity, while the native group had the lowest. The odds ratios of skin lesions in relation to arsenic metabolites and arsenic methylation capacity varied widely among the three groups. Urinary MMA and iAs concentrations were positively associated with risk of skin lesions in the three groups of adult women, while primary and secondary methylation capacities were negatively related to risk of skin lesions in native and provincial groups. The external group might be more susceptible to MMA and iAs, while the provincial and native groups were more tolerance to MMA and iAs. Lower primary and secondary arsenic methylation capacities increased the risk of skin lesions in native and provincial groups. Moreover, higher nail arsenic concentration increased the risk of skin lesions of adult women.

Risk assessment and pathway study of arsenic in industrially contaminated sites of Hyderabad: a case study.

PubMed

Chandra Sekhar, K; Chary, N S; Kamala, C T; Venkateswara Rao, J; Balaram, V; Anjaneyulu, Y

2003-08-01

Different areas in the industrial region of Patancheru near Hyderabad, Andhra Pradesh (A.P), India are contaminated with high concentration of arsenic, which is attributed to industrial source like veterinary chemicals, pharmaceuticals, pesticide industries, etc. Fourteen villages of this area of Patancheru were assessed for arsenic contamination by collecting samples of water (surface and ground), soil, fodder, milk, and vegetables. The total arsenic content in the whole blood, urine, hair, and nails of the residents showing arsenical skin lesions and other clinical manifestations were also studied. To understand the bioavailability of arsenic in this environment and its possible entry into human food chain, speciation studies of arsenic was carried out and the results are presented in this paper.

Extraction and speciation of arsenic in lacustrine sediments

USGS Publications Warehouse

Ficklin, W.H.

1990-01-01

Arsenic was partially extracted with 4.OM hydrochloric acid, from samples collected at 25-cm intervals in a 350-cm column of sediment at Milltown Reservoir, Montana and from a 60-cm core of sediment collected at the Cheyenne River Embayment of Lake Oahe, South Dakota. The sediment in both reservoirs is highly contaminated with arsenic. The extracted arsenic was separated into As(III) and As(V) on acetate form Dowex 1-X8 ion-exchange resin with 0.12M HCl eluent. Residual arsenic was sequentially extracted with KClO3 and HCl. Arsenic was determined by graphite-furnace atomic-absorption spectrometry. The analytical results define oxidized and reduced zones in the sediment columns. ?? 1990.

Blood Pressure Associated with Arsenic Methylation and Arsenic Metabolism Caused by Chronic Exposure to Arsenic in Tube Well Water.

PubMed

Wei, Bing Gan; Ye, Bi Xiong; Yu, Jiang Ping; Yang, Lin Sheng; Li, Hai Rong; Xia, Ya Juan; Wu, Ke Gong

2017-05-01

The effects of arsenic exposure from drinking water, arsenic metabolism, and arsenic methylation on blood pressure (BP) were observed in this study. The BP and arsenic species of 560 participants were determined. Logistic regression analysis was applied to estimate the odds ratios of BP associated with arsenic metabolites and arsenic methylation capability. BP was positively associated with cumulative arsenic exposure (CAE). Subjects with abnormal diastolic blood pressure (DBP), systolic blood pressure (SBP), and pulse pressure (PP) usually had higher urinary iAs (inorganic arsenic), MMA (monomethylated arsenic), DMA (dimethylated arsenic), and TAs (total arsenic) than subjects with normal DBP, SBP, and PP. The iAs%, MMA%, and DMA% differed slightly between subjects with abnormal BP and those with normal BP. The PMI and SMI were slightly higher in subjects with abnormal PP than in those with normal PP. Our findings suggest that higher CAE may elevate BP. Males may have a higher risk of abnormal DBP, whereas females have a higher risk of abnormal SBP and PP. Higher urinary iAs may increase the risk of abnormal BP. Lower PMI may elevate the BP. However, higher SMI may increase the DBP and SBP, and lower SMI may elevate the PP. Copyright © 2017 The Editorial Board of Biomedical and Environmental Sciences. Published by China CDC. All rights reserved.

RECENT ADVANCES IN ARSENIC CARCINOGENESIS: MODES OF ACTION, ANIMAL MODEL SYSTEMS AND METHYLATED ARSENIC METABOLITES

EPA Science Inventory

Abstract:

Recent advances in our knowledge of arsenic carcinogenesis include the development of rat or mouse models for all human organs in which inorganic arsenic is known to cause cancer -skin, lung, urinary bladder, liver and kidney. Tumors can be produced from eit...

Arsenic speciation in biological samples using XAS and mixed oxidation state calibration standards of inorganic arsenic.

PubMed

Parsons, J G; Lopez, M L; Castillo-Michel, H; Peralta-Videa, J R; Gardea-Torresdey, J L

2009-08-01

The speciation of elements without pre-edge features preformed with X-ray absorption near edge structure (XANES) can lead to problems when the energy difference between two species is small. The speciation of arsenic (As) in plant samples was investigated using the mixtures As2S3/As2O5, As2S3/As2O3, or As2O3/As2O5. The data showed that the energy separation (eV) between As2O5 and As2S3 was 5.8, between As2O3 and As2O5 was 3.6, and between As2S3 and As2O3 was 2.1. From the intensity of the white-line feature and the concentration of As species, calibration curves showing a limit of detection of approximately 10% were generated. In addition, an error of +/-10% was determined for the linear combination-XANES (LC-XANES) fitting technique. The difference between the LC-XANES fittings and calculations from the calibration curves was <10%. The data also showed that the speciation of As in a sample can be determined using EXAFS (extended X-ray absorption fine structure). Finally, it was also shown that both EXAFS and XANES of the sample should be examined to determine the true speciation of an element. Even though there is a difference of 2 eV between As(III) bound to O and As(III) bound to S, in the EXAFS region the As(III)-S and As(III)-O ligands are clearly visible. However, distinction between the As(III)-O and As(V)-O ligands in the EXAFS spectra was not clearly visible in this study.

Coupled high performance liquid chromatography-microwave digestion-hydride generation-atomic absorption spectrometry for inorganic and organic arsenic speciation in fish tissue.

PubMed

Villa-Lojo, M C; Alonso-Rodríguez, E; López-Mahía, P; Muniategui-Lorenzo, S; Prada-Rodríguez, D

2002-06-10

A high performance liquid chromatography-microwave digestion-hydride generation-atomic absorption spectrometry (HPLC-MW-HG-AAS) coupled method is described for As(III), As(V), monomethylarsonic acid (MMA), dimethylarsinic acid (DMA), arsenobetaine (AsB) and arsenocholine (AsC) determination. A Hamilton PRP-X100 anion-exchange column is used for carrying out the arsenic species separation. As mobile phase 17 mM phosphate buffer (pH 6.0) is used for As(III), As(V), MMA and DMA separation, and ultrapure water (pH 6.0) for AsB and AsC separation. Prior to injection into the HPLC system AsB and AsC are isolated from the other arsenic species using a Waters Accell Plus QMA cartridge. A microwave digestion with K(2)S(2)O(8) as oxidizing agent is used for enhancing the efficiency of conversion of AsB and AsC into arsenate. Detection limits achieved were between 0.3 and 1.1 ng for all species. The method was applied to arsenic speciation in fish samples.

Arsenic Exposure and Impaired Lung Function. Findings from a Large Population-based Prospective Cohort Study

PubMed Central

Parvez, Faruque; Chen, Yu; Yunus, Mahbub; Olopade, Christopher; Segers, Stephanie; Slavkovich, Vesna; Argos, Maria; Hasan, Rabiul; Ahmed, Alauddin; Islam, Tariqul; Akter, Mahmud M.; Graziano, Joseph H.

2013-01-01

Rationale: Exposure to arsenic through drinking water has been linked to respiratory symptoms, obstructive lung diseases, and mortality from respiratory diseases. Limited evidence for the deleterious effects on lung function exists among individuals exposed to a high dose of arsenic. Objectives: To determine the deleterious effects on lung function that exist among individuals exposed to a high dose of arsenic. Methods: In 950 individuals who presented with any respiratory symptom among a population-based cohort of 20,033 adults, we evaluated the association between arsenic exposure, measured by well water and urinary arsenic concentrations measured at baseline, and post-bronchodilator–administered pulmonary function assessed during follow-up. Measurements and Main Results: For every one SD increase in baseline water arsenic exposure, we observed a lower level of FEV1 (−46.5 ml; P < 0.0005) and FVC (−53.1 ml; P < 0.01) in regression models adjusted for age, sex, body mass index, smoking, socioeconomic status, betel nut use, and arsenical skin lesions status. Similar inverse relationships were observed between baseline urinary arsenic and FEV1 (−48.3 ml; P < 0.005) and FVC (−55.2 ml; P < 0.01) in adjusted models. Our analyses also demonstrated a dose-related decrease in lung function with increasing levels of baseline water and urinary arsenic. This association remained significant in never-smokers and individuals without skin lesions, and was stronger in male smokers. Among male smokers and individuals with skin lesions, every one SD increase in water arsenic was related to a significant reduction of FEV1 (−74.4 ml, P < 0.01; and −116.1 ml, P < 0.05) and FVC (−72.8 ml, P = 0.02; and −146.9 ml, P = 0.004), respectively. Conclusions: This large population-based study confirms that arsenic exposure is associated with impaired lung function and the deleterious effect is evident at low- to moderate-dose range. PMID:23848239

Arsenic speciation in fish from Greek coastal areas.

PubMed

Kalantzi, Ioanna; Mylona, Kyriaki; Sofoulaki, Katerina; Tsapakis, Manolis; Pergantis, Spiros A

2017-06-01

Arsenic speciation analysis was conducted on fish samples (sardine and anchovy) collected from six areas along the Greek coastline, i.e. Artemisium Straits, Thermaikos Gulf, Amvrakikos Gulf, Strymonian Gulf, Thracian Sea, and Elefsina Gulf. Total arsenic levels ranging from 11.8 to 62.6mg As/kg dry weight were determined. Arsenobetaine, a non-toxic form of arsenic, was found to be the main arsenic species, present at 8.6 to 58.8mg As/kg dry weight, accounting for 67-95% of the total arsenic. Also detected in all fish samples was dimethylarsinic acid, although at considerably lower concentrations, ranging from 0.072-0.956mg As/kg dry weight. Monomethylarsonic acid was detected at low levels in all anchovy samples, and only in sardines from one area. Finally, inorganic arsenic in the form of arsenate was detected only in fish at one area, indicating the possible effect of an environmental parameter on its presence at detectable amounts. Statistical analysis revealed the environmental variables, such as salinity, total organic carbon and nitrogen, ammonium, phosphate, total phosphorus, dissolved oxygen and pressure index, are potentially correlated to As species concentrations. Furthermore, based on factor analysis, the biological parameters, such as fish weight, lipids, protein and ash content, that are correlated to As species concentrations of fish were also identified. The interrelationship of arsenobetaine and dimethylarsinic acid concentrations within each fish species was evaluated. Copyright © 2017. Published by Elsevier B.V.

Renin–angiotensin–aldosterone system related gene polymorphisms and urinary total arsenic is related to chronic kidney disease

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Wei-Jen; Huang, Ya-Li; Shiue, Horng-Sheng

A recent study demonstrated that an increased risk of chronic kidney disease (CKD) was associated with high urinary total arsenic levels. However, whether genomic instability is related to CKD remains unclear. An association between CKD and genetic polymorphisms of regulation enzymes of the renin–angiotensin–aldosterone system (RAAS), such as angiotensin-converting enzyme (ACE), angiotensinogen (AGT), angiotensin II type I receptor (AT1R), and aldosterone synthase (CYP11B2) has not been shown. The aim of the present study was to investigate the relationship between arsenic, genetic polymorphisms of RAAS enzymes and CKD. A total of 233 patients and 449 age- and gender-matched controls were recruitedmore » from the Taipei Medical University Hospital, Taipei Municipal Wan Fang Hospital and the Shin Kong Wu Ho-Su Memorial Hospital. Concentrations of urinary arsenic were determined by a high-performance liquid chromatography-linked hydride generator, and atomic absorption spectrometry. Polymorphisms of ACE(I/D), AGT(A[− 20]C), (T174M), (M235T), AT1R(A1166C) and CYP11B2(C[− 344]T) were examined by polymerase chain reaction and restriction fragment length polymorphism. Subjects carrying the CYP11B2 TT genotype had a higher odds ratio (OR), 1.39 (0.96–2.01), of CKD; while those with the AGT(A[− 20]C) CC genotype had an inverse OR of CKD (0.20 (0.05–0.81)), and a high-risk genotype was defined as A/A + A/C for AGT(A[− 20C]) and T/T for CYP11B2(C[− 344]T). The trend test showed a higher OR for CKD in patients who had either high urinary total arsenic levels or carried the high-risk genotype, or both, compared to patients with low urinary total arsenic levels, who carried the low-risk genotype, and could also be affected by the hypertension or diabetes status. - Highlights: • AGT(− 20 C) and CYP11B2(− 344 T) genotypes were significantly associated with CKD. • Combined effect of high-risk genotypes and high urinary total arsenic on OR of CKD. • Combined effect on the CKD was modified by the hypertension and diabetes status.« less

Association between arsenic exposure from drinking water and hematuria: Results from the Health Effects of Arsenic Longitudinal Study

DOE Office of Scientific and Technical Information (OSTI.GOV)

McClintock, Tyler R.; Department of Environmental Medicine, New York University School of Medicine, New York, NY; Department of Urology, New York University School of Medicine, New York, NY

2014-04-01

Arsenic (As) exposure has been associated with both urologic malignancy and renal dysfunction; however, its association with hematuria is unknown. We evaluated the association between drinking water As exposure and hematuria in 7843 men enrolled in the Health Effects of Arsenic Longitudinal Study (HEALS). Cross-sectional analysis of baseline data was conducted with As exposure assessed in both well water and urinary As measurements, while hematuria was measured using urine dipstick. Prospective analyses with Cox proportional regression models were based on urinary As and dipstick measurements obtained biannually since baseline up to six years. At baseline, urinary As was significantly relatedmore » to prevalence of hematuria (P-trend < 0.01), with increasing quintiles of exposure corresponding with respective prevalence odds ratios of 1.00 (reference), 1.29 (95% CI: 1.04–1.59), 1.41 (95% CI: 1.15–1.74), 1.46 (95% CI: 1.19–1.79), and 1.56 (95% CI: 1.27–1.91). Compared to those with relatively little absolute urinary As change during follow-up (− 10.40 to 41.17 μg/l), hazard ratios for hematuria were 0.99 (95% CI: 0.80–1.22) and 0.80 (95% CI: 0.65–0.99) for those whose urinary As decreased by > 47.49 μg/l and 10.87 to 47.49 μg/l since last visit, respectively, and 1.17 (95% CI: 0.94–1.45) and 1.36 (95% CI: 1.10–1.66) for those with between-visit increases of 10.40 to 41.17 μg/l and > 41.17 μg/l, respectively. These data indicate a positive association of As exposure with both prevalence and incidence of dipstick hematuria. This exposure effect appears modifiable by relatively short-term changes in drinking water As. - Highlights: • Hematuria is the most common symptom of urinary tract disease. • Arsenic exposure is associated with renal dysfunction and urologic malignancy. • Water arsenic was positively associated with prevalence and incidence of hematuria. • Reduction in exposure lowered hematuria risk especially in low-to-moderate exposed. • Arsenic-related hematuria may represent nonmalignant or premalignant condition.« less

Speciation analysis of inorganic arsenic by magnetic solid phase extraction on-line with inductively coupled mass spectrometry determination.

PubMed

Montoro Leal, P; Vereda Alonso, E; López Guerrero, M M; Cordero, M T Siles; Cano Pavón, J M; García de Torres, A

2018-07-01

Arsenic, one of the main environmental pollutants and potent natural poison, is a chemical element that is spread throughout the Earth's crust. It is well known that the toxicity of arsenic is highly dependent on its chemical forms. Generally, the inorganic species are more toxic than its organics forms, and As(III) is 60 times more toxic than As(V). In environmental waters, arsenic exists predominantly in two chemical forms: As(III) and As(V). In view of these facts, fast, sensitive, accurate and simple analytical methods for the speciation of inorganic arsenic in environmental waters are required. In this work, a new magnetic solid phase extraction with a hydride generation system was coupled on line with inductively coupled plasma mass spectrometry (MSPE-HG-ICP-MS). The new system was based on the retention of As(III) and As(V) in two knotted reactors filled with (Fe 3 O 4 ) magnetic nanoparticles functionalized with [1,5-bis (2-pyridyl) 3-sulfophenylmethylene] thiocarbonohydrazide (PSTH-MNPs). As(III) and total inorganic As were sequentially eluted in different reduction conditions. The concentration of As(V) was obtained by subtracting As(III) from total As. The system runs in a fully automated way and the method has proved to have a wide linear range and to be precise, sensitive and fast. The detection limits found were 2.7 and 3.2 ng/L for As(III) and total As, respectively; with relative standard deviations (RSDs) of 2.5% and 2.7% and a sample throughput of 14.4 h -1 . In order to validate the developed method, several certified reference samples of environmental waters including sea water, were analyzed and the determined values were in good agreement with the certified values. The proposed method was successfully applied to the speciation analysis of inorganic arsenic in well-water and sea water. Copyright © 2018 Elsevier B.V. All rights reserved.

COMPARATIVE TISSUE DISTRIBUTION AND URINARY EXCRETION OF INORGANIC ARSENIC (IAS) AND ITS METHYLATED METABOLITES IN MICE FOLLOWING ORAL ADMINISTRATION OF ARSENATE (ASV) AND ARSENITE (ASIII)

EPA Science Inventory

COMPARATIVE TISSUE DISTRIBUTION AND URINARY EXCRETION OF INORGANIC ARSENIC (iAs) AND ITS METHYLATED METABOLITES IN MICE FOLLOWING ORAL ADMINISTRATION OF ARSENATE (AsV) AND ARSENITE (AsIII). E M Kenyon, L M Del Razo and M F Hughes. U.S. EPA, ORD, NHEERL, ETD, PKB, RTP, NC, USA; ...

Transcriptomic Responses During Early Development Following Arsenic Exposure in Western Clawed Frogs, Silurana tropicalis.

PubMed

Zhang, Jing; Koch, Iris; Gibson, Laura A; Loughery, Jennifer R; Martyniuk, Christopher J; Button, Mark; Caumette, Guilhem; Reimer, Kenneth J; Cullen, William R; Langlois, Valerie S

2015-12-01

Arsenic compounds are widespread environmental contaminants and exposure elicits serious health issues, including early developmental anomalies. Depending on the oxidation state, the intermediates of arsenic metabolism interfere with a range of subcellular events, but the fundamental molecular events that lead to speciation-dependent arsenic toxicity are not fully elucidated. This study therefore assesses the impact of arsenic exposure on early development by measuring speciation and gene expression profiles in the developing Western clawed frog (Silurana tropicalis) larvae following the environmental relevant 0.5 and 1 ppm arsenate exposure. Using HPLC-ICP-MS, arsenate, dimethylarsenic acid, arsenobetaine, arsenocholine, and tetramethylarsonium ion were detected. Microarray and pathway analyses were utilized to characterize the comprehensive transcriptomic responses to arsenic exposure. Clustering analysis of expression data showed distinct gene expression patterns in arsenate treated groups when compared with the control. Pathway enrichment revealed common biological themes enriched in both treatments, including cell signal transduction, cell survival, and developmental pathways. Moreover, the 0.5 ppm exposure led to the enrichment of pathways and biological processes involved in arsenic intake or efflux, as well as histone remodeling. These compensatory responses are hypothesized to be responsible for maintaining an in-body arsenic level comparable to control animals. With no appreciable changes observed in malformation and mortality between control and exposed larvae, this is the first study to suggest that the underlying transcriptomic regulations related to signal transduction, cell survival, developmental pathways, and histone remodeling may contribute to maintaining ongoing development while coping with the potential arsenic toxicity in S. tropicalis during early development. © The Author 2015. Published by Oxford University Press on behalf of the Society of Toxicology. All rights reserved. For Permissions, please e-mail: journals.permissions@oup.com.

Influence of water management on the active root-associated microbiota involved in arsenic, iron, and sulfur cycles in rice paddies.

PubMed

Zecchin, Sarah; Corsini, Anna; Martin, Maria; Cavalca, Lucia

2017-09-01

In recent years, the role of microorganisms inhabiting rice rhizosphere in promoting arsenic contamination has emerged. However, little is known concerning the species and metabolic properties involved in this phenomenon. In this study, the influence of water management on the rhizosphere microbiota in relation to arsenic dissolution in soil solution was tested. Rice plants were cultivated in macrocosms under different water regimes: continuous flooding, continuous flooding with a 2-week period drainage before flowering, and dry soil watered every 10 days. The active bacterial communities in rhizosphere soil and in rhizoplane were characterized by 16S rRNA pyrosequencing. An in-depth analysis of microbial taxa with direct or indirect effects on arsenic speciation was performed and related contribution was evaluated. Continuous flooding promoted high diversity in the rhizosphere, with the plant strongly determining species richness and evenness. On the contrary, under watering the communities were uniform, with little differences between rhizosphere soil and rhizoplane. Arsenic-releasing and arsenite-methylating bacteria were selected by continuous flooding, where they represented 8% of the total. On the contrary, bacteria decreasing arsenic solubility were more abundant under watering, with relative abundance of 10%. These values reflected arsenic concentrations in soil solution: 135 μg L -1 and negligible in continuous flooding and under watering, respectively. When short-term drainage was applied before flowering, intermediate conditions were achieved. This evidence strongly indicates an active role of the rhizosphere microbiota in driving arsenic biogeochemistry in rice paddies, influenced by water management, explaining amounts and speciation of arsenic often found in rice grains.

Speciation of arsenic in pyrite by micro-X-ray absorption fine- structure spectroscopy (XAFS)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Paktunc, D.

2008-09-30

Pyrite (FeS2) often contains variable levels of arsenic, regardless of the environment of formation. Arsenian pyrite has been reported in coals, sediments and ore deposits. Arsenian pyrite having As concentrations of up to 10 wt % in sedimentary rocks (Kolker et al. 1997), about 10 wt% in gold deposits (Fleet et al. 1993), 12 wt % in a refractory gold ore (Paktunc et al. 2006) and 20 wt % in a Carlin-type gold deposit in Nevada (Reich et al. 2005) have been reported. Arsenian pyrite is the carrier of gold in hydrothermal Carlin-type gold deposits, and gold concentrations of upmore » to 0.9 wt % have been reported (Reich et al. 2005; Paktunc et al. 2006). In general, high Au concentrations correlate with As-rich zones in pyrite (Paktunc et al. 2006). Pyrite often ends up in mining and metallurgical wastes as an unwanted mineral and consititutes one of the primary sources of As in the wastes. Arsenic can be readily released to the environment due to rapid oxidative dissolution of host pyrite under atmospheric conditions. Pyrite is also the primary source of arsenic in emissions and dust resulting from combustion of bituminous coals. Despite the importance of arsenian pyrite as a primary source of anthropogenic arsenic in the environment and its economic significance as the primary carrier of gold in Carlin-type gold deposits, our understanding of the nature of arsenic in pyrite is limited. There are few papers dealing with the mode of occurrence of arsenic by bulk XAFS in a limited number of pyrite-bearing samples. The present study documents the analysis of pyrite particles displaying different morphologies and a range of arsenic and gold concentrations to determine the nature and speciation of arsenic.« less

Assessment of total arsenic and arsenic species stability in alga samples and their aqueous extracts.

PubMed

García Salgado, S; Quijano Nieto, M A; Bonilla Simón, M M

2008-05-30

In order to achieve reliable information on speciation analysis, it is necessary to assess previously the species stability in the sample to analyse. Furthermore, in those cases where the sample treatment for species extraction is time-consuming, an assessment of the species integrity in the extracts is of paramount importance. Thus, the present paper reports total arsenic and arsenic species stability in alga samples (Sargassum fulvellum and Hizikia fusiformis), as well as in their aqueous extracts, which were stored in amber glass and polystyrene containers at different temperatures. Total arsenic determination was carried out by inductively coupled plasma atomic emission spectroscopy (ICP-AES), after sample acid digestion in a microwave oven, while arsenic speciation was conducted by anion exchange high performance liquid chromatography on-line coupled to ICP-AES, with and without sample introduction by hydride generation (HPLC-ICP-AES and HPLC-HG-ICP-AES), after aqueous microwave-assisted extraction. The results obtained for solid alga samples showed that total arsenic (for Hijiki alga) and arsenic species present (As(V) for Hijiki and NIES No. 9 Sargasso) are stable for at least 12 months when samples are stored in polystyrene containers at +20 degrees C. On the other hand, a different behaviour was observed in the stability of total arsenic and As(V) species in aqueous extracts for both samples, being the best storage conditions for Sargasso extracts a temperature of -18 degrees C and polystyrene containers, under which they are stable for at least 15 days, while Hijiki extracts must be stored in polystyrene containers at +4 degrees C in order to ensure the stability for 10 days.

A STUDY OF THE INTERCONVERSION OF METHYLATED ARSENIC OXIDES TO METHYLATED ARSENIC SULFIDES IN SOLUTIONS CONTAINING FREE SULFIDE

EPA Science Inventory

Evidence suggests that thiolated arsenicals are urinary metabolites in both humans and rats. These thiolated species may be formed in the digestive system or as metabolites within the body. The role they may play in the overall toxicity of arsenic is an active area of research....

Arsenic Metabolism in Children Differs From That in Adults

PubMed Central

Skröder Löveborn, Helena; Lu, Ying; Ahmed, Sultan; Kuehnelt, Doris; Raqib, Rubhana; Vahter, Marie

2016-01-01

Arsenic toxicity in adults is associated with methylation efficiency, influenced by factors such as gender, genetics, and nutrition. The aim of this study was to evaluate influencing factors for arsenic metabolism in children. For 488 children (9 years), whose mothers participated in a study on arsenic exposure during pregnancy (nested into the MINIMat trial) in rural Bangladesh, we measured urinary concentrations of inorganic arsenic (iAs) and its metabolites methylarsonic acid (MMA) and dimethylarsinic acid (DMA) by HPLC-HG-ICPMS. Methylation efficiency was assessed by relative amounts (%) of the metabolites. We evaluated the impact of factors such as maternal urinary metabolite pattern, arsenic exposure, gender, socioeconomic status, season of sampling, and nutritional factors, including erythrocyte selenium (Ery-Se), and plasma folate and vitamin B12. Children had higher %DMA and lower %iAs in urine compared to their mothers, unrelated to their lower exposure [median urinary arsenic (U-As) 53 vs 78 µg/l]. Surprisingly, selenium status (Ery-Se) was strongly associated with children’s arsenic methylation; an increase in Ery-Se from the 5–95th percentile was associated with: +1.8 percentage points (pp) for %iAs (P  =  .001), +1.4 pp for %MMA (P  =  .003), and −3.2 pp for %DMA (P  <  .001). Despite this, Ery-Se was positively associated with U-As (5–95th percentile: +41 µg/l, P  =  .026). As expected, plasma folate was inversely associated with %iAs (5–95th percentile: −1.9 pp, P  =  .001) and positively associated with %DMA (5–95th percentile: +2.2 pp, P  =  .008). Children methylated arsenic more efficiently than their mothers. Also influencing factors, mainly selenium and folate, differed. This warrants further research. PMID:27056082

AS3MT, GSTO, and PNP polymorphisms: impact on arsenic methylation and implications for disease susceptibility.

PubMed

Antonelli, Ray; Shao, Kan; Thomas, David J; Sams, Reeder; Cowden, John

2014-07-01

Oral exposure to inorganic arsenic (iAs) is associated with adverse health effects. Epidemiological studies suggest differences in susceptibility to these health effects, possibly due to genotypic variation. Genetic polymorphisms in iAs metabolism could lead to increased susceptibility by altering urinary iAs metabolite concentrations. To examine the impact of genotypic polymorphisms on iAs metabolism. We screened 360 publications from PubMed and Web of Science for data on urinary mono- and dimethylated arsenic (MMA and DMA) percentages and polymorphic genes encoding proteins that are hypothesized to play roles in arsenic metabolism. The genes we examined were arsenic (+3) methyltransferase (AS3MT), glutathione-s-transferase omega (GSTO), and purine nucleoside phosphorylase (PNP). Relevant data were pooled to determine which polymorphisms are associated across studies with changes in urinary metabolite concentration. In our review, AS3MT polymorphisms rs3740390, rs11191439, and rs11191453 were associated with statistically significant changes in percent urinary MMA. Studies of GSTO polymorphisms did not indicate statistically significant associations with methylation, and there are insufficient data on PNP polymorphisms to evaluate their impact on metabolism. Collectively, these data support the hypothesis that AS3MT polymorphisms alter in vivo metabolite concentrations. Preliminary evidence suggests that AS3MT genetic polymorphisms may impact disease susceptibility. GSTO polymorphisms were not associated with iAs-associated health outcomes. Additional data are needed to evaluate the association between PNP polymorphisms and iAs-associated health outcomes. Delineation of these relationships may inform iAs mode(s) of action and the approach for evaluating low-dose health effects for iAs. Genotype impacts urinary iAs metabolite concentrations and may be a potential mechanism for iAs-related disease susceptibility. Published by Elsevier Inc.

Interaction between arsenic exposure from drinking water and genetic susceptibility in carotid intima–media thickness in Bangladesh

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wu, Fen; Department of Environmental Medicine, New York University School of Medicine, New York, NY; Jasmine, Farzana

Epidemiologic studies that evaluated genetic susceptibility for the effects of arsenic exposure from drinking water on subclinical atherosclerosis are limited. We conducted a cross-sectional study of 1078 participants randomly selected from the Health Effects of Arsenic Longitudinal Study in Bangladesh to evaluate whether the association between arsenic exposure and carotid artery intima–media thickness (cIMT) differs by 207 single-nucleotide polymorphisms (SNPs) in 18 genes related to arsenic metabolism, oxidative stress, inflammation, and endothelial dysfunction. Although not statistically significant after correcting for multiple testing, nine SNPs in APOE, AS3MT, PNP, and TNF genes had a nominally statistically significant interaction with well-water arsenicmore » in cIMT. For instance, the joint presence of a higher level of well-water arsenic (≥ 40.4 μg/L) and the GG genotype of AS3MT rs3740392 was associated with a difference of 40.9 μm (95% CI = 14.4, 67.5) in cIMT, much greater than the difference of cIMT associated with the genotype alone (β = − 5.1 μm, 95% CI = − 31.6, 21.3) or arsenic exposure alone (β = 7.2 μm, 95% CI = − 3.1, 17.5). The pattern and magnitude of the interactions were similar when urinary arsenic was used as the exposure variable. Additionally, the at-risk genotypes of the AS3MT SNPs were positively related to the proportion of monomethylarsonic acid (MMA) in urine, which is indicative of arsenic methylation capacity. The findings provide novel evidence that genetic variants related to arsenic metabolism may play an important role in arsenic-induced subclinical atherosclerosis. Future replication studies in diverse populations are needed to confirm the findings. - Highlights: • Nine SNPs had a nominally significant interaction with well-water arsenic in cIMT. • Three SNPs in AS3MT showed nominally significant interactions with urinary arsenic. • cIMT was much higher among subjects with higher arsenic exposure and AS3MT SNPs. • The at-risk genotypes of AS3MT SNPs were positively related to urinary MMA%.« less

Arsenic microdistribution and speciation in toenail clippings of children living in a historic gold mining area

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pearce, Dora C.; Dowling, Kim; Gerson, Andrea R.

2010-05-04

Arsenic is naturally associated with gold mineralization and elevated in some soils and mine waste around historical gold mining activity in Victoria, Australia. To explore uptake, arsenic concentrations in children's toenail clippings and household soils were measured, and the microdistribution and speciation of arsenic in situ in toenail clipping thin sections investigated using synchrotron-based X-ray microprobe techniques. The ability to differentiate exogenous arsenic was explored by investigating surface contamination on cleaned clippings using depth profiling, and direct diffusion of arsenic into incubated clippings. Total arsenic concentrations ranged from 0.15 to 2.1 {micro}g/g (n = 29) in clipping samples and frommore » 3.3 to 130 {micro}g/g (n = 22) in household soils, with significant correlation between transformed arsenic concentrations (Pearson's r = 0.42, P = 0.023) when household soil was treated as independent. In clipping thin sections (n = 2), X-ray fluorescence (XRF) mapping showed discrete layering of arsenic consistent with nail structure, and irregular arsenic incorporation along the nail growth axis. Arsenic concentrations were heterogeneous at 10 x 10 {micro}m microprobe spot locations investigated (< 0.1 to 13.3 {micro}g/g). X-ray absorption near-edge structure (XANES) spectra suggested the presence of two distinct arsenic species: a lower oxidation state species, possibly with mixed sulphur and methyl coordination (denoted As{sub (-S, -ch3)}{sup {approx}III}); and a higher oxidation state species (denoted As{sub (-O)}{sup {approx}V}). Depth profiling suggested that surface contamination was unlikely (n = 4), and XRF and XANES analyses of thin sections of clippings incubated in dry or wet mine waste, or untreated, suggested direct diffusion of arsenic occurred under moist conditions. These findings suggest that arsenic in soil contributes to some systemic absorption associated with periodic exposures among children resident in areas of historic gold mining activity in Victoria, Australia. Future studies are required to ascertain if adverse health effects are associated with current levels of arsenic uptake.« less

Speciation and distribution of arsenic and localization of nutrients in rice grains

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lombi, E.; Scheckel, K.G.; Pallon, J.

2012-09-05

Arsenic (As) contamination of rice grains and the generally low concentration of micronutrients in rice have been recognized as a major concern for human health. Here, we investigated the speciation and localization of As and the distribution of (micro)nutrients in rice grains because these are key factors controlling bioavailability of nutrients and contaminants. Bulk total and speciation analyses using high-pressure liquid chromatography (HPLC)-inductively coupled plasma mass spectrometry (ICP-MS) and X-ray absorption near-edge spectroscopy (XANES) was complemented by spatially resolved microspectroscopic techniques ({mu}-XANES, {mu}-X-ray fluorescence ({mu}-XRF) and particle induced X-ray emission (PIXE)) to investigate both speciation and distribution of As andmore » localization of nutrients in situ. The distribution of As and micronutrients varied between the various parts of the grains (husk, bran and endosperm) and was characterized by element-specific distribution patterns. The speciation of As in bran and endosperm was dominated by As(III)-thiol complexes. The results indicate that the translocation from the maternal to filial tissues may be a bottleneck for As accumulation in the grain. Strong similarities between the distribution of iron (Fe), manganese (Mn) and phosphorus (P) and between zinc (Zn) and sulphur (S) may be indicative of complexation mechanisms in rice grains.« less

Proteomic Analysis of Arsenic-Induced Oxidative Stress in Human Epidermal Keratinocytes

EPA Science Inventory

Chronic exposure to inorganic arsenic (IAs) has been associated with the development of several human cancers, including those found in the skin, lung, urinary bladder, liver, prostate and kidney. The precise mechanisms by which arsenic causes cancer are unknown. Defining the mod...

Arsenic Methylation, Oxidative Stress and Cancer - Is there a Link?

EPA Science Inventory

Arsenic is a multiorgan human carcinogen. The best-known example of this effect occurred in subgroups of the Taiwanese population who were chronically exposed to high levels of naturally occurring arsenic in drinking water and developed cancers of the skin, lung, urinary bladde...

Individual variability in the human metabolism of an arsenic-containing carbohydrate, 2',3'-dihydroxypropyl 5-deoxy-5-dimethylarsinoyl-beta-D-riboside, a naturally occurring arsenical in seafood.

PubMed

Raml, Reingard; Raber, Georg; Rumpler, Alice; Bauernhofer, Thomas; Goessler, Walter; Francesconi, Kevin A

2009-09-01

We report studies on the variability in human metabolism of an oxo-arsenosugar involving the ingestion of a chemically synthesized arsenosugar and quantitative determination of the arsenic metabolites in urine and serum by HPLC coupled with arsenic-selective mass spectrometric detection (ICPMS, inductively coupled plasma mass spectrometry). The total, four-day, urinary excretion of arsenic for six volunteers ranged widely from ca. 4-95%. The arsenic metabolites present in the urine also showed great variability: high arsenic excretion was accompanied by almost complete biotransformation of the ingested oxo-arsenosugar into a multitude of metabolites (>10), whereas the subjects that excreted low amounts of arsenic produced low quantities of metabolites relative to unchanged oxo-arsenosugar and its thio-analogue. Major arsenic urinary metabolites were dimethylarsinate (DMA) and possible intermediates in the degradation of arsenosugar to DMA, namely, dimethylarsinoylethanol (DMAE) and dimethylarsinoylacetate (DMAA) present both as their oxo- and thio-analogues. Thio-DMAE and thio-DMAA were also found in blood serum indicating that these species were formed in the liver rather than on storage of the urine in the bladder. The large variability in the way individuals metabolize arsenosugars has implications for risk assessment of arsenic intake from seafood.

EFFECTS OF PH AND PHOSPHATE ON METAL DISTRIBUTION WITH EMPHASIS ON AS SPECIATION AND MOBILIZATION IN SOILS FROM A LEAD SMELTING SITE

EPA Science Inventory

Arsenic in soils from the Asarco Lead Smelter in East Helena, Montana was characterized by X-ray absorption spectroscopy (XAS). As oxidation state and geochemical speciation were analyzed as a function of depth (two sampling sites) and surface distribution. These results were c...

Arsenic in the groundwater: Occurrence, toxicological activities, and remedies.

PubMed

Jha, S K; Mishra, V K; Damodaran, T; Sharma, D K; Kumar, Parveen

2017-04-03

Arsenic (As) contamination in groundwater has become a geo-environmental as well as a toxicological problem across the globe affecting more than 100-million people in nearly 21 countries with its associated disease "arsenicosis." Arsenic poisoning may lead to fatal skin and internal cancers. In present review, an attempt has been made to generate awareness among the readers about various sources of occurrence of arsenic, its geochemistry and speciation, mobilization, metabolism, genotoxicity, and toxicological exposure on humans. The article also emphasizes the possible remedies for combating the problem. The knowledge of these facts may help to work on some workable remedial measure.

Microbiology: A microbial arsenic cycle in a salt-saturated, extreme environment

USGS Publications Warehouse

Oremland, R.S.; Kulp, T.R.; Blum, J.S.; Hoeft, S.E.; Baesman, S.; Miller, L.G.; Stolz, J.F.

2005-01-01

Searles Lake is a salt-saturated, alkaline brine unusually rich in the toxic element arsenic. Arsenic speciation changed from arsenate [As(V)] to arsenite [As(III)] with sediment depth. Incubated anoxic sediment slurries displayed dissimilatory As(V)-reductase activity that was markedly stimulated by H2 or sulfide, whereas aerobic slurries had rapid As(III)-oxidase activity. An anaerobic, extremely haloalkaliphilic bacterium was isolated from the sediment that grew via As(V) respiration, using either lactate or sulfide as its electron donor. Hence, a full biogeochemical cycle of arsenic occurs in Searles Lake, driven in part by inorganic electron donors.

Arsenic speciation in solids using X-ray absorption spectroscopy

USGS Publications Warehouse

Foster, Andrea L.; Kim, Chris S.

2014-01-01

One of the most important aims of this review is to clarify the different types of analysis that are performed on As-XAS spectra, and to describe the benefits, drawbacks, and limitations of each. Arsenic XAS spectra are analyzed to obtain one or more of the following types of information (in increasing order of sophistication):

ARSENIC SPECIATION, SEASONAL TRANSFORMATIONS, AND CO-DISTRIBUTION WITH IRON IN A MINE WASTE-INFLUENCED PALUSTRINE EMERGENT WETLAND. (R825399)

EPA Science Inventory

Arsenic is commonly associated with mined ores and thus may be detrimental to naturally occurring wetlands that reside in mine waste-impacted regions. Understanding the relationship between Fe and As in both the aqueous and solid phase is critical for assessing the risk As impose...

DIMETHYLARSINIC ACID ALTERS EXPRESSION OF OXIDATIVE STRESS AND DNA REPAIR GENES IN A DOSE DEPENDENT MANNER IN THE TRANSITIONAL EPITHELIUM OF THE URINARY BLADDER FROM FEMALE F344 RATS.

EPA Science Inventory

Dose-dependent alteration of oxidative stress and DNA repair gene expression by Dimethylarsinic acid [DMA(V)] in transitional epithelium of urinary bladder from female F344 rats.
Arsenic (As) is a major concern as millions of people are at risk from drinking arsenic contaminat...

Differential toxicity of arsenic on renal oxidative damage and urinary metabolic profiles in normal and diabetic mice.

PubMed

Yin, Jinbao; Liu, Su; Yu, Jing; Wu, Bing

2017-07-01

Diabetes is a common metabolic disease, which might influence susceptibility of the kidney to arsenic toxicity. However, relative report is limited. In this study, we compared the influence of inorganic arsenic (iAs) on renal oxidative damage and urinary metabolic profiles of normal and diabetic mice. Results showed that iAs exposure increased renal lipid peroxidation in diabetic mice and oxidative DNA damage in normal mice, meaning different effects of iAs exposure on normal and diabetic individuals. Nuclear magnetic resonance (NMR)-based metabolome analyses found that diabetes significantly changed urinary metabolic profiles of mice. Oxidative stress-related metabolites, such as arginine, glutamine, methionine, and β-hydroxybutyrate, were found to be changed in diabetic mice. The iAs exposure altered amino acid metabolism, lipid metabolism, carbohydrate metabolism, and energy metabolism in normal and diabetic mice, but had higher influence on metabolic profiles of diabetic mice than normal mice, especially for oxidative stress-related metabolites and metabolisms. Above results indicate that diabetes increased susceptibility to iAs exposure. This study provides basic information on differential toxicity of iAs on renal toxicity and urinary metabolic profiles in normal and diabetic mice and suggests that diabetic individuals should be considered as susceptible population in toxicity assessment of arsenic.

Arsenic speciation and spatial and interspecies differences of metal concentrations in mollusks and crustaceans from a South China estuary.

PubMed

Zhang, Wei; Wang, Wen-Xiong; Zhang, Li

2013-05-01

Arsenic speciation and concentrations were determined in mollusks and crustaceans in the intertidal zone from twelve locations in Zhanjiang estuary, South China. Metal concentrations (Ag, As, Cd, Cu, Hg, Ni, Pb, and Zn) were also concurrently determined in these species. Arsenic speciation analysis showed that the less-toxic arsenobetaine (AsB) constituted 80.6-98.8 % of all As compounds, and dimethylarsinic acid (DMA) constituted 0.47-3.44 %. Monomethylarsonic acid (MMA) and As(V) were only detected in the whelk Drupa fiscella and the crab Heteropilumnus ciliatus, respectively. Arsenite [As(III)] was not detected in any of the sampled specimens, but there were also unidentified other As species. A strong spatial variation of metals in the oyster Saccostrea cucullata was found in the estuary, confirming that oysters can be used as a good biomonitor of metal contamination in the studied area. The concentrations of eight metals in the studied mollusks and crustaceans clearly revealed that these invertebrates accumulated different metals to different degrees. Furthermore, As, Cd, Cu, Hg, and Pb contents in mollusks and crustacean samples were below the Food and Agricultural Organization (FAO) safe concentrations, thus there was no obvious health risk from the intake of the metals through marine mollusks and crustaceans consumption.

Tissue, Dosimetry, Metabolism and Excretion of Pentavalent and Trivalent Dimethylated Arsenic in Mice after Oral Administration

EPA Science Inventory

Dimethylarsinic acid (DMA(V)) is a rat bladder carcinogen and the major urinary metabolite of administered inorganic arsenic in most mammals. This study examined the disposition of pentavalent and trivalent dimethylated arsenic inmice after acute oral administration. Adult fema...

Environmental exposure to arsenic, AS3MT polymorphism and prevalence of diabetes in Mexico

PubMed Central

Drobná, Zuzana; Del Razo, Luz M.; García-Vargas, Gonzalo G.; Sánchez-Peña, Luz C.; Barrera-Hernández, Angel; Stýblo, Miroslav; Loomis, Dana

2014-01-01

Exposure to arsenic in drinking water is associated with increased prevalence of diabetes. We previously reported an association of diabetes and urinary concentration of dimethylarsinite (DMAsIII), a toxic product of arsenic methylation by arsenic ( +3 oxidation state) methyltransferase (AS3MT). Here we examine associations between AS3MT polymorphism, arsenic metabolism and diabetes. Fasting blood glucose, oral glucose tolerance and self-reported diagnoses were used to identify diabetic individuals. Inorganic arsenic and its metabolites were measured in urine. Genotyping analysis focused on six polymorphic sites of AS3MT. Individuals with M287T and G4965C polymorphisms had higher levels of urinary DMAsIII and were more frequently diabetic than the respective wild-type carriers, although the excess was not statistically significant. Odds ratios were 11.4 (95% confidence interval (CI) 2.2–58.8) and 8.8 (95% CI 1.6–47.3) for the combined effects of arsenic exposure >75th percentile and 287T and 4965C genotypes, respectively. Carriers of 287T and 4965C may produce more DMAsIII and be more likely to develop diabetes when exposed to arsenic. PMID:23093101

Gene-Specific Differential DNA Methylation and Chronic Arsenic Exposure in an Epigenome-Wide Association Study of Adults in Bangladesh

PubMed Central

Argos, Maria; Chen, Lin; Jasmine, Farzana; Tong, Lin; Pierce, Brandon L.; Roy, Shantanu; Paul-Brutus, Rachelle; Gamble, Mary V.; Harper, Kristin N.; Parvez, Faruque; Rahman, Mahfuzar; Rakibuz-Zaman, Muhammad; Slavkovich, Vesna; Baron, John A.; Graziano, Joseph H.; Kibriya, Muhammad G.

2014-01-01

Background: Inorganic arsenic is one of the most common naturally occurring contaminants found in the environment. Arsenic is associated with a number of health outcomes, with epigenetic modification suggested as a potential mechanism of toxicity. Objective: Among a sample of 400 adult participants, we evaluated the association between arsenic exposure, as measured by blood and urinary total arsenic concentrations, and epigenome-wide white blood cell DNA methylation. Methods: We used linear regression models to examine the associations between arsenic exposure and methylation at each CpG site, adjusted for sex, age, and batch. Differentially methylated loci were subsequently examined in relation to corresponding gene expression for functional evidence of gene regulation. Results: In adjusted analyses, we observed four differentially methylated CpG sites with urinary total arsenic concentration and three differentially methylated CpG sites with blood arsenic concentration, based on the Bonferroni-corrected significance threshold of p < 1 × 10–7. Methylation of PLA2G2C (probe cg04605617) was the most significantly associated locus in relation to both urinary (p = 3.40 × 10–11) and blood arsenic concentrations (p = 1.48 × 10–11). Three additional novel methylation loci—SQSTM1 (cg01225779), SLC4A4 (cg06121226), and IGH (cg13651690)—were also significantly associated with arsenic exposure. Further, there was evidence of methylation-related gene regulation based on gene expression for a subset of differentially methylated loci. Conclusions: We observed significant associations between arsenic exposure and gene-specific differential white blood cell DNA methylation, suggesting that epigenetic modifications may be an important pathway underlying arsenic toxicity. The specific differentially methylated loci identified may inform potential pathways for future interventions. Citation: Argos M, Chen L, Jasmine F, Tong L, Pierce BL, Roy S, Paul-Brutus R, Gamble MV, Harper KN, Parvez F, Rahman M, Rakibuz-Zaman M, Slavkovich V, Baron JA, Graziano JH, Kibriya MG, Ahsan H. 2015. Gene-specific differential DNA methylation and chronic arsenic exposure in an epigenome-wide association study of adults in Bangladesh. Environ Health Perspect 123:64–71; http://dx.doi.org/10.1289/ehp.1307884 PMID:25325195

A Potential Synergy between Incomplete Arsenic Methylation Capacity and Demographic Characteristics on the Risk of Hypertension: Findings from a Cross-Sectional Study in an Arsenic-Endemic Area of Inner Mongolia, China

PubMed Central

Li, Yongfang; Wang, Da; Li, Xin; Zheng, Quanmei; Sun, Guifan

2015-01-01

Inefficient arsenic methylation capacity has been associated with various health hazards induced by arsenic. In this study, we aimed to explore the interaction effect of lower arsenic methylation capacity with demographic characteristics on hypertension risk. A total of 512 adult participants (126 hypertension subjects and 386 non-hypertension subjects) residing in an arsenic-endemic area in Inner Mongolia, China were included. Urinary levels of inorganic arsenic (iAs), monomethylarsonic acid (MMA), and dimethylarsinic acid (DMA) were measured for all subjects. The percentage of urinary arsenic metabolites (iAs%, MMA%, and DMA%), primary methylation index (PMI) and secondary methylation index (SMI) were calculated to assess arsenic methylation capacity of individuals. Results showed that participants carrying a lower methylation capacity, which is characterized by lower DMA% and SMI, have a higher risk of hypertension compared to their corresponding references after adjusting for multiple confounders. A potential synergy between poor arsenic methylation capacity (higher MMA%, lower DMA% and SMI) and older age or higher BMI were detected. The joint effects of higher MMA% and lower SMI with cigarette smoking also suggest some evidence of synergism. The findings of present study indicated that inefficient arsenic methylation capacity was associated with hypertension and the effect might be enhanced by certain demographic factors. PMID:25837203

Association Between Arsenic Exposure From Drinking Water and Plasma Levels of Cardiovascular Markers

PubMed Central

Wu, Fen; Jasmine, Farzana; Kibriya, Muhammad G.; Liu, Mengling; Wójcik, Oktawia; Parvez, Faruque; Rahaman, Ronald; Roy, Shantanu; Paul-Brutus, Rachelle; Segers, Stephanie; Slavkovich, Vesna; Islam, Tariqul; Levy, Diane; Mey, Jacob L.; van Geen, Alexander; Graziano, Joseph H.; Ahsan, Habibul; Chen, Yu

2012-01-01

The authors conducted a cross-sectional study to assess the relation between arsenic exposure from drinking water and plasma levels of markers of systemic inflammation and endothelial dysfunction (matrix metalloproteinase-9, myeloperoxidase, plasminogen activator inhibitor-1, soluble E-selectin, soluble intercellular adhesion molecule-1 (ICAM-1), and soluble vascular adhesion molecule-1 (VCAM-1)) using baseline data from 668 participants (age, >30 years) in the Health Effects of Arsenic Longitudinal Study in Bangladesh (2007–2008). Both well water arsenic and urinary arsenic were positively associated with plasma levels of soluble VCAM-1. For every 1-unit increase in log-transformed well water arsenic (ln μg/L) and urinary arsenic (ln μg/g creatinine), plasma soluble VCAM-1 was 1.02 (95% confidence interval: 1.01, 1.03) and 1.04 (95% confidence interval: 1.01, 1.07) times greater, respectively. There was a significant interaction between arsenic exposure and higher body mass index, such that the increased levels of plasminogen activator inhibitor-1 and soluble VCAM-1 associated with arsenic exposure were stronger among people with higher body mass index. The findings indicate an effect of chronic arsenic exposure from drinking water on vascular inflammation and endothelial dysfunction that could be modified by body mass index and also suggest a potential mechanism underlying the association between arsenic exposure and cardiovascular disease. PMID:22534204

Association between arsenic exposure from drinking water and plasma levels of cardiovascular markers.

PubMed

Wu, Fen; Jasmine, Farzana; Kibriya, Muhammad G; Liu, Mengling; Wójcik, Oktawia; Parvez, Faruque; Rahaman, Ronald; Roy, Shantanu; Paul-Brutus, Rachelle; Segers, Stephanie; Slavkovich, Vesna; Islam, Tariqul; Levy, Diane; Mey, Jacob L; van Geen, Alexander; Graziano, Joseph H; Ahsan, Habibul; Chen, Yu

2012-06-15

The authors conducted a cross-sectional study to assess the relation between arsenic exposure from drinking water and plasma levels of markers of systemic inflammation and endothelial dysfunction (matrix metalloproteinase-9, myeloperoxidase, plasminogen activator inhibitor-1, soluble E-selectin, soluble intercellular adhesion molecule-1 (ICAM-1), and soluble vascular adhesion molecule-1 (VCAM-1)) using baseline data from 668 participants (age, >30 years) in the Health Effects of Arsenic Longitudinal Study in Bangladesh (2007-2008). Both well water arsenic and urinary arsenic were positively associated with plasma levels of soluble VCAM-1. For every 1-unit increase in log-transformed well water arsenic (ln μg/L) and urinary arsenic (ln μg/g creatinine), plasma soluble VCAM-1 was 1.02 (95% confidence interval: 1.01, 1.03) and 1.04 (95% confidence interval: 1.01, 1.07) times greater, respectively. There was a significant interaction between arsenic exposure and higher body mass index, such that the increased levels of plasminogen activator inhibitor-1 and soluble VCAM-1 associated with arsenic exposure were stronger among people with higher body mass index. The findings indicate an effect of chronic arsenic exposure from drinking water on vascular inflammation and endothelial dysfunction that could be modified by body mass index and also suggest a potential mechanism underlying the association between arsenic exposure and cardiovascular disease.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liao, Ya-Tang; Graduate Institute of Epidemiology and Preventive Medicine, College of Public Health, National Taiwan University, Taiwan; Genomics Research Center, Academia Sinica, Taiwan

Arsenic ingestion has been linked to increasing global prevalence of and mortality from cardiovascular disease (CVD); arsenic can be removed from drinking water to reduce related health effects. Lactate dehydrogenase (LDH) is used for the evaluation of acute arsenic toxicity in vivo and in vitro, but it is not validated for the evaluation of long-term, chronic arsenic exposure. The present study examined the long-term effect of chronic arsenic exposure on CVD and serum LDH levels, after consideration of arsenic metabolism capacity. A total of 380 subjects from an arseniasis-endemic area and 303 from a non-endemic area of southwestern Taiwan weremore » recruited in 2002. Various urinary arsenic species were analyzed using high-performance liquid chromatography (HPLC) and hydride generation systems. Fasting serum was used for quantitative determination of the total LDH activity. A significant dose–response relationship was observed between arsenic exposure and LDH elevation, independent of urinary arsenic profiles (P < 0.001). Furthermore, abnormal LDH elevation was associated with CVD mortality after adjustment for Framingham risk scores for 10-year CVD and arsenic exposure (hazard ratio, 3.98; 95% confidence interval, 1.07–14.81). LDH was elevated in subjects with arsenic exposure in a dose-dependent manner. LDH is a marker of arsenic toxicity associated with CVD mortality. Results of this study have important implications for use in ascertaining long-term arsenic exposure risk of CVD. -- Highlights: ► We showed that arsenic exposure was correlated with LDH elevation. ► LDH elevation was related to arsenic methylation capacity. ► Abnormal LDH elevation can be a marker of susceptibility to CVD mortality.« less

GENE EXPRESSION PROFILING OF RESPONSES TO DIMETHYLARSINIC ACID IN FEMALE F344 RAT UROTHELIUM

EPA Science Inventory

Arsenic is a human carcinogen and epidemiologic evidence implicates it in the development of urinary bladder cancer. Even though several mechanisms have been proposed for arsenic carcinogenicity, the mode of action of inorganic arsenic (iAs) is confounded by the limited availabil...

TISSUE DOSIMETRY, METABOLISM AND EXCRETION OF PENTAVALENT AND TRIVALENT DIMETHYLATED ARSENIC IN MICE AFTER ORAL ADMINISTRATION

EPA Science Inventory

Dimethylarsinic acid (DMA(V)) is a rat bladder carcinogen and the major urinary metabolite of inorganic arsenic in most mammals. This study examined the disposition of pentavalent and trivalent dimethylated arsenic in mice after acute oral administration. Adult female mice were...

Trends in urinary arsenic among the U.S. population by drinking water source: Results from the National Health and Nutritional Examinations Survey 2003-2014.

PubMed

Welch, Barrett; Smit, Ellen; Cardenas, Andres; Hystad, Perry; Kile, Molly L

2018-04-01

In 2001, the United States revised the arsenic maximum contaminant level for public drinking water systems from 50µg/L to 10µg/L. This study aimed to examine temporal trends in urinary arsenic concentrations in the U.S. population from 2003 to 2014 by drinking water source among individuals aged 12 years and older who had no detectable arsenobetaine - a biomarker of arsenic exposure from seafood intake. We examined data from 6 consecutive cycles of the National Health and Nutrition Examination Survey (2003-2014; N=5848). Total urinary arsenic (TUA) was calculated by subtracting arsenobetaine's limit of detection and detectable arsenocholine from total arsenic. Additional sensitivity analyses were conducted using a second total urinary arsenic index (TUA2, calculated by adding arsenite, arsenate, monomethylarsonic acid, dimethylarsinic acid). We classified drinking water source using 24-h dietary questionnaire data as community supply (n=3427), well or rain cistern (n=506), and did not drink tap water (n=1060). Geometric means (GM) of survey cycles were calculated from multivariate regression models adjusting for age, gender, race/ethnicity, BMI, income, creatinine, water source, type of water consumed, recent smoking, and consumption of seafood, rice, poultry, and juice. Compared to 2003-2004, adjusted TUA was 35.5% lower in 2013-2014 among the general U.S. Stratified analysis by smoking status indicated that the trend in lower TUA was only consistent among non-smokers. Compared to 2003-2004, lower adjusted TUA was observed in 2013-2014 among non-smoking participants who used community water supplies (1.98 vs 1.16µg/L, p<0.001), well or rain cistern users (1.54 vs 1.28µg/L, p<0.001) and who did not drink tap water (2.24 vs 1.53µg/L, p<0.001). Sensitivity analyses showed consistent results for participants who used a community water supplier and to a lesser extent those who did not drink tap water. However, the sensitivity analysis showed overall exposure stayed the same or was higher among well or rain cistern users. Finally, the greatest decrease in TUA was among participants within the highest exposure percentiles (e.g. 95th percentile had 34% lower TUA in 2013/2014 vs 2003/2004, p<0.001). Overall, urinary arsenic levels in the U.S. population declined over a 12-year period that encompassed the adoption of the revised Arsenic Rule. The most consistent trends in declining exposure were observed among non-smoking individuals using public community water systems. These results suggest regulation and prevention strategies to reduce arsenic exposures in the U.S. may be succeeding. Copyright © 2017 Elsevier Inc. All rights reserved.

Arsenic levels in the groundwater of Korea and the urinary excretion among contaminated area.

PubMed

Park, Jung-Duck; Choi, Seong-Jin; Choi, Byung-Sun; Lee, Choong-Ryeol; Kim, Heon; Kim, Yong-Dae; Park, Kyung-Soo; Lee, Young-Jo; Kang, Seojin; Lim, Kyung-Min; Chung, Jin-Ho

2016-09-01

Drinking water is a main source of human exposure to arsenic. Hence, the determination of arsenic in groundwater is essential to assess its impact on public health. Here, we report arsenic levels in the groundwater of 722 sites covering all six major provinces of Korea. Water was sampled in two occasions (summer, 722 sites and winter, 636 sites) and the arsenic levels were measured with highly sensitive inductively coupled plasma-mass spectrometry method (limit of detection, 0.1 μg/l) to encompass the current drinking water standard (<10 μg/l). Seasonal variation was negligible, but the geographical difference was prominent. Total arsenic in groundwater ranged from 0.1 to 48.4 μg/l. A 88.0-89.0% of sites were <2.0 μg/l and the remaining ones generally did not exceed 10 μg/l (6.4-7.0%, 2.0-4.9 μg/l; 2.4-3.0%, 5.0-9.9 μg/l). However, some areas (1.0-9.2%) exhibited >10 μg/l. Notably, urinary arsenic excretion of people around these regions was markedly higher compared with non-contaminated areas (<5 μg/l) (79.7±5.2 μg/g (N=122) vs 68.4±5.4 μg/g (N=65) creatinine, P=0.052). All stratified analysis also revealed higher urinary excretion, where a statistically significant difference was noted for non-smokers (85.9±12.7 vs 54.0±6.3, P=0.030), suggesting that arsenic-contaminated groundwater may contribute to its systemic exposure.

Preliminary analysis of in utero low-level arsenic exposure and fetal growth using biometric measurements extracted from fetal ultrasound reports.

PubMed

Davis, Matthew A; Higgins, John; Li, Zhigang; Gilbert-Diamond, Diane; Baker, Emily R; Das, Amar; Karagas, Margaret R

2015-03-30

Early life exposure to arsenic is associated with decreased birth weight in highly exposed populations but little is known about effects of low-level arsenic exposure on growth in utero. Using a sample of 272 pregnancies from New Hampshire we obtained biometric measurements directly from fetal ultrasound reports commonly found in electronic medical records. We used information extraction methods to develop and validate an automated approach for mining biometric measurements from the text of clinical reports. As a preliminary analysis, we examined associations between in utero low-level arsenic exposure (as measured by maternal urinary arsenic concentration) and fetal growth measures (converted to Z-scores based on reference populations for estimated fetal weight, head, and other body measures) at approximately 18 weeks of gestation. In a preliminary cross-sectional analysis of 223 out of 272 pregnancies, maternal urinary arsenic concentration (excluding arsenobetaine) was associated with a reduction in head circumference Z-score (Spearman correlation coefficient, rs = -0.08, p-value = 0.21) and a stronger association was observed among female fetuses at approximately 18 weeks of gestation (rs = - 0.21, p-value < 0.05). Although, associations were attenuated in adjusted analyses - among female fetuses a 1 μg/L increase in maternal urinary arsenic concentration was associated with a decrease of 0.047 (95% CI: -0.115, 0.021) in head circumference and 0.072 (95% CI: -0.151, 0.007) decrease in biparietal head diameter Z-score. Our study demonstrates that useful data can be extracted directly from electronic medical records for epidemiologic research. We also found evidence that exposure to low-level arsenic may be associated with reduced head circumference in a sex dependent manner that warrants further investigation.

Bioaccumulation of arsenic species in rays from the northern Adriatic Sea.

PubMed

Šlejkovec, Zdenka; Stajnko, Anja; Falnoga, Ingrid; Lipej, Lovrenc; Mazej, Darja; Horvat, Milena; Faganeli, Jadran

2014-12-01

The difference in arsenic concentration and speciation between benthic (Pteromylaeus bovinus, Myliobatis aquila) and pelagic rays (Pteroplatytrygon violacea) from the northern Adriatic Sea (Gulf of Trieste) in relation to their size (age) was investigated. High arsenic concentrations were found in both groups with tendency of more efficient arsenic accumulation in benthic species, particularly in muscle (32.4 to 362 µg·g-1 of total arsenic). This was attributed to species differences in arsenic access, uptake and retention. In liver most arsenic was present in a form of arsenobetaine, dimethylarsinic acid and arsenoipids, whereas in muscle mainly arsenobetaine was found. The good correlations between total arsenic/arsenobetaine and size reflect the importance of accumulation of arsenobetaine with age. Arsenobetaine is an analogue of glycine betaine, a known osmoregulator in marine animals and both are very abundant in mussels, representing an important source of food for benthic species P. bovinus and M. aquila.

Bioaccumulation of Arsenic Species in Rays from the Northern Adriatic Sea

PubMed Central

Šlejkovec, Zdenka; Stajnko, Anja; Falnoga, Ingrid; Lipej, Lovrenc; Mazej, Darja; Horvat, Milena; Faganeli, Jadran

2014-01-01

The difference in arsenic concentration and speciation between benthic (Pteromylaeus bovinus, Myliobatis aquila) and pelagic rays (Pteroplatytrygon violacea) from the northern Adriatic Sea (Gulf of Trieste) in relation to their size (age) was investigated. High arsenic concentrations were found in both groups with tendency of more efficient arsenic accumulation in benthic species, particularly in muscle (32.4 to 362 µg·g−1 of total arsenic). This was attributed to species differences in arsenic access, uptake and retention. In liver most arsenic was present in a form of arsenobetaine, dimethylarsinic acid and arsenoipids, whereas in muscle mainly arsenobetaine was found. The good correlations between total arsenic/arsenobetaine and size reflect the importance of accumulation of arsenobetaine with age. Arsenobetaine is an analogue of glycine betaine, a known osmoregulator in marine animals and both are very abundant in mussels, representing an important source of food for benthic species P. bovinus and M. aquila. PMID:25470025

Levels and speciation of arsenic in the atmosphere in Beijing, China.

PubMed

Yang, Guosheng; Ma, Lingling; Xu, Diandou; Li, Jie; He, Tingting; Liu, Liyan; Jia, Hongliang; Zhang, Yongbao; Chen, Yang; Chai, Zhifang

2012-05-01

Arsenic levels and speciation in the total suspended particles (TSPs) were quantitatively determined by high performance liquid chromatography on-line coupled with hydride generation atomic fluorescence spectrometry in Beijing, China from February 2009 to March 2011. The high TSP levels fluctuated between 0.07 and 0.79 mg m(-3), with a mean level of 0.32 ± 0.17 mg m(-3). The total arsenic concentrations ranged from 0.03 to 0.31 μg m(-3) (mean: 0.13 ± 0.06 μg m(-3)) in Beijing's air. The concentrations of As(III) and As(V) ranged from 0.73 to 20 ng m(-3) (mean: 4.7 ± 3.6 ng m(-3)) and from 14 to 2.5 × 10(2) ng m(-3) (mean: 67 ± 35 ng m(-3)), respectively. As levels and speciation demonstrated relative higher levels in spring and autumn and lower values in summer and winter. As(V) accounted for 81-99% of the extractable species in the TSP samples which showed that As(V) was the major fraction of the extractable As. Organoarsenic species, monomethylarsonate (MMA) and dimethylarsinate (DMA) were not found in all samples. Higher values of enrichment factors demonstrated that arsenic in TSP mainly come from anthropogenic sources. High As and its species levels in air and respiratory exposure (0.30-0.84 μg d(-1)) attributed to higher excess cancer risk ((4.2 ± 2.0) × 10(-4)) for people in Beijing. Copyright © 2012 Elsevier Ltd. All rights reserved.

EFFECTS OF PH AND COMPETING ANIONS ON THE SPECIATION OF ARSENIC IN FIXED IONIC STRENGTH SOLUTIONS BY SOLID PHASE EXTRACTION CARTRIDGES

EPA Science Inventory

Anion-exchange resins (AERs) separate As(V) and As(lIl) in solution by retaining As(V) and allowing As(lIl) to pass through. AERs offer several advantages including portability, ease of use, and affordability (relative to other As speciation methods). The use of AERs for the inst...

Urinary arsenic, pesticides, heavy metals, phthalates, polyaromatic hydrocarbons, and polyfluoroalkyl compounds are associated with sleep troubles in adults: USA NHANES, 2005-2006.

PubMed

Shiue, Ivy

2017-01-01

Links between environmental chemicals and human health have emerged, but the effects on sleep health were less studied. Therefore, the aim of the present study was to investigate the relationships of different sets of environmental chemicals and common sleep troubles in a national and population-based setting. Data were retrieved from the United States National Health and Nutrition Examination Surveys, 2005-2006 including demographics, serum measurements, lifestyle factors, self-reported sleep troubles, and urinary environmental chemical concentrations. Statistical analyses including descriptive statistics, t-test, chi-square test, and survey-weighted logistic regression models were performed. Of all 5563 Americans aged 18-85, 2331 (42.0%) had wake-up at night, 2914 (52.5%) felt unrested during the day, 740 (13.4%) had leg jerks while sleeping, and 1059 (19.1%) had leg cramps for 2+ times a month. Higher levels of urinary arsenic, phthalates, and polyfluoroalkyl compounds were associated with wake-up at night. Higher levels of urinary 4-tert-octylphenol and polyfluoroalkyl compounds were associated with being unrested during the day. Higher levels of urinary arsenic, polyaromatic hydrocarbons, and polyfluoroalkyl compounds were associated with leg jerks while sleeping. Higher levels of urinary pesticides, heavy metals, phthalates, and polyaromatic hydrocarbons were associated with leg cramps while sleeping. However, there were no significant associations with other environmental chemicals such as parabens, bisphenol A, benzophenone-3, triclosan, perchlorate, nitrate, or thiocyanate. Eliminating arsenic, heavy metals, phthalate, pesticides, polyaromatic hydrocarbons, and polyfluoroalkyl compounds to improve sleep health might be considered while understanding the biological pathway with a longitudinal or experimental approach in future research would be suggested.

Application of an in vivo swine model for the determination of arsenic bioavailability in contaminated vegetables.

PubMed

Juhasz, Albert L; Smith, Euan; Weber, John; Rees, Matthew; Rofe, Allan; Kuchel, Tim; Sansom, Lloyd; Naidu, Ravi

2008-05-01

Considerable information is available in the literature regarding the uptake of arsenic (As) from contaminated soil and irrigation water by vegetables. However, few studies have investigated As speciation in these crops while a dearth of information is available on As bioavailability following their consumption. In this study, the concentration and speciation of As in chard, radish, lettuce and mung beans was determined following hydroponic growth of the vegetables using As-contaminated water. In addition, As bioavailability was assessed using an in vivo swine feeding assay. While As concentrations ranged from 3.0 to 84.2mg As kg(-1) (dry weight), only inorganic As (arsenite and arsenate) was detected in the edible portions of the vegetables. When As bioavailability was assessed through monitoring blood plasma As concentrations following swine consumption of As-contaminated vegetables, between 50% and 100% of the administered As dose was absorbed and entered systemic circulation. Arsenic bioavailability decreased in the order mung beans>radish>lettuce=chard.

Reversed Phase Column HPLC-ICP-MS Conditions for Arsenic Speciation Analysis of Rice Flour.

PubMed

Narukawa, Tomohiro; Matsumoto, Eri; Nishimura, Tsutomu; Hioki, Akiharu

2015-01-01

New measurement conditions for arsenic speciation analysis of rice flour were developed using HPLC-ICP-MS equipped with a reversed phase ODS column. Eight arsenic species, namely, arsenite [As(III)], arsenate [As(V)], monomethylarsonic acid (MMAA), dimethylarsinic acid (DMAA), trimethylarsine oxide (TMAO), tetramethylarsonium (TeMA), arsenobetaine (AsB) and arsenocholine (AsC), were separated and determined under the proposed conditions. In particular, As(III) and MMAA and DMAA and AsB were completely separated using a newly proposed eluent containing ammonium dihydrogen phosphate. Importantly, the sensitivity changes, in particular those of As(V) and As(III) caused by coexisting elements and by complex matrix composition, which had been problematical in previously reported methods, were eliminated. The new eluent can be applied to C8, C18 and C30 ODS columns with the same effectiveness and with excellent repeatability. The proposed analytical method was successfully applied to extracts of rice flour certified reference materials.

THE LIBERATION OF ARSENOSUGARS FROM MATRIX COMPONENTS IN DIFFICULT TO EXTRACT SEAFOOD SAMPLES UTILIZING TMAOH/ACETIC ACID SEQUENTIALLY IN A TWO-STAGE EXTRACTION PROCESS

EPA Science Inventory

Sample extraction is one of the most important steps in arsenic speciation analysis of solid dietary samples. One of the problem areas in this analysis is the partial extraction of arsenicals from seafood samples. The partial extraction allows the toxicity of the extracted arse...

Differences of urinary arsenic metabolites and methylation capacity between individuals with and without skin lesions in Inner Mongolia, Northern China.

PubMed

Zhang, Qiang; Li, Yongfang; Liu, Juan; Wang, Da; Zheng, Quanmei; Sun, Guifan

2014-07-18

Incomplete arsenic (As) methylation has been considered a risk factor of As-related diseases. This study aimed to examine the difference of urinary As metabolites and the methylation capacity between subjects with and without skin lesions. Urinary inorganic arsenic (iAs), monomethylarsonic acid (MMA), and dimethylarsinic acid (DMA) were analyzed. The percentage of each As species (iAs%, MMA%, and DMA%), the primary methylation index (PMI) and secondary methylation index (SMI) were calculated. The results showed that subjects with skin lesions have higher levels of urinary iAs (99.08 vs. 70.63 μg/g Cr, p = 0.006) and MMA (69.34 vs. 42.85 μg/g Cr, p = 0.016) than subjects without skin lesions after adjustment for several confounders. Significant differences of urianry MMA% (15.49 vs. 12.11, p = 0.036) and SMI (0.74 vs. 0.81, p = 0.025) were found between the two groups. The findings of the present study suggest that subjects with skin lesions may have a lower As methylation capacity than subjects without skin lesions.

Elevated childhood exposure to arsenic despite reduced drinking water concentrations--A longitudinal cohort study in rural Bangladesh.

PubMed

Kippler, Maria; Skröder, Helena; Rahman, Syed Moshfiqur; Tofail, Fahmida; Vahter, Marie

2016-01-01

The aim of this study was to evaluate the massive efforts to lower water arsenic concentrations in Bangladesh. In our large mother-child cohort in rural Matlab, we measured the arsenic concentrations (and other elements) in drinking water and evaluated the actual exposure (urinary arsenic), from early gestation to 10 years of age (n=1017). Median drinking water arsenic decreased from 23 (2002-2003) to <2 μg/L (2013), and the fraction of wells exceeding the national standard (50 μg/L) decreased from 58 to 27%. Still, some children had higher water arsenic at 10 years than earlier. Installation of deeper wells (>50 m) explained much of the lower water arsenic concentrations, but increased the manganese concentrations. The highest manganese concentrations (~900 μg/L) appeared in 50-100 m wells. Low arsenic and manganese concentrations (17% of the children) occurred mainly in >100 m wells. The decrease in urinary arsenic concentrations over time was less apparent, from 82 to 58 μg/L, indicating remaining sources of exposure, probably through food (mean 133 μg/kg in rice). Despite decreased water arsenic concentrations in rural Bangladesh, the children still have elevated exposure, largely from food. Considering the known risks of severe health effects in children, additional mitigation strategies are needed. Copyright © 2015 The Authors. Published by Elsevier Ltd.. All rights reserved.

Sulfur redox chemistry governs diurnal antimony and arsenic cycles at Champagne Pool, Waiotapu, New Zealand

NASA Astrophysics Data System (ADS)

Ullrich, Maria K.; Pope, James G.; Seward, Terry M.; Wilson, Nathaniel; Planer-Friedrich, Britta

2013-07-01

Champagne Pool, a sulfidic hot spring in New Zealand, exhibits distinct diurnal variations in antimony (Sb) and arsenic (As) concentrations, with daytime high and night-time low concentrations. To identify the underlying mobilization mechanisms, five sites along the drainage channel of Champagne Pool were sampled every 2 h during a 24 h period. Temporal variations in elemental concentrations and Sb, As, and sulfur (S) speciation were monitored in the discharging fluid. Total trace element concentrations in filtered and unfiltered samples were analyzed using ICP-MS, and Sb, As and S species were determined by IC-ICP-MS. Sulfur speciation in the drainage channel was dominated by thiosulfate and sulfide at night, while sulfate dominated during the day. The distinct diurnal changes suggest that the transformations are caused by phototrophic sulfur-oxidizing bacteria. These bacteria metabolize thiosulfate and sulfide in daylight to form sulfate and, as suggested by modeling with PhreeqC, elemental sulfur. Sulfide consumption during the day results in undersaturation of antimony sulfides, which triggers the additional release of dissolved Sb. For As, diurnal cycles were much more pronounced in speciation than in total concentrations, with di- and trithioarsenate forming at night due to excess sulfide, and monothioarsenate forming from arsenite and elemental sulfur during the day. Sulfur speciation was thus found to control Sb and As in terms of both solubility and speciation.

Transcriptional Modulation of the ERK1/2 MAPK and NF-kB pathways in Human Urothelial cells after trivalent arsenical exposure: Implications for urinary bladder cancer

EPA Science Inventory

Chronic exposure to drinking water contaminated with inorganic arsenic (iAs) is associated with an increased risk ofurinary bladder (DB) cancers in humans. Rodent models administered particular arsenicals have indicated urothelial necrosis followed by regenerative proliferation i...

EXCRETION OF ARSENIC IN URINE AS A FUNCTION OF EXPOSURE TO ARSENIC IN DRINKING WATER

EPA Science Inventory

Urinary arsenic (As) concentrations were evaluated as a biomarker of exposure in a U.S. population chronically exposed to inorganic As (InAs) in their drinking water. Ninety-six individuals who consumed drinking water with As concentrations of 8-620 microg/L provided first mornin...

Chronic early childhood exposure to arsenic is associated with a TNF-mediated proteomic signaling response.

PubMed

Smeester, Lisa; Bommarito, Paige A; Martin, Elizabeth M; Recio-Vega, Rogelio; Gonzalez-Cortes, Tania; Olivas-Calderon, Edgar; Lantz, R Clark; Fry, Rebecca C

2017-06-01

Exposure to inorganic arsenic (iAs) in drinking water is a global public health concern and is associated with a range of health outcomes, including immune dysfunction. Children are a particularly sensitive population to the effects of inorganic arsenic, yet the biological mechanisms underlying adverse health outcomes are understudied. Here we used a proteomic approach to examine the effects of iAs exposure on circulating serum protein levels in a cross-sectional children's cohort in Mexico. To identify iAs-associated proteins, levels of total urinary arsenic (U-tAs) and its metabolites were determined and serum proteins assessed for differences in expression. The results indicate an enrichment of Tumor Necrosis Factor-(TNF)-regulated immune and inflammatory response proteins that displayed decreased expression levels in relation to increasing U-tAs. Notably, when analyzed in the context of the proportions of urinary arsenic metabolites in children, the most robust response was observed in relation to the monomethylated arsenicals. This study is among the first serum proteomics assessment in children exposed to iAs. Copyright © 2017 Elsevier B.V. All rights reserved.

Arsenic Metabolism in Children Differs From That in Adults.

PubMed

Skröder Löveborn, Helena; Kippler, Maria; Lu, Ying; Ahmed, Sultan; Kuehnelt, Doris; Raqib, Rubhana; Vahter, Marie

2016-07-01

Arsenic toxicity in adults is associated with methylation efficiency, influenced by factors such as gender, genetics, and nutrition. The aim of this study was to evaluate influencing factors for arsenic metabolism in children. For 488 children (9 years), whose mothers participated in a study on arsenic exposure during pregnancy (nested into the MINIMat trial) in rural Bangladesh, we measured urinary concentrations of inorganic arsenic (iAs) and its metabolites methylarsonic acid (MMA) and dimethylarsinic acid (DMA) by HPLC-HG-ICPMS. Methylation efficiency was assessed by relative amounts (%) of the metabolites. We evaluated the impact of factors such as maternal urinary metabolite pattern, arsenic exposure, gender, socioeconomic status, season of sampling, and nutritional factors, including erythrocyte selenium (Ery-Se), and plasma folate and vitamin B12.Children had higher %DMA and lower %iAs in urine compared to their mothers, unrelated to their lower exposure [median urinary arsenic (U-As) 53 vs 78 µg/l]. Surprisingly, selenium status (Ery-Se) was strongly associated with children's arsenic methylation; an increase in Ery-Se from the 5-95th percentile was associated with: +1.8 percentage points (pp) for %iAs (P  =  .001), +1.4 pp for %MMA (P  =  .003), and -3.2 pp for %DMA (P  <  .001). Despite this, Ery-Se was positively associated with U-As (5-95th percentile: +41 µg/l, P  =  .026). As expected, plasma folate was inversely associated with %iAs (5-95th percentile: -1.9 pp, P  =  .001) and positively associated with %DMA (5-95th percentile: +2.2 pp, P  =  .008). Children methylated arsenic more efficiently than their mothers. Also influencing factors, mainly selenium and folate, differed. This warrants further research. © The Author 2016. Published by Oxford University Press on behalf of the Society of Toxicology.

Arsenic accumulation in three species of sea turtles.

PubMed

Saeki, K; Sakakibara, H; Sakai, H; Kunito, T; Tanabe, S

2000-09-01

Arsenic in the liver, kidney and muscle of three species of sea turtles, e.g., green turtles (Chelonia mydas), loggerhead turtles (Caretta caretta) and hawksbill turtles (Eretmochelys imbricata), were determined using HG-AAS, followed by arsenic speciation analysis using HPLC-ICP-MS. The order of arsenic concentration in tissues was muscle > kidney > liver. Unexpectedly, the arsenic concentrations in the hawksbill turtles feeding mainly on sponges were higher than the two other turtles primarily eating algae and mollusk which accumulate a large amount of arsenic. Especially, the muscles of the hawksbill turtles contained remarkably high arsenic concentrations averaging 153 mg kg(-1) dry weight with the range of 23.1-205 mg kg(-1) (n = 4), even in comparison with the data from other organisms. The arsenic concentrations in the tissues of the green turtles were significantly decreased with standard carapace length as an indicator of growth. In arsenic compounds, arsenobetaine was mostly detected in the tissues of all the turtles. Besides arsenobetaine, a small amount of dimethylarsinic acid was also observed in the hawksbill turtles.

Method optimization and quality assurance in speciation analysis using high performance liquid chromatography with detection by inductively coupled plasma mass spectrometry

NASA Astrophysics Data System (ADS)

Larsen, Erik H.

1998-02-01

Achievement of optimum selectivity, sensitivity and robustness in speciation analysis using high performance liquid chromatography (HPLC) with inductively coupled mass spectrometry (ICP-MS) detection requires that each instrumental component is selected and optimized with a view to the ideal operating characteristics of the entire hyphenated system. An isocratic HPLC system, which employs an aqueous mobile phase with organic buffer constituents, is well suited for introduction into the ICP-MS because of the stability of the detector response and high degree of analyte sensitivity attained. Anion and cation exchange HPLC systems, which meet these requirements, were used for the seperation of selenium and arsenic species in crude extracts of biological samples. Furthermore, the signal-to-noise ratios obtained for these incompletely ionized elements in the argon ICP were further enhanced by a factor of four by continously introducing carbon as methanol via the mobile phase into the ICP. Sources of error in the HPLC system (column overload), in the sample introduction system (memory by organic solvents) and in the ICP-MS (spectroscopic interferences) and their prevention are also discussed. The optimized anion and cation exchange HPLC-ICP-MS systems were used for arsenic speciation in contaminated ground water and in an in-house shrimp reference sample. For the purpose of verification, HPLC coupled with tandem mass spectrometry with electrospray ionization was additionally used for arsenic speciation in the shrimp sample. With this analytical technique the HPLC retention time in combination with mass analysis of the molecular ions and their collision-induced fragments provide almost conclusive evidence of the identity of the analyte species. The speciation methods are validated by establishing a mass balance of the analytes in each fraction of the extraction procedure, by recovery of spikes and by employing and comparing independent techniques. The urgent need for reference materials certified for elemental species is stressed.

AS SPECIATION AND EFFECTS OF PH AND PHOSPHATE ON THE MOBILIZATION OF AS IN SOILS FROM A LEAD SMELTING SITE. PUBLISHED IN ADVANCED PHOTON SOURCE ACTIVITY REPORT 2003.

EPA Science Inventory

Arsenic in soils from the Asarco lead smelter in East Helena, Montana was characterized by X-ray absorption spectroscopy (XAS). Arsenic oxidation state and mineralogy were analyzed as a function of depth and surface distribution using bulk and microprobe XAS. These results were c...

SPECIATION OF SELENIUM AND ARSENIC COMPOUNDS BY CAPILLARY ELECTROPHORESIS WITH HYDRODYNAMICALLY MODIFIED ELECTROOSMOTIC FLOW AND ON-LINE REDUCTION OF SELENIUM(VI) TO SELENIUM(IV) WITH HYDRIDE GENERATION INDUCTIVELY COUPLED PLASMA MASS SPECTROMETRIC DETECTION

EPA Science Inventory

Capillary electrophoresis (CE) with hydride generation inductively coupled plasma mass spectrometry was used to determine four arsenicals and two selenium species. Selenate (SeVI) was reduced on-line to selenite (SeIV') by mixing the CE effluent with concentrated HCl. A microporo...

COMPLEMENTARY MOLECULAR AND ELEMENTAL DETECTION OF SPECIATED THIOARSENICALS USING ESI-MS IN COMBINATION WITH A XENON-BASED COLLISION-CELL ICP-MS WITH APPLICATION TO FORTIFIED NIST FREEZE-DRIED URINE

EPA Science Inventory

The simultaneous detection of arsenic and sulfur in thio-arsenicals was achieved using xenonbased collision cell ICP-MS in combination with HPLC. In an attempt to minimize the 16O16O+ interference at m/z 32, both sample introduction and collision cell experimental parameters were...

Impact of arsenic in foodstuffs on the people living in the arsenic-affected areas of West Bengal, India.

PubMed

Mandal, Badal K; Suzuki, Kazuo T; Anzai, Kazunori

2007-10-01

Although the accumulation of arsenic (As) in human blood is linked with some diseases and with occupational exposure, there are few reports on speciation of As in blood. On the basis of our earlier article, elevated level of arsenicals in human urine and blood were found in the ex-exposed population via As-containing drinking water. The aim of the present study was to get an insight on impact of As in foodstuffs on the people living in the As-affected areas. Moreover, speciation of arsenicals in urine, and water-samples found in arsenobetaine (AsB). Since sampling population (n=25) was not taking any seafood, As in foodstuffs was thought to be the prime source for this discrepancy. So, speciation of methanol extract of freeze-dried red blood cells (RBCs) and foodstuffs, and trichloro acetic acid (TCA) treated plasma by high performance liquid chromatography-inductively coupled argon plasma mass spectrometer (HPLC-ICP MS) collected from the study population (n=33) was carried out to support our hypothesis. Results showed that urine contained AsB (1.7%), arsenite (iAs(III)) (14.3), arsenate (iAs(V)) (4.9), monomethylarsonous acid (MMA(III)) (0.64), monomethylarsonic acid (MMA(V)) (13.6), dimethylarsinous acid (DMA(III)) (7.7), and dimethylarsinic acid (DMA(V)) (65.4). Blood contained 21.3 microg L(- 1) (mean) As and of which 27.3% was in plasma and 72.7% in RBCs. RBCs contained AsB (21.6%) and DMA(V) (78.4) and blood plasma contained AsB (12.4%), iAs(III) (25.9), MMA(V) (30.3), and DMA(V) (31.4). Furthermore, speciation of As in foodstuffs showed that most of them contained AsB (3.54-25.81 microg kg(- 1)) (25.81-312.44 microg kg(- 1)) along with iAs(III) (9.62-194.93), iAs(V) (17.63-78.33), MMA(V) (9.47-73.22) and DMA(V) (13.43-101.15) that supported the presence of AsB and elevated As in urine and blood samples of the present study group. Inorganic As (iAs) predominates in rice (67.17-86.62%) and in spices (40-90.35%), respectively over organic As. So, As in the food chain is a real threat to human health.

Inverse association between toenail arsenic and body mass index in a population of welders.

PubMed

Grashow, Rachel; Zhang, Jinming; Fang, Shona C; Weisskopf, Marc G; Christiani, David C; Kile, Molly L; Cavallari, Jennifer M

2014-05-01

Recent data show that arsenic may play a role in obesity-related diseases. However, urinary arsenic studies report an inverse association between arsenic level and body mass index (BMI). We explored whether toenail arsenic, a long-term exposure measure, was associated with BMI in 74 welders with known arsenic exposure. BMI showed significant inverse associations with toenail arsenic (p=0.01), which persisted in models adjusted for demographics, diet and work history. It is unclear whether low arsenic biomarker concentrations in high BMI subjects truly reflect lower exposures, or instead reflect internal or metabolic changes that alter arsenic metabolism and tissue deposition. Copyright © 2014 Elsevier Inc. All rights reserved.

An approach for identification and determination of arsenic species in the extract of kelp.

PubMed

Yu, Lee L; Wei, Chao; Zeisler, Rolf; Tong, Junting; Oflaz, Rabia; Bao, Haixia; Wang, Jun

2015-05-01

The National Institute of Standards and Technology is developing a kelp powder standard reference material (SRM) in support of dietary supplement measurements. Edible seaweeds such as kelp and laver consumed as diet or dietary supplement contain tens of mg/kg arsenic. The speciation information of arsenic in the seaweed should be provided because the total arsenic alone does not fully address the safety issue of the dietary supplement as the value assignment is originally intended. The inability to avail all arsenic species for value assignment measurements prevented the certification of arsenic species in the candidate SRM; however, approximately 70 % of total arsenic extracted with a 1:1 volume fraction of methanol:water mixture allowed arsenic speciation values to be assigned to a procedure-defined extract, which may be used for method validation in research to improve upon current extraction and measurement practices. Arsenic species in kelp and laver were identified using electrospray ionization ion trap time of flight mass spectrometry (ESI-IT-TOF). Arsenosugars As(328), As(482), and As(392) were found in the kelp candidate SRM while As(328) and As(482) were found in GBW 08521, a certified reference material (CRM) of laver produced by the National Institute of Metrology of China (NIM). A discovery that the digests of kelp and laver contained only dimethylarsinic acid led to the conclusion that the seaweeds did not contain detectible levels of arsenobetaine, arsenocholine or trimethylarsine oxide that could overlap with the peaks of arsenosugars in the separation. The mean ± s of (5.68 ± 0.28) mg/kg and (13.43 ± 0.31) mg/kg found for As(482) and As(392) in kelp, respectively, using instrumental neutron activation analysis (INAA) demonstrated that value assignment measurement of arsenosugars was possible without arsenosugar calibration standards.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chung, Chi-Jung; Department of Medical Research, China Medical University Hospital, Taichung, Taiwan; Huang, Chao-Yuan

Inter-individual variation in the metabolism of xenobiotics, caused by factors such as cigarette smoking or inorganic arsenic exposure, is hypothesized to be a susceptibility factor for urothelial carcinoma (UC). Therefore, our study aimed to evaluate the role of gene–environment interaction in the carcinogenesis of UC. A hospital-based case–control study was conducted. Urinary arsenic profiles were measured using high-performance liquid chromatography–hydride generator-atomic absorption spectrometry. Genotyping was performed using a polymerase chain reaction-restriction fragment length polymorphism technique. Information about cigarette smoking exposure was acquired from a lifestyle questionnaire. Multivariate logistic regression was applied to estimate the UC risk associated with certain riskmore » factors. We found that UC patients had higher urinary levels of total arsenic, higher percentages of inorganic arsenic (InAs%) and monomethylarsonic acid (MMA%) and lower percentages of dimethylarsinic acid (DMA%) compared to controls. Subjects carrying the GSTM1 null genotype had significantly increased UC risk. However, no association was observed between gene polymorphisms of CYP1A1, EPHX1, SULT1A1 and GSTT1 and UC risk after adjustment for age and sex. Significant gene–environment interactions among urinary arsenic profile, cigarette smoking, and GSTM1 wild/null polymorphism and UC risk were observed after adjustment for potential risk factors. Overall, gene–environment interactions simultaneously played an important role in UC carcinogenesis. In the future, large-scale studies should be conducted using tag-SNPs of xenobiotic-metabolism-related enzymes for gene determination. -- Highlights: ► Subjects with GSTM1 null genotype had significantly increased UC risk. ► UC patients had poor arsenic metabolic ability compared to controls. ► GSTM1 null genotype may modify arsenic related UC risk.« less

Periphyton and abiotic factors influencing arsenic speciation in aquatic environments: Periphyton alters arsenic speciation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lopez, Adeline R.; Silva, Silmara Costa; Webb, Samuel M.

Benthic periphytic biofilms are important food sources at the base of aquatic ecosystems. These biofilms also sit at the interface of oxic waters and hypoxic sediments, and can be influenced by or influence trace element speciation. In the present study, we compared arsenic (As) enrichment in periphyton exposed to arsenate (As[V]) or arsenite (As[III]) (20 μg/L, static renewal, 7 d), and we found similar accumulation patterns of total As (101 ± 27 and 88 ± 22mgkg -1 dry wt, respectively). Periphyton As was 6281- and 6684-fold higher than their aqueous exposures and occurred primarily as As(V). When these biofilms weremore » fed to larval mayflies, similar total As tissue concentrations (13.9 and 14.6mgkg -1 dry wt, respectively) were observed, revealing significant biodilution (~10% of their dietary concentrations). Finally, we investigated the influence of aeration and periphyton presence on As speciation in solutions and solid phases treated with As(III). Predominantly As(III) solutions were slowly oxidized over a 7-d time period, in the absence of periphyton, and aeration did not strongly affect oxidation rates. However, in the presence of periphyton, solution and solid-phase analyses (by microscale x-ray absorption spectroscopy) showed rapid As(III) oxidation to As(V) and an increasing proportion of organo-As forming over time. Thus periphyton plays several roles in As environmental behavior: 1) decreasing total dissolved As concentrations via abiotic and biotic accumulation, 2) rapidly oxidizing As(III) to As(V), 3) effluxing organo-As forms into solution, and 4) limiting trophic transfer to aquatic grazers.« less

Periphyton and abiotic factors influencing arsenic speciation in aquatic environments: Periphyton alters arsenic speciation

DOE PAGES

Lopez, Adeline R.; Silva, Silmara Costa; Webb, Samuel M.; ...

2017-11-02

Benthic periphytic biofilms are important food sources at the base of aquatic ecosystems. These biofilms also sit at the interface of oxic waters and hypoxic sediments, and can be influenced by or influence trace element speciation. In the present study, we compared arsenic (As) enrichment in periphyton exposed to arsenate (As[V]) or arsenite (As[III]) (20 μg/L, static renewal, 7 d), and we found similar accumulation patterns of total As (101 ± 27 and 88 ± 22mgkg -1 dry wt, respectively). Periphyton As was 6281- and 6684-fold higher than their aqueous exposures and occurred primarily as As(V). When these biofilms weremore » fed to larval mayflies, similar total As tissue concentrations (13.9 and 14.6mgkg -1 dry wt, respectively) were observed, revealing significant biodilution (~10% of their dietary concentrations). Finally, we investigated the influence of aeration and periphyton presence on As speciation in solutions and solid phases treated with As(III). Predominantly As(III) solutions were slowly oxidized over a 7-d time period, in the absence of periphyton, and aeration did not strongly affect oxidation rates. However, in the presence of periphyton, solution and solid-phase analyses (by microscale x-ray absorption spectroscopy) showed rapid As(III) oxidation to As(V) and an increasing proportion of organo-As forming over time. Thus periphyton plays several roles in As environmental behavior: 1) decreasing total dissolved As concentrations via abiotic and biotic accumulation, 2) rapidly oxidizing As(III) to As(V), 3) effluxing organo-As forms into solution, and 4) limiting trophic transfer to aquatic grazers.« less

Effect of Sodium Arsenite Dose Administered in the Drinking Water on the Urinary Bladder Epithelium of Female Arsenic (+3 oxidation state) Methyltransferase Knockout Mice

EPA Science Inventory

The enzyme arsenic (+3 oxidation state) methyltransferase (As3mt) catalyzes reactions converting inorganic arsenic to methylated metabolites, some of which are highly cytotoxic. In a previous study, we evaluated whether the As3mt null genotype in mice modified cytotoxic and proli...

Dimethylarsinic acid in drinking water changed the morphology but not the expression of DNA repair genes of bladder transitional epithelium in F344 rats

EPA Science Inventory

Inorganic arsenic increases urinary bladder transitional cell carcinoma in humans. In laboratory animals, it is dimethylarsinic acid [DMA(V)], a major arsenic metabolite in the urine of inorganic arsenic-exposed people, that increases transitional cell carcinoma, namely in F344 r...

Simultaneous speciation analysis of inorganic arsenic, chromium and selenium in environmental waters by 3-(2-aminoethylamino) propyltrimethoxysilane modified multi-wall carbon nanotubes packed microcolumn solid phase extraction and ICP-MS.

PubMed

Peng, Hanyong; Zhang, Nan; He, Man; Chen, Beibei; Hu, Bin

2015-01-01

Speciation analysis of inorganic arsenic, chromium and selenium in environmental waters is of great significance for the monitoring of environmental pollution. In this work, 3-(2-aminoethylamino) propyltrimethoxysilane (AAPTS) functionalized multi-wall carbon nanotubes (MWCNTs) were synthesized and employed as the adsorbent for simultaneous speciation analysis of inorganic arsenic, chromium and selenium in environmental waters by microcolumn solid-phase extraction (SPE)-inductively coupled plasma mass spectrometry (ICP-MS). It was found that As(V), Cr(VI) and Se(VI) could be selectively adsorbed on the microcolumn packed with AAPTS-MWCNTs adsorbent at pH around 2.2, while As(III), Cr(III) and Se(IV) could not be retained at this pH and passed through the microcolumn directly. Total inorganic arsenic, chromium and selenium was determined after the oxidation of As(III), Cr(III) and Se(IV) to As(V), Cr(VI) and Se(VI) with 10.0 μmol L(-1) KMnO4. The assay of As(III), Cr(III) and Se(IV) was based on subtracting As(V), Cr(VI) and Se(VI) from the total As, Cr and Se, respectively. Under the optimized conditions, the detection limits of 15, 38 and 16 ng L(-1) with the relative standard deviations (RSDs) of 7.4, 2.4 and 6.2% (c=1 µg L(-1), n=7) were obtained for As(V), Cr(VI) and Se(VI), respectively. The developed method was validated by analyzing four Certified Reference Materials, rainwater, Yangtze River and East Lake waters. Copyright © 2014 Elsevier B.V. All rights reserved.

Arsenic methylation capability and hypertension risk in subjects living in arseniasis-hyperendemic areas in southwestern Taiwan

DOE Office of Scientific and Technical Information (OSTI.GOV)

Huang, Y.-K.; Tseng, C.-H.; Department of Internal Medicine, National Taiwan University Hospital, Taipei, Taiwan

Background: Cumulative arsenic exposure (CAE) from drinking water has been shown to be associated with hypertension in a dose-response pattern. This study further explored the association between arsenic methylation capability and hypertension risk among residents of arseniasis-hyperendemic areas in Taiwan considering the effect of CAE and other potential confounders. Method: There were 871 subjects (488 women and 383 men) and among them 372 were diagnosed as having hypertension based on a positive history or measured systolic blood pressure {>=} 140 mm Hg and/or diastolic blood pressure {>=} 90 mm Hg. Urinary arsenic species were determined by high-performance liquid chromatography-hydride generatormore » and atomic absorption spectrometry. Primary arsenic methylation index [PMI, defined as monomethylarsonic acid (MMA{sup V}) divided by (As{sup III} + As{sup V})] and secondary arsenic methylation index (SMI, defined as dimethylarsinic acid divided by MMA{sup V}) were used as indicators for arsenic methylation capability. Results: The level of urinary arsenic was still significantly correlated with cumulative arsenic exposure (CAE) calculated from a questionnaire interview (p = 0.02) even after the residents stopped drinking the artesian well water for 2-3 decades. Hypertensive subjects had higher percentages of MMA{sup V} and lower SMI than subjects without hypertension. However, subjects having CAE > 0 mg/L-year had higher hypertension risk than those who had CAE = 0 mg/L-year disregard a high or low methylation index. Conclusion: Inefficient arsenic methylation ability may be related with hypertension risk.« less

Arsenite and Ferrous Iron Oxidation Linked to Chemolithotrophic Denitrification for the Immobilization of Arsenic in Anoxic Environments

PubMed Central

Sun, Wenjie; Sierra-Alvarez, Reyes; Milner, Lily; Oremland, Ron; Field, Jim A.

2014-01-01

The objective of this study was to explore a bioremediation strategy based on injecting NO3− to support the anoxic oxidation of ferrous iron (Fe(II)) and arsenite (As(III)) in the subsurface as a means to immobilize As in the form of arsenate (As(V)) adsorbed onto biogenic ferric (Fe(III)) (hydr)oxides. Continuous flow sand filled columns were used to simulate a natural anaerobic groundwater and sediment system with co-occurring As(III) and Fe(II) in the presence (SF1) or absence (SF2) of nitrate, respectively. During operation for 250 days, the average influent arsenic concentration of 567 µg l−1 was reduced to 10.6 (±9.6) µg l−1 in the effluent of column SF1. The cumulative removal of Fe(II) and As(III) in SF1 was 6.5–10-fold higher than that in SF2. Extraction and measurement of the mass of iron and arsenic immobilized on the sand packing of the columns was close to the iron and arsenic removed from the aqueous phase during column operation. The dominant speciation of the immobilized iron and arsenic was Fe(III) and As(V) in SF1, compared with Fe(II) and As(III) in SF2. The speciation was confirmed by XRD and XPS. The results indicate that microbial oxidation of As(III) and Fe(II) linked to denitrification resulted in the enhanced immobilization of aqueous arsenic in anaerobic environments by forming Fe(III) (hydr)oxides coated sands with adsorbed As(V). PMID:19764221

Systemic distribution and speciation of diphenylarsinic acid fed to rats

DOE Office of Scientific and Technical Information (OSTI.GOV)

Naranmandura, Hua; Analytical and Environmental Toxicology, Department of Laboratory Medicine and Pathology, University of Alberta, Edmonton, Alberta, T6G 2G3; Suzuki, Noriyuki

Diphenylarsinic acid (DPAA) is an environmental degradation product of diphenylarsine chloride or diphenylarsine cyanide, which were chemical warfare agents produced by Japan during the World War II. DPAA is now considered a dangerous environmental pollutant in Kamisu, Japan, where it is suspected of inducing health effects that include articulation disorders (cerebellar ataxia of the extremities and trunk), involuntary movements (myoclonus and tremor), and sleep disorders. In order to elucidate the toxic mechanism of DPAA, we focused on the distribution and metabolism of DPAA in rats. Systemic distribution of DPAA was determined by administering DPAA orally to rats at a singlemore » dose of 5.0 mg As/kg body weight, followed by speciation analysis of selected organs and body fluids. Most of the total arsenic burden was recovered in the urine (23% of the dose) and feces (27%), with the distribution in most other organs/tissues being less than 1%. However, compared with the typical distribution of inorganic dietary arsenic, DPAA administration resulted in elevated levels in the brain, testes and pancreas. In contrast to urine, in which DPAA was found mostly in its unmodified form, the tissues and organs contained arsenic that was mostly bound to non-soluble and soluble high molecular weight proteins. These bound arsenic species could be converted back to DPAA after oxidation with H{sub 2}O{sub 2}, suggesting that the DPAA bound to proteins had been reduced within the body and was in a trivalent oxidation state. Furthermore, we also detected two unknown arsenic metabolites in rat urine, which were assumed to be hydroxylated arsenic metabolites.« less

Gas and liquid chromatography with inductively coupled plasma mass spectrometry detection for environmental speciation analysis — advances and limitations

NASA Astrophysics Data System (ADS)

Szpunar, Joanna; McSheehy, Shona; Połeć, Kasia; Vacchina, Véronique; Mounicou, Sandra; Rodriguez, Isaac; Łobiński, Ryszard

2000-07-01

Recent advances in the coupling of gas chromatography (GC) and high performance liquid chromatography (HPLC) with inductively coupled plasma mass spectrometry (ICP MS) and their role in trace element speciation analysis of environmental materials are presented. The discussion is illustrated with three research examples concerning the following topics: (i) development and coupling of multicapillary microcolumn GC with ICP MS for speciation of organotin in sediment and biological tissue samples; (ii) speciation of arsenic in marine algae by size-exclusion-anion-exchange HPLC-ICP MS; and (iii) speciation of cadmium in plant cell cultures by size-exclusion HPLC-ICP MS. Particular attention is paid to the problem of signal identification in ICP MS chromatograms; the potential of electrospray MS/MS for this purpose is highlighted.

Heat-assisted aqueous extraction of rice flour for arsenic speciation analysis.

PubMed

Narukawa, Tomohiro; Chiba, Koichi

2010-07-28

A versatile heat-assisted pretreatment aqueous extraction method for the analysis of arsenic species in rice was developed. Rice flour certified reference materials NIST SRM1568a and NMIJ CRM 7503-a and a flour made from polished rice were used as samples, and HPLC-ICP-MS was employed for the determination of arsenic species. Arsenite [As(III)], arsenate [As(V)], monomethylarsonic acid (MMAA) and dimethylarsinic acid (DMAA) were detected in NIST SRM, and As(III), As(V) and DMAA were found in NMIJ CRM and the prepared polished rice flour. The sums of the concentrations of all species in each rice flour sample were 97-102% of the total arsenic concentration in each sample.

Arsenic speciation in hair and nails of acute promyelocytic leukemia (APL) patients undergoing arsenic trioxide treatment.

PubMed

Chen, Baowei; Cao, Fenglin; Lu, Xiufen; Shen, Shengwen; Zhou, Jin; Le, X Chris

2018-07-01

Arsenic in hair and nails has been used to assess chronic exposure of humans to environmental arsenic. However, it remains to be seen whether it is appropriate to evaluate acute exposure to sub-lethal doses of arsenic typically used in therapeutics. In this study, hair, fingernail and toenail samples were collected from nine acute promyelocytic leukemia (APL) patients who were administered intravenously the daily dose of 10 mg arsenic trioxide (7.5 mg arsenic) for up to 54 days. These hair and nail samples were analyzed for arsenic species using high performance liquid chromatography separation and inductively coupled plasma mass spectrometry detection (HPLC-ICPMS). Inorganic arsenite was the predominant form among water-extractable arsenicals. Dimethylarsinic acid (DMA V ), monomethylarsonic acid (MMA V ), monomethylarsonous acid (MMA III ), monomethylmonothioarsonic acid (MMMTA V ), and dimethylmonothioarsinic acid (DMMTA V ) were also detected in both hair and nail samples. This is the first report of the detection of MMA III and MMMTA V as metabolites of arsenic in hair and nails of APL patients. Copyright © 2018 Elsevier B.V. All rights reserved.

Multimedia Exposures to Arsenic and Lead for Children Near an Inactive Mine Tailings and Smelter Site

PubMed Central

Loh, Miranda M.; Sugeng, Anastasia; Lothrop, Nathan; Klimecki, Walter; Cox, Melissa; Wilkinson, Sarah T.; Lu, Zhenqiang; Beamer, Paloma I.

2016-01-01

Children living near contaminated mining waste areas may have high exposures to metals from the environment. This study investigates whether exposure to arsenic and lead is higher in children in a community near a legacy mine and smelter site in Arizona compared to children in other parts of the United States and the relationship of that exposure to the site. Arsenic and lead were measured in residential soil, house dust, tap water, urine, and toenail samples from 70 children in 34 households up to 7 miles from the site. Soil and house dust were sieved, digested, and analyzed via ICP-MS. Tap water and urine were analyzed without digestion, while toenails were washed, digested and analyzed. Blood lead was analyzed by an independent, certified laboratory. Spearman correlation coefficients were calculated between each environmental media and urine and toenails for arsenic and lead. Geometric mean arsenic (standard deviation) concentrations for each matrix were: 22.1 (2.59) ppm and 12.4 (2.27) ppm for soil and house dust (<63 μm), 5.71 (6.55) ppb for tap water, 14.0 (2.01) μg/L for specific gravity-corrected total urinary arsenic, 0.543 (3.22) ppm for toenails. Soil and vacuumed dust lead concentrations were 16.9 (2.03) ppm and 21.6 (1.90) ppm. The majority of blood lead levels were below the limit of quantification. Arsenic and lead concentrations in soil and house dust decreased with distance from the site. Concentrations in soil, house dust, tap water, along with floor dust loading were significantly associated with toenail and urinary arsenic but not lead. Mixed models showed that soil and tap water best predicted urinary arsenic. In our study, despite being present in mine tailings at similar levels, internal lead exposure was not high, but arsenic exposure was of concern, particularly from soil and tap water. Naturally occurring sources may be an additional important contributor to exposures in certain legacy mining areas. PMID:26803211

Determination of Total Arsenic and Speciation in Apple Juice by Liquid Chromatography-Inductively Coupled Plasma Mass Spectrometry: An Experiment for the Analytical Chemistry Laboratory

ERIC Educational Resources Information Center

He, Ping; Colon, Luis A.; Aga, Diana S.

2016-01-01

A two-part laboratory experiment was designed for upper-level analytical chemistry students to provide hands-on experience in the use of high performance liquid chromatography (HPLC) for separation and inductively coupled plasma mass spectrometry (ICP-MS) for detection. In the first part of the experiment, the students analyze total arsenic in…

Comparative study of atomic fluorescence spectroscopy and inductively coupled plasma mass spectrometry for mercury and arsenic multispeciation.

PubMed

Gómez-Ariza, José Luis; Lorenzo, Fernando; García-Barrera, Tamara

2005-05-01

Mercury and arsenic are two elements of undoubted importance owing to their toxic character. Although speciation of these elements has been developed separately, in this work for the first time the speciation of As and Hg using two atomic fluorescence detectors in a sequential ensemble is presented. A coupling based on the combination of high-performance liquid chromatography (where mercury and arsenic species are separated) and two atomic fluorescence detectors in series, with several online treatments, including photooxidation (UV) and hydride generation, has allowed the determination of mercury and arsenic compounds simultaneously. The detection limits for this device were 16, 3, 17, 12 and 8 ng mL(-1) for As(III), monomethylarsinic acid, As(V), Hg2+ and methylmercury, respectively. This coupling was compared with an analogous one based on inductively coupled plasma-mass spectrometry (ICP-MS) detection, with detection limits of 0.7, 0.5, 0.8, 0.9 and 1.1 ng mL(-1), respectively. Multispeciation based on ICP-MS exhibits better sensitivity than the coupling based on tandem atomic fluorescence, but this second device is a very robust system and exhibits obvious advantages related to the low cost of acquisition and maintenance, as well as easy handling, which makes it a suitable system for routine laboratories.

Creatinine, diet, micronutrients, and arsenic methylation in West Bengal, India.

PubMed

Basu, Arin; Mitra, Soma; Chung, Joyce; Guha Mazumder, D N; Ghosh, Nilima; Kalman, David; von Ehrenstein, Ondine S; Steinmaus, Craig; Liaw, Jane; Smith, Allan H

2011-09-01

Ingested inorganic arsenic (InAs) is methylated to monomethylated (MMA) and dimethylated metabolites (DMA). Methylation may have an important role in arsenic toxicity, because the monomethylated trivalent metabolite [MMA(III)] is highly toxic. We assessed the relationship of creatinine and nutrition--using dietary intake and blood concentrations of micronutrients--with arsenic metabolism, as reflected in the proportions of InAS, MMA, and DMA in urine, in the first study that incorporated both dietary and micronutrient data. We studied methylation patterns and nutritional factors in 405 persons who were selected from a cross-sectional survey of 7,638 people in an arsenic-exposed population in West Bengal, India. We assessed associations of urine creatinine and nutritional factors (19 dietary intake variables and 16 blood micronutrients) with arsenic metabolites in urine. Urinary creatinine had the strongest relationship with overall arsenic methylation to DMA. Those with the highest urinary creatinine concentrations had 7.2% more arsenic as DMA compared with those with low creatinine (p < 0.001). Animal fat intake had the strongest relationship with MMA% (highest tertile animal fat intake had 2.3% more arsenic as MMA, p < 0.001). Low serum selenium and low folate were also associated with increased MMA%. Urine creatinine concentration was the strongest biological marker of arsenic methylation efficiency, and therefore should not be used to adjust for urine concentration in arsenic studies. The new finding that animal fat intake has a positive relationship with MMA% warrants further assessment in other studies. Increased MMA% was also associated, to a lesser extent, with low serum selenium and folate.

Individual differences in arsenic metabolism and lung cancer in a case-control study in Cordoba, Argentina

DOE Office of Scientific and Technical Information (OSTI.GOV)

Steinmaus, Craig, E-mail: craigs@berkeley.ed; School of Public Health, University of California, Berkeley, CA; Yuan Yan

2010-09-01

In humans, ingested inorganic arsenic is metabolized to monomethylarsenic (MMA) then to dimethylarsenic (DMA), although in most people this process is not complete. Previous studies have identified associations between the proportion of urinary MMA (%MMA) and increased risks of several arsenic-related diseases, although none of these reported on lung cancer. In this study, urinary arsenic metabolites were assessed in 45 lung cancer cases and 75 controls from arsenic-exposed areas in Cordoba, Argentina. Folate has also been linked to arsenic-disease susceptibility, thus an exploratory assessment of associations between single nucleotide polymorphisms in folate metabolizing genes, arsenic methylation, and lung cancer wasmore » also conducted. In analyses limited to subjects with metabolite concentrations above detection limits, the mean %MMA was higher in cases than in controls (17.5% versus 14.3%, p = 0.01). The lung cancer odds ratio for subjects with %MMA in the upper tertile compared to those in the lowest tertile was 3.09 (95% CI, 1.08-8.81). Although the study size was too small for a definitive conclusion, there was an indication that lung cancer risks might be highest in those with a high %MMA who also carried cystathionine {beta}-synthase (CBS) rs234709 and rs4920037 variant alleles. This study is the first to report an association between individual differences in arsenic metabolism and lung cancer, a leading cause of arsenic-related mortality. These results add to the increasing body of evidence that variation in arsenic metabolism plays an important role in arsenic-disease susceptibility.« less

The effect of the Environmental Protection Agency maximum contaminant level on arsenic exposure in the USA from 2003 to 2014: an analysis of the National Health and Nutrition Examination Survey (NHANES).

PubMed

Nigra, Anne E; Sanchez, Tiffany R; Nachman, Keeve E; Harvey, David; Chillrud, Steven N; Graziano, Joseph H; Navas-Acien, Ana

2017-11-01

The current US Environmental Protection Agency (EPA) maximum contaminant level (MCL) for arsenic in public water systems (10 µg/L) took effect in 2006. Arsenic is not federally regulated in private wells. The impact of the 2006 MCL on arsenic exposure in the US, as confirmed through biomarkers, is presently unknown. We evaluated national trends in water arsenic exposure in the US, hypothesizing that urinary arsenic levels would decrease over time among participants using public water systems but not among those using well water. We further estimated the expected number of avoided lung, bladder, and skin cancer cases. We evaluated 14,127 participants in the National Health and Nutrition Examination Survey (NHANES) 2003-2014 with urinary dimethylarsinate (DMA) and total arsenic available. To isolate water exposure, we expanded a residual-based method to remove tobacco and dietary contributions of arsenic. We applied EPA risk assessment approaches to estimate the expected annual number of avoided cancer cases comparing arsenic exposure in 2013-2014 vs. 2003-2004. Among public water users, fully adjusted geometric means (GMs) of DMA decreased from 3.01 µg/L in 2003-2004 to 2.49 µg/L in 2013-2014 (17% reduction; 95% confidence interval 10%, 24%; p-trend<0.01); no change was observed among well water users (p-trend= 0.35). Assuming these estimated exposure reductions will remain similar across a lifetime, we estimate a reduction of 200 to 900 lung and bladder cancer cases per year depending on the approach used. The decline in urinary arsenic among public water but not private well users in NHANES 2003-2014 indicates that the implementation of the current MCL has reduced arsenic exposure in the US population. Our study supports prior work showing that well water users are inadequately protected against drinking water arsenic, and confirms the critical role of federal drinking water regulations in reducing toxic exposures and protecting human health. This work was supported by the National Institute of Environmental Health Sciences (1R01ES025216, R01ES021367, 5P30ES009089 and P42ES010349). A. E. Nigra was supported by 5T32ES007322.

Urinary Trivalent Methylated Arsenic Species in a Population Chronically Exposed to Inorganic Arsenic

PubMed Central

Valenzuela, Olga L.; Borja-Aburto, Victor H.; Garcia-Vargas, Gonzalo G.; Cruz-Gonzalez, Martha B.; Garcia-Montalvo, Eliud A.; Calderon-Aranda, Emma S.; Del Razo, Luz M.

2005-01-01

Chronic exposure to inorganic arsenic (iAs) has been associated with increased risk of various forms of cancer and of noncancerous diseases. Metabolic conversions of iAs that yield highly toxic and genotoxic methylarsonite (MAsIII) and dimethylarsinite (DMAsIII) may play a significant role in determining the extent and character of toxic and cancer-promoting effects of iAs exposure. In this study we examined the relationship between urinary profiles of MAsIII and DMAsIII and skin lesion markers of iAs toxicity in individuals exposed to iAs in drinking water. The study subjects were recruited among the residents of an endemic region of central Mexico. Drinking-water reservoirs in this region are heavily contaminated with iAs. Previous studies carried out in the local populations have found an increased incidence of pathologies, primarily skin lesions, that are characteristic of arseniasis. The goal of this study was to investigate the urinary profiles for the trivalent and pentavalent As metabolites in both high- and low-iAs–exposed subjects. Notably, methylated trivalent arsenicals were detected in 98% of analyzed urine samples. On average, the major metabolite, DMAsIII, represented 49% of total urinary As, followed by DMAsV (23.7%), iAsV (8.6%), iAsIII (8.5%), MAsIII (7.4%), and MAsV (2.8%). More important, the average MAsIII concentration was significantly higher in the urine of exposed individuals with skin lesions compared with those who drank iAs-contaminated water but had no skin lesions. These data suggest that urinary levels of MAsIII, the most toxic species among identified metabolites of iAs, may serve as an indicator to identify individuals with increased susceptibility to toxic and cancer-promoting effects of arseniasis. PMID:15743710

Arbuscular mycorrhizal symbiosis influences arsenic accumulation and speciation in Medicago truncatula L. in arsenic-contaminated soil.

PubMed

Zhang, Xin; Ren, Bai-Hui; Wu, Song-Lin; Sun, Yu-Qing; Lin, Ge; Chen, Bao-Dong

2015-01-01

In two pot experiments, wild type and a non-mycorrhizal mutant (TR25:3-1) of Medicago truncatula were grown in arsenic (As)-contaminated soil to investigate the influences of arbuscular mycorrhizal fungi (AMF) on As accumulation and speciation in host plants. The results indicated that the plant biomass of M. truncatula was dramatically increased by AM symbiosis. Mycorrhizal colonization significantly increased phosphorus concentrations and decreased As concentrations in plants. Moreover, mycorrhizal colonization generally increased the percentage of arsenite in total As both in shoots and roots, while dimethylarsenic acid (DMA) was only detected in shoots of mycorrhizal plants. The results suggested that AMF are most likely to get involved in the methylating of inorganic As into less toxic organic DMA and also in the reduction of arsenate to arsenite. The study allowed a deeper insight into the As detoxification mechanisms in AM associations. By using the mutant M. truncatula, we demonstrated the importance of AMF in plant As tolerance under natural conditions. Copyright © 2014 Elsevier Ltd. All rights reserved.

GENE EXPRESSION CAN DIFFERENTIATE CARCINOGENIC FROM NON-CARCINOGENIC DOSES OF DIMETHYLARSINIC ACID (DMAv) IN THE TRANSITIONAL EPITHELIUM OF THE URINARY BLADDER FROM FEMALE F344 RATS

EPA Science Inventory

Arsenic is an environmental concern worldwide, and drinking arsenic contaminated water has been associated with increased incidences of skin, lung and bladder cancer. Dimethylarsinic acid (DMAv) is a major metabolite of inorganic arsenic in rodents and humans and is the predomina...

Arsenic Speciation and Extraction and the Significance of Biodegradable Acid on Arsenic Removal—An Approach for Remediation of Arsenic-Contaminated Soil

PubMed Central

Nguyen Van, Thinh; Osanai, Yasuhito; Do Nguyen, Hai; Kurosawa, Kiyoshi

2017-01-01

A series of arsenic remediation tests were conducted using a washing method with biodegradable organic acids, including oxalic, citric and ascorbic acids. Approximately 80% of the arsenic in one sample was removed under the effect of the ascorbic and oxalic acid combination, which was roughly twice higher than the effectiveness of the ascorbic and citric acid combination under the same conditions. The soils treated using biodegradable acids had low remaining concentrations of arsenic that are primarily contained in the crystalline iron oxides and organic matter fractions. The close correlation between extracted arsenic and extracted iron/aluminum suggested that arsenic was removed via the dissolution of Fe/Al oxides in soils. The fractionation of arsenic in four contaminated soils was investigated using a modified sequential extraction method. Regarding fractionation, we found that most of the soil contained high proportions of arsenic (As) in exchangeable fractions with phosphorus, amorphous oxides, and crystalline iron oxides, while a small amount of the arsenic fraction was organic matter-bound. This study indicated that biodegradable organic acids can be considered as a means for arsenic-contaminated soil remediation.

Arsenic and selenium in microbial metabolism

USGS Publications Warehouse

Stolz, John F.; Basu, Partha; Santini, Joanne M.; Oremland, Ronald S.

2006-01-01

Arsenic and selenium are readily metabolized by prokaryotes, participating in a full range of metabolic functions including assimilation, methylation, detoxification, and anaerobic respiration. Arsenic speciation and mobility is affected by microbes through oxidation/reduction reactions as part of resistance and respiratory processes. A robust arsenic cycle has been demonstrated in diverse environments. Respiratory arsenate reductases, arsenic methyltransferases, and new components in arsenic resistance have been recently described. The requirement for selenium stems primarily from its incorporation into selenocysteine and its function in selenoenzymes. Selenium oxyanions can serve as an electron acceptor in anaerobic respiration, forming distinct nanoparticles of elemental selenium that may be enriched in (76)Se. The biogenesis of selenoproteins has been elucidated, and selenium methyltransferases and a respiratory selenate reductase have also been described. This review highlights recent advances in ecology, biochemistry, and molecular biology and provides a prelude to the impact of genomics studies.

Chemical speciation and ecological risk assessment of arsenic in marine sediments from Izmir Bay (Eastern Aegean Sea).

PubMed

Gonul, L T

2015-12-01

Total arsenic, arsenic(III) and (V), Fe, and Mn were measured in 17 surface sediment samples from Izmir Bay. The concentrations and ecological risk of As were characterized in the sediment affected by urban and agricultural activities. Total As ranged from 8.87 to 28.3 μg g(-1) dry weight (96.5-99.9 % as inorganic As). Distribution of total As and total As/Fe followed a different trend in sediments at all sampling sites. Arsenite (As(III)) was the most dominant form followed by As(V), while organic arsenic represented a minor constituent (0.03 to 3.49 %). The highest concentration of total As was observed at Gediz River estuary and exceeded lower threshold value (threshold effects level (TEL)). Due to the biological reduction of As(V) and abundance of Fe (oxyhydr)oxides in the sediments, most inorganic As in the Izmir Bay was present as As(III). Besides, the levels of As were >TEL and

Arsenic Methylation and Lung and Bladder Cancer in a Case-control Study in Northern Chile

PubMed Central

Melak, Dawit; Ferreccio, Catterina; Kalman, David; Parra, Roxana; Acevedo, Johanna; Pérez, Liliana; Cortés, Sandra; Smith, Allan H; Yuan, Yan; Liaw, Jane; Steinmaus, Craig

2014-01-01

In humans, ingested inorganic arsenic is metabolized to monomethylarsenic (MMA) then to dimethylarsenic (DMA), although this process is not complete in most people. The trivalent form of MMA is highly toxic in vitro and previous studies have identified associations between the proportion of urinary arsenic as MMA (%MMA) and several arsenic-related diseases. To date, however, relatively little is known about its role in lung cancer, the most common cause of arsenic-related death, or about its impacts on people drinking water with lower arsenic concentrations (e.g., <200 μg/L). In this study, urinary arsenic metabolites were measured in 94 lung and 117 bladder cancer cases and 347 population-based controls from areas in northern Chile with a wide range of drinking water arsenic concentrations. Lung cancer odds ratios adjusted for age, sex, and smoking by increasing tertiles of %MMA were 1.00, 1.91 (95% confidence interval (CI), 0.99–3.67), and 3.26 (1.76–6.04) (p-trend <0.001). Corresponding odds ratios for bladder cancer were 1.00, 1.81 (1.06–3.11), and 2.02 (1.15–3.54) (p-trend <0.001). In analyses confined to subjects only with arsenic water concentrations <200 μg/L (median=60 μg/L), lung and bladder cancer odds ratios for subjects in the upper tertile of %MMA compared to subjects in the lower two tertiles were 2.48 (1.08–5.68) and 2.37 (1.01–5.57), respectively. Overall, these findings provide evidence that inter-individual differences in arsenic metabolism may be an important risk factor for arsenic-related lung cancer, and may play a role in cancer risks among people exposed to relatively low arsenic water concentrations. PMID:24296302

Mouse arsenic (+3 oxidation state) methyltransferase genotype affects metabolism and tissue dosimetry of arsenicals after arsenite administration in drinking water.

PubMed

Chen, Baowei; Arnold, Lora L; Cohen, Samuel M; Thomas, David J; Le, X Chris

2011-12-01

Arsenic (+3 oxidation state) methyltransferase (As3mt) catalyzes methylation of inorganic arsenic (iAs) producing a number of methylated arsenic metabolites. Although methylation has been commonly considered a pathway for detoxification of arsenic, some highly reactive methylated arsenicals may contribute to toxicity associated with exposure to inorganic arsenic. Here, adult female wild-type (WT) C57BL/6 mice and female As3mt knockout (KO) mice received drinking water that contained 1, 10, or 25 ppm (mg/l) of arsenite for 33 days and blood, liver, kidney, and lung were taken for arsenic speciation. Genotype markedly affected concentrations of arsenicals in tissues. Summed concentrations of arsenicals in plasma were higher in WT than in KO mice; in red blood cells, summed concentrations of arsenicals were higher in KO than in WT mice. In liver, kidney, and lung, summed concentrations of arsenicals were greater in KO than in WT mice. Although capacity for arsenic methylation is much reduced in KO mice, some mono-, di-, and tri-methylated arsenicals were found in tissues of KO mice, likely reflecting the activity of other tissue methyltransferases or preabsorptive metabolism by the microbiota of the gastrointestinal tract. These results show that the genotype for arsenic methylation determines the phenotypes of arsenic retention and distribution and affects the dose- and organ-dependent toxicity associated with exposure to inorganic arsenic.

Bioaccessibility, release kinetics, and molecular speciation of arsenic and lead in geo-dusts from the Iron King Mine Federal Superfund site in Humboldt, Arizona.

PubMed

Menka, Nazune; Root, Rob; Chorover, Jon

2014-01-01

Mine tailings contain multiple toxic metal(loid)s that pose a threat to human health via inhalation and ingestion. The goals of this research include understanding the speciation and molecular environment of these toxic metal(loid)s (arsenic and lead) as well as the impacts particle size and residence time have on their bioaccessibilty in simulated gastric and lung fluid. Additionally, future work will include smaller size fractions (PM10 and PM2.5) of surface mine tailings, with the goal of increasing our understanding of multi-metal release from contaminated geo-dusts in simulated bio-fluids. This research is important to environmental human health risk assessment as it increases the accuracy of exposure estimations to toxic metal(loid)s.

Chromated copper arsenate-treated fence posts in the agronomic landscape: soil properties controlling arsenic speciation and spatial distribution.

PubMed

Schwer Iii, Donald R; McNear, David H

2011-01-01

Soils adjacent to chromated copper arsenate (CCA)-treated fence posts along a fence line transecting different soil series, parent material, drainage classes, and slope were used to determine which soil properties had the most influence on As spatial distribution and speciation. Metal distribution was evaluated at macroscopic (total metal concentration contour maps) and microscopic scales (micro-synchrotron X-ray fluorescence maps), As speciation was determined using extended X-ray absorption fine structure spectroscopy, and redox status and a myriad of other basic soil properties were elucidated. All geochemical parameters measured point to a condition in which the mobilization of As becomes more favorable moving down the topographic gradient, likely resulting through competition (Meh-P, SOM), neutral or slightly basic pH, and redox conditions that are favorable for As mobilization (higher Fe(II) and total-Fe concentrations in water extracts). On the landscape scale, with hundreds of kilometers of fence, the arsenic loading into the soil can be substantial (∼8-12 kg km). Although a significant amount of the As is stable, extended use of CCA-treated wood has resulted in elevated As concentrations in the local environment, increasing the risk of exposure and ecosystem perturbation. Therefore, a move toward arsenic-free alternatives in agricultural applications for which it is currently permitted should be considered. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

Champagne Pool (New Zealand) Thermophiles Yield Insights into the Evolution of Microbial Arsenic Resistance

NASA Astrophysics Data System (ADS)

Hug, K.; Krikowa, F.; Morgan, X.; Maher, W. A.; Stott, M. B.; Moreau, J. W.

2011-12-01

Arsenic is a highly toxic metalloid typically enriched in geothermal waters due to aqueous weathering of arsenic-bearing minerals. Investigation of enzymatic pathways by which thermophilic microorganisms cope with toxic arsenic levels may yield insights into the evolution of arsenic resistance mechanisms on the early Earth. At Wai-O-Tapu in the Taupo Volcanic Zone on the North Island of New Zealand, hot springs with temperatures of 30-90°C and elemental sulfur concentrations (expressed as equivalent sulfate) from 340 to 850 mg/l establish a range of environmental conditions. Total arsenic concentrations varied from 0.083 mg/l to 56 mg/l. Arsenic speciation analysis elucidated various biogeochemical arsenic transformations occurring within different springs. For example, in the Alum Cliff spring oxidizing conditions (Eh = 225 mV) were expected to stabilize dissolved arsenate (AsO43-). However, HPLC-ICPMS analyses yielded dissolved arsenate and arsenite (AsO33-) concentrations of 0.25 mg/l versus 43.3 mg/l, respectively, and point towards microbial arsenate reduction as the likely mechanism for arsenic redox transformation. 16S rRNA gene cloning of Alum Cliff DNA showed a predominantly archaeal population with the dominant clone "AC1_A1" most closely related (99% sequence similarity, NCBI BLAST°) to the uncultured Sulfolobus clone "ChP_97P" found in Champagne Pool (Childs et al., 2008). The closest isolated relative to AC1_A1 is Sulfolobus tokodaii str. TW with a sequence similarity of 94%. Arsenic speciation measurements from the Alum Cliff spring suggest that clone AC1_A1 features the arsenate reduction resistance mechanism, and we hypothesize therefore that an arsC (homolog or analog) provides this functionality. The organic arsenic species monomethylarsonic acid (MMA) and dimethylarsinic acid (DMA), detected via HPLC-ICPMS at concentrations ranging from 1 μg/l to 12 μg/l in various springs, may also implicate microbial methyl-group transfers as an active detoxification mechanism. These results yield insights into potential arsenic detoxification strategies that may have fostered the evolution of thermophiles in ancient geothermal systems. Ref. : Childs A.M., Mountain B.W., O'Toole R., Stott M.B. (2008). "Relating Microbial Community and Physiochemical parameters of a Hot Spring: Champagne Pool, Wai-o-tapu, New Zealand." Geomicrobiology Journal 25 (7-8):441-453.

[Effect of the interaction of microorganisms and iron oxides on arsenic releasing into groundwater in Chinese Loess].

PubMed

Xie, Yun-Yun; Chen, Tian-Hu; Zhou, Yue-Fei; Xie, Qiao-Qin

2013-10-01

A large part of groundwater in the Chinese Loess Plateau area is characterized by high arsenic concentration. Anaerobic bacteria have been considered to play key roles in promoting arsenic releasing from loess to groundwater. However, this hypothesis remains unconfirmed. Based on modeling experiments, this study investigated the speciation of arsenic in loess, and then determined the release rates and quantities of arsenic with the mediation of anaerobic bacteria. The results showed that arsenic contents in loess were between 23 mg.kg-1 and 30 mg.kg-1. No obvious arsenic content difference among loess samples was observed. The ratios for specific adsorbed, iron oxides co-precipitated and silicate co-precipitated arsenic were 37.76% , 36. 15% and 25. 69% , respectively. Indigenous microorganisms, dissimilatory iron reducing bacteria (DIRB) and sulfate reducing bacteria (SRB) could all promote the release of arsenic from loess. Organic matters highly affected the release rates. More than 100 mg.L-1 sodium lactate was required for all bacterial experiments to facilitate obvious arsenic release. Considering the redox condition in loess, the contribution of SRB to arsenic release in loess area was less feasible than that of DIRB and indigenous microorganisms.

Considerations in As analysis and speciation

USGS Publications Warehouse

Edwards, M.; Patel, S.; McNeil, L.; Chen, H.W.; Frey, M.; Eaton, A.D.; Antweiler, Ronald C.; Taylor, Howard E.

1998-01-01

This article summarizes recent experiences in arsenic (As) quantification, preservation, and speciation developed during AWWA Research Foundation (AWWARF) and Water Industry Technical Action Fund (WITAF) projects. The goal of this article is to alert analysts and decision-makers to potential problems in As analysis and speciation, because there appear to be several unresolved problems with routine analytical approaches. In true split drinking water samples As was quantified by three accepted analytical methods in three laboratories. The techniques used were graphite furnace atomic absorption spectrometry (GFAAS), inductively coupled plasma mass spectrometry (ICP-MS), and hydride generation inductively coupled plasma-emission spectrometry (HG-ICP-AES). Experimental findings are organized into sections on As analysis, particulate As in water supplies, and examination of As speciation methods.

Speciation and monitoring test for inorganic arsenic in white rice flour.

PubMed

Narukawa, Tomohiro; Hioki, Akiharu; Chiba, Koichi

2012-02-01

A monitoring test for arsenic species in white rice flour was developed and applied to flours made from 20 samples of polished rice collected from locations all over Japan. The arsenic species in white rice flour made from five samples each of four types of rice were analyzed by HPLC-ICP-MS after a heat-assisted aqueous extraction. The total arsenic and major and minor element concentrations in the white rice flours were measured by ICP-MS and ICP-OES after microwave-assisted digestion. 91 ± 1% of the arsenic in the flours was extractable. Concentrations of arsenite [As(III)], arsenate [As(V)], and dimethylarsinic acid (DMAA) were closely positively correlated with the total arsenic concentrations. The total arsenic concentration in flours made from rice collected around Japan was 0.15 ± 0.07 mg kg(-1) (highest, 0.32 mg kg(-1)), which is very low. It was thus confirmed that the white rice flour samples collected in this experiment were not suffered from noticeable As contamination.

DIETARY ARSENIC EXPOSURE ASSESSMENT USING ENZYMATIC BASED EXTRACTION CONDITIONS AND DETECTION OF URINARY THIO-ARSENICALS AS METABOLITES OF EXPOSURE - MCEARD2

EPA Science Inventory

Inorganic arsenic is classified as a carcinogen and has been linked to lung and bladder cancer as well as other non-cancerous health effects. Because of these health effects the U.S. EPA has set a Maximum Contaminant Level (MCL) at 10ppb based on a linear extrapolation of risk an...

Accumulation of Arsenic Speciation and In Vivo Toxicity Following Oral Administration of a Chinese Patent Medicine Xiao-Er-Zhi-Bao-Wan in Rats

PubMed Central

Luo, Jiaoyang; Han, Xu; Dou, Xiaowen; Zhang, Lei; Yang, Shihai; Yang, Meihua

2017-01-01

Realgar-containing traditional Chinese medicines such as Xiao-Er-Zhi-Bao-Wan (XEZBW), have been widely used for thousands of years. However, events associated with arsenic-induced ailments have increasingly become a public concern. To address the toxicity of XEZBW, we studied the histopathology and blood biochemistry of rats exposed to XEZBW using technology like high-performance liquid chromatography-inductively coupled mass spectrometry to determine arsenic speciation. Our results demonstrated that dimethylarsinic acid (DMA) increased from 18.57 ± 7.45 to 22.74 ± 7.45 ng/g in rat kidney after oral administration for 7 and 14 days, which was 10-fold higher than the levels observed in controls. Trivalent arsenite As(III) showed a large increase on day 7 (26.99 ± 1.98 ng/g), followed by a slight decrease on day 14 (13.67 ± 6.48 ng/g). Total arsenic levels on day 7 (185.52 ± 24.56 ng/g) and day 14 (198.57 ± 26.26 ng/g) were nearly twofold higher than that in the control group (92.77 ± 14.98 ng/g). Histopathological analysis showed mild injury in the liver and kidney of rats subjected to oral administration of realgar for 14 days. As in the XEZBW groups, a mild injury in these organs was observed after administration for 14 days. This study inferred that the toxicity of arsenic was concentration- and time-dependent. The accumulation of DMA, a byproduct of choline metabolism, was responsible for inducing higher toxicity. Therefore, we concluded that measuring the levels of DMA, instead of total arsenic, might be more suitable for evaluating the toxicity of realgar-containing traditional Chinese medicines. PMID:28790918

Arsenite and ferrous iron oxidation linked to chemolithotrophic denitrification for the immobilization of arsenic in anoxic environments

USGS Publications Warehouse

Sun, W.; Sierra-Alvarez, R.; Milner, L.; Oremland, R.; Field, J.A.

2009-01-01

The objective of this study was to explore a bioremediation strategy based on injecting NO3- to support the anoxic oxidation of ferrous iron (Fe(II)) and arsenite (As(III)) in the subsurface as a means to immobilize As in the form of arsenate (As(V)) adsorbed onto biogenic ferric (Fe(III)) (hydr)oxides. Continuous flows and filled columns were used to simulate a natural anaerobic groundwater and sediment system with co-occurring As(III) and Fe(II) in the presence (column SF1) or absence (column SF2) of nitrate, respectively. During operation for 250 days, the average influent arsenic concentration of 567 ??g L-1 was reduced to 10.6 (??9.6) ??g L-1 in the effluent of column SF1. The cumulative removal of Fe(II) and As(III) in SF1 was 6.5 to 10-fold higher than that in SF2. Extraction and measurement of the mass of iron and arsenic immobilized on the sand packing of the columns were close to the iron and arsenic removed from the aqueous phase during column operation. The dominant speciation of the immobilized iron and arsenic was Fe(III) and As(V) in SF1, compared with Fe(II) and As(III) in SF2. The speciation was confirmed by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The results indicate that microbial oxidation of As(III) and Fe(II) linked to denitrification resulted in the enhanced immobilization of aqueous arsenic in anaerobic environments by forming Fe(III) (hydr)oxide coated sands with adsorbed As(V). ?? 2009 American Chemical Society.

LC-ICP-MS analysis of arsenic compounds in dominant seaweeds from the Thermaikos Gulf (Northern Aegean Sea, Greece).

PubMed

Pell, Albert; Kokkinis, Giannis; Malea, Paraskevi; Pergantis, Spiros A; Rubio, Roser; López-Sánchez, José Fermín

2013-11-01

The content of total arsenic and arsenic compounds in the dominant seaweed species in the Thermaikos Gulf, Northern Aegean Sea was determined in samples collected in different seasons. Total arsenic was determined by acid digestion followed by ICP-MS. Arsenic speciation was analyzed by water extraction followed by LC-ICP-MS. Total arsenic concentrations in the seaweeds ranged from 1.39 to 55.0 mg kg(-1). Cystoseira species and Codium fragile showed the highest total As contents, while Ulva species (U. intestinalis, U. rigida,U. fasciata) had the lowest Arsenosugars, the most common arsenic species in seaweeds, were found in all samples, and glycerol-arsenosugar was the most common form; however, phosphate-arsenosugar and sulfate-arsenosugar were also present. Inorganic arsenic was measured in seven algae species and detected in another. Arsenate was the most abundant species in Cystoseira barbata (27.0 mg kg(-1)). Arsenobetaine was measured in only one sample. Methylated arsenic species were measured at very low concentrations. The information should contribute to further understanding the presence of arsenic compounds in dominant seaweeds from the Thermaikos Gulf. Copyright © 2013 Elsevier Ltd. All rights reserved.

The relationships between arsenic methylation and both skin lesions and hypertension caused by chronic exposure to arsenic in drinking water.

PubMed

Wei, Binggan; Yu, Jiangping; Wang, Jing; Yang, Linsheng; Li, Hairong; Kong, Chang; Xia, Yajuan; Wu, Kegong

2017-07-01

The associations between arsenic exposure, arsenic methylation, and the prevalence of skin lesions and hypertension are investigated. The results indicate that the HS (hypertension and skin lesions) group and the S (skin lesions) group have higher urinary concentrations of iAs (inorganic arsenic), MMA (monomethylarsonic acid), DMA (dimethylarsinous acid) and%MMA, and lower SMI (secondary arsenic methylation index) compared to the H (hypertension) and N (without both hypertension and skin lesions) groups. The arsenic content in water which caused H may be lower than that which caused HS and S. In addition, the odds ratios suggest that higher urinary concentrations of iAs and MMA, %iAs, %MMA and PMI elevate the prevalence of only hypertension and skin lesions, and both hypertension and skin lesions. However, higher%DMA and SMI, and lower%MMA increase the prevalence of both hypertension and skin lesions compared to that of only skin lesions. It can be concluded that skin lesions subjects have higher prevalence of hypertension. Hypertension subjects may have higher prevalence of skin lesions. Lower%DMA and SMI, higher%iAs, %MMA and PMI enhance the prevalence of only hypertension and skin lesions, and both hypertension and skin lesions. Moreover, iAs and MMA may have higher toxicity and lead to both hypertension and skin lesions than to only hypertension. Copyright © 2017 Elsevier B.V. All rights reserved.

Arsenic Redistribution Between Sediments and Water Near a Highly Contaminated Source

DOE Office of Scientific and Technical Information (OSTI.GOV)

Keimowitz,A.; Zheng, Y.; Chillrud, S.

2005-01-01

Mechanisms controlling arsenic partitioning between sediment, groundwater, porewaters, and surface waters were investigated at the Vineland Chemical Company Superfund site in southern New Jersey. Extensive inorganic and organic arsenic contamination at this site (historical total arsenic >10 000 {micro}g L{sup -1} or >130 {micro}M in groundwater) has spread downstream to the Blackwater Branch, Maurice River, and Union Lake. Stream discharge was measured in the Blackwater Branch, and water samples and sediment cores were obtained from both the stream and the lake. Porewaters and sediments were analyzed for arsenic speciation as well as total arsenic, iron, manganese, and sulfur, and theymore » indicate that geochemical processes controlling mobility of arsenic were different in these two locations. Arsenic partitioning in the Blackwater Branch was consistent with arsenic primarily being controlled by sulfur, whereas in Union Lake, the data were consistent with arsenic being controlled largely by iron. Stream discharge and arsenic concentrations indicate that despite large-scale groundwater extraction and treatment, >99% of arsenic transport away from the site results from continued discharge of high arsenic groundwater to the stream, rather than remobilization of arsenic in stream sediments. Changing redox conditions would be expected to change arsenic retention on sediments. In sulfur-controlled stream sediments, more oxic conditions could oxidize arsenic-bearing sulfide minerals, thereby releasing arsenic to porewaters and streamwaters; in iron-controlled lake sediments, more reducing conditions could release arsenic from sediments via reductive dissolution of arsenic-bearing iron oxides.« less

Arsenic levels in immigrant children from countries at risk of consuming arsenic polluted water compared to children from Barcelona.

PubMed

Piñol, S; Sala, A; Guzman, C; Marcos, S; Joya, X; Puig, C; Velasco, M; Velez, D; Vall, O; Garcia-Algar, O

2015-11-01

Arsenic is a highly toxic element that pollutes groundwater, being a major environmental problem worldwide, especially in the Bengal Basin. About 40% of patients in our outpatient clinics come from those countries, and there is no published data about their arsenic exposure. This study compares arsenic exposure between immigrant and native children. A total of 114 children (57 natives, 57 immigrants), aged 2 months to 16 years, were recruited and sociodemographic and environmental exposure data were recorded. Total arsenic in urine, hair, and nails and arsenic-speciated compounds in urine were determined. We did not find significant differences in total and inorganic arsenic levels in urine and hair, but in organic arsenic monomethylarsenic acid (MMA) and dimethylarsinous acid (DMA) in urine and in total arsenic in nails. However, these values were not in the toxic range. There were significant differences between longer than 5 years exposure and less than 5 years exposure (consumption of water from tube wells), with respect to inorganic and organic MMA arsenic in urine and total arsenic in nails. There was partial correlation between the duration of exposure and inorganic arsenic levels in urine. Immigrant children have higher arsenic levels than native children, but they are not toxic. At present, there is no need for specific arsenic screening or follow-up in immigrant children recently arrived in Spain from exposure high-risk countries.

INVESTIGATION OF ARSENIC SPECIATION ON DRINKING WATER TREATMENT MEDIA UTILIZING AUTOMATED SEQUENTIAL CONTINUOUS FLOW EXTRACTION WITH IC-ICP-MS DETECTION

EPA Science Inventory

Three treatment media, used for the removal of arsenic from drinking water, were sequentially extracted using 10mM MgCl2 (pH 8), 10mM NaH2PO4 (pH 7) followed by 10mM (NH4)2C2O4 (pH 3). The media were extracted using an on-line automated continuous extraction system which allowed...

Phytotoxicity and uptake of roxarsone by wheat (Triticum aestivum L.) seedlings.

PubMed

Fu, Qing-Long; Blaney, Lee; Zhou, Dong-Mei

2016-12-01

Roxarsone (ROX), the primary aromatic arsenical additive (AAA) used in animal feeding operations, is of increasing concern to environmental and human health due to land application of ROX-laden animal manure. Few studies have investigated the phytotoxicity, uptake mechanisms, and speciation of AAA in crop plants. In this study, wheat seedlings were employed to address these issues under hydroponic conditions. Compared to inorganic arsenic, ROX was less toxic to wheat root elongation. Wheat roots were more sensitive to ROX stress than shoots. For the first time, metabolized inorganic arsenic was detected in plants, although ROX was the predominant detected arsenic species in wheat seedlings. ROX uptake and toxicity to roots were inhibited by humic acid at concentrations higher than 50 mg/L due to interaction with ROX. Phosphate enhanced ROX uptake, but no trends were observed for ROX uptake in the presence of glycerol at concentrations lower than 250 mM. In addition, ROX uptake was significantly decreased by silicate (Si(IV), 0.5-10 mM) and the metabolic inhibitor, 2,4-dinitrophenol (0.5-2 mM), indicating that ROX transport into wheat roots was actively mediated by Si(IV)-sensitive transporters. These findings provide important insights into the fate and speciation of AAA in soil-water-plant systems relevant to human health. Copyright © 2016 Elsevier Ltd. All rights reserved.

XRCC1 Arg194Trp and Arg399Gln polymorphisms and arsenic methylation capacity are associated with urothelial carcinoma

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chiang, Chien-I; Huang, Ya-Li; Chen, Wei-Jen

The association between DNA repair gene polymorphisms and bladder cancer has been widely studied. However, few studies have examined the correlation between urothelial carcinoma (UC) and arsenic or its metabolites. The aim of this study was to examine the association between polymorphisms of the DNA repair genes, XRCC1 Arg194Trp, XRCC1 Arg399Gln, XRCC3 Thr241Met, and XPD Lys751Gln, with urinary arsenic profiles and UC. To this end, we conducted a hospital-based case–control study with 324 UC patients and 647 age- and gender-matched non-cancer controls. Genomic DNA was used to examine the genotype of XRCC1 Arg194Trp, XRCC1 Arg399Gln, XRCC3 Thr241Met, and XPD Lys751Glnmore » by PCR-restriction fragment length polymorphism analysis (PCR-RFLP). Urinary arsenic profiles were measured by high performance liquid chromatography (HPLC) linked with hydride generator and atomic absorption spectrometry. The XRCC1 399 Gln/Gln and 194 Arg/Trp and Trp/Trp genotypes were significantly related to UC, and the odds ratio (OR) and 95% confidence interval (95%CI) were 1.68 (1.03–2.75) and 0.66 (0.48–0.90), respectively. Participants with higher total urinary arsenic levels, a higher percentage of inorganic arsenic (InAs%) and a lower percentage of dimethylarsinic acid (DMA%) had a higher OR of UC. Participants carrying XRCC1 risk diplotypes G-C/G-C, A-C/A-C, and A-T/G-T, and who had higher total arsenic levels, higher InAs%, or lower DMA% compared to those with other XRCC1 diplotypes had a higher OR of UC. Our results suggest that the XRCC1 399 Gln/Gln and 194 Arg/Arg DNA repair genes play an important role in poor arsenic methylation capacity, thereby increasing the risk of UC in non-obvious arsenic exposure areas. - Highlights: • The XRCC1 399Gln/Gln genotype was significantly associated with increased OR of UC. • The XRCC1 194 Arg/Trp and Trp/Trp genotype had a significantly decreased OR of UC. • Combined effect of the XRCC1 genotypes and poor arsenic methylation capacity on UC.« less

Legacy of the California Gold Rush: Environmental geochemistry of arsenic in the southern Mother Lode Gold District

USGS Publications Warehouse

Savage, K.S.; Bird, D.K.; Ashley, R.P.

2000-01-01

Gold mining activity in the Sierra Nevada foothills, both recently and during the California Gold Rush, has exposed arsenic-rich pyritic rocks to weathering and erosion. This study describes arsenic concentration and speciation in three hydrogeologic settings in the southern Mother Lode Gold District: mineralized outcrops and mine waste rock (overburden); mill tailings submerged in a water reservoir; and lake waters in this monomictic reservoir and in a monomictic lake developing within a recent open-pit mine. These environments are characterized by distinct modes of rock-water interaction that influence the local transport and fate of arsenic. Arsenic in outcrops and waste rock occurs in arsenian pyrite containing an average of 2 wt% arsenic. Arsenic is concentrated up to 1300 ppm in fine-grained, friable iron-rich weathering products of the arsenian pyrite (goethite, jarosite, copiapite), which develop as efflorescences and crusts on weathering outcrops. Arsenic is sorbed as a bidentate complex on goethite, and substitutes for sulfate in jarosite. Submerged mill tailings obtained by gravity core at Don Pedro Reservoir contain arsenic up to 300 ppm in coarse sand layers. Overlying surface muds have less arsenic in the solid fraction but higher concentrations in porewaters (up to 500 ??g/L) than the sands. Fine quartz tailings also contain up to 3.5 ppm mercury related to the ore processing. The pH values in sediment porewaters range from 3.7 in buried gypsum-bearing sands and tailings to 7 in the overlying lake sediments. Reservoir waters immediately above the cores contain up to 3.5 ??g/L arsenic; lake waters away from the submerged tailings typically contain less than 1 ??g/L arsenic. Dewatering during excavation of the Harvard open-pit mine produced a hydrologic cone of depression that has been recovering toward the pre-mining groundwater configuration since mining ended in 1994. Aqueous arsenic concentrations in the 80 m deep pit lake are up to 1000 ??g/L. Redistribution of the arsenic occurs during summer stratification, with highest concentrations at middle depths. The total mass of arsenic in the pit lake increases coinciding with early winter rains that erode, partially dissolve, and transport arsenic-bearing salts into the pit lake. Arsenic concentration, speciation, and distribution in the Sierra Nevada foothills depend on many factors, including the lithologic sources of arsenic, climatic influences on weathering of host minerals, and geochemical characteristics of waters with which source and secondary minerals react. Oxidation of arsenian pyrite to goethite, jarosite, and copiapite causes temporary attenuation of arsenic during summer, when these secondary minerals accumulate; subsequent rapid dissemination of arsenic into the aqueous environment is caused by annual winter storms. As the population of the Mother Lode area grows, it is increasingly important to consider these effects during planning and development of land and groundwater resources.

Genetic polymorphisms in glutathione S-transferase (GST) superfamily and arsenic metabolism in residents of the Red River Delta, Vietnam

DOE Office of Scientific and Technical Information (OSTI.GOV)

Agusa, Tetsuro; Center for Marine Environmental Studies; Iwata, Hisato, E-mail: iwatah@agr.ehime-u.ac.j

To elucidate the role of genetic factors in arsenic metabolism, we investigated associations of genetic polymorphisms in the members of glutathione S-transferase (GST) superfamily with the arsenic concentrations in hair and urine, and urinary arsenic profile in residents in the Red River Delta, Vietnam. Genotyping was conducted for GST omega1 (GSTO1) Ala140Asp, Glu155del, Glu208Lys, Thr217Asn, and Ala236Val, GST omega2 (GSTO2) Asn142Asp, GST pi1 (GSTP1) Ile105Val, GST mu1 (GSTM1) wild/null, and GST theta1 (GSTT1) wild/null. There were no mutation alleles for GSTO1 Glu208Lys, Thr217Asn, and Ala236Val in this population. GSTO1 Glu155del hetero type showed higher urinary concentration of As{sup V} thanmore » the wild homo type. Higher percentage of DMA{sup V} in urine of GSTM1 wild type was observed compared with that of the null type. Strong correlations between GSTP1 Ile105Val and arsenic exposure level and profile were observed in this study. Especially, heterozygote of GSTP1 Ile105Val had a higher metabolic capacity from inorganic arsenic to monomethyl arsenic, while the opposite trend was observed for ability of metabolism from As{sup V} to As{sup III}. Furthermore, other factors including sex, age, body mass index, arsenic level in drinking water, and genotypes of As (+ 3 oxidation state) methyltransferase (AS3MT) were also significantly co-associated with arsenic level and profile in the Vietnamese. To our knowledge, this is the first study indicating the associations of genetic factors of GST superfamily with arsenic metabolism in a Vietnamese population.« less

Genetic polymorphisms in glutathione S-transferase (GST) superfamily and arsenic metabolism in residents of the Red River Delta, Vietnam.

PubMed

Agusa, Tetsuro; Iwata, Hisato; Fujihara, Junko; Kunito, Takashi; Takeshita, Haruo; Minh, Tu Binh; Trang, Pham Thi Kim; Viet, Pham Hung; Tanabe, Shinsuke

2010-02-01

To elucidate the role of genetic factors in arsenic metabolism, we investigated associations of genetic polymorphisms in the members of glutathione S-transferase (GST) superfamily with the arsenic concentrations in hair and urine, and urinary arsenic profile in residents in the Red River Delta, Vietnam. Genotyping was conducted for GST omega1 (GSTO1) Ala140Asp, Glu155del, Glu208Lys, Thr217Asn, and Ala236Val, GST omega2 (GSTO2) Asn142Asp, GST pi1 (GSTP1) Ile105Val, GST mu1 (GSTM1) wild/null, and GST theta1 (GSTT1) wild/null. There were no mutation alleles for GSTO1 Glu208Lys, Thr217Asn, and Ala236Val in this population. GSTO1 Glu155del hetero type showed higher urinary concentration of As(V) than the wild homo type. Higher percentage of DMA(V) in urine of GSTM1 wild type was observed compared with that of the null type. Strong correlations between GSTP1 Ile105Val and arsenic exposure level and profile were observed in this study. Especially, heterozygote of GSTP1 Ile105Val had a higher metabolic capacity from inorganic arsenic to monomethyl arsenic, while the opposite trend was observed for ability of metabolism from As(V) to As(III). Furthermore, other factors including sex, age, body mass index, arsenic level in drinking water, and genotypes of As (+3 oxidation state) methyltransferase (AS3MT) were also significantly co-associated with arsenic level and profile in the Vietnamese. To our knowledge, this is the first study indicating the associations of genetic factors of GST superfamily with arsenic metabolism in a Vietnamese population. Copyright 2009 Elsevier Inc. All rights reserved.

Effect of plasma homocysteine level and urinary monomethylarsonic acid on the risk of arsenic-associated carotid atherosclerosis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wu, M.-M.; Graduate Institute of Medicine, College of Medicine, Fu-Jen Catholic University, Taipei, Taiwan; Chiou, H.-Y.

2006-10-01

Arsenic-contaminated well water has been shown to increase the risk of atherosclerosis. Because of involving S-adenosylmethionine, homocysteine may modify the risk by interfering with the biomethylation of ingested arsenic. In this study, we assessed the effect of plasma homocysteine level and urinary monomethylarsonic acid (MMA{sup V}) on the risk of atherosclerosis associated with arsenic. In total, 163 patients with carotid atherosclerosis and 163 controls were studied. Lifetime cumulative arsenic exposure from well water for study subjects was measured as index of arsenic exposure. Homocysteine level was determined by high-performance liquid chromatography (HPLC). Proportion of MMA{sup V} (MMA%) was calculated bymore » dividing with total arsenic species in urine, including arsenite, arsenate, MMA{sup V}, and dimethylarsinic acid (DMA{sup V}). Results of multiple linear regression analysis show a positive correlation of plasma homocysteine levels to the cumulative arsenic exposure after controlling for atherosclerosis status and nutritional factors (P < 0.05). This correlation, however, did not change substantially the effect of arsenic exposure on the risk of atherosclerosis as analyzed in a subsequent logistic regression model. Logistic regression analyses also show that elevated plasma homocysteine levels did not confer an independent risk for developing atherosclerosis in the study population. However, the risk of having atherosclerosis was increased to 5.4-fold (95% CI, 2.0-15.0) for the study subjects with high MMA% ({>=}16.5%) and high homocysteine levels ({>=}12.7 {mu}mol/l) as compared to those with low MMA% (<9.9%) and low homocysteine levels (<12.7 {mu}mol/l). Elevated homocysteinemia may exacerbate the formation of atherosclerosis related to arsenic exposure in individuals with high levels of MMA% in urine.« less

Arsenic Bioavailability, Bioaccessibility, And Speciation

EPA Science Inventory

The term bioavailability has many different meanings across various disciplines. Often bioavailability is concerned with human health aspects such as the case of urban children interacting with contaminated soil. The still utilized approach to base risk assessment on total meta...

The concentration and chemical speciation of arsenic in the Nanpan River, the upstream of the Pearl River, China.

PubMed

Yang, Silin; Zhao, Ning; Zhou, Dequn; Wei, Rong; Yang, Bin; Pan, Bo

2016-04-01

The concentration and chemical speciation of arsenic (As) in different environmental matrixes (water, sediment, agricultural soils, and non-agricultural soils) were investigated in the Nanpan River area, the upstream of Pearl River, China. The results did not show any obvious transport of As along the flow direction of the river (from upstream to downstream). Total As concentrations in sediment were significantly different from those in agricultural soil. According to the comparison to quality standards, the As in sediments of the studied area have potential ecological risks and a minority of the sampling sites of agricultural soils in the studied area were polluted with As. As speciations were analyzed using sequential extraction and the percentage of non-residual fraction in sediment predominated over residual fraction. We thus believe that As in the studied area was with low mobility and bioavailability in sediment, agricultural soils, and non-agricultural soils. However, the bioavailability and mobility of As in sediment were higher than in both agricultural and non-agricultural soils, and thus, special attention should be paid for the risk assessment of As in the river in future studies.

Mechanisms of Arsenic Sequestration by Prosopis juliflora during the Phytostabilization of Metalliferous Mine Tailings.

PubMed

Hammond, Corin M; Root, Robert A; Maier, Raina M; Chorover, Jon

2018-02-06

Phytostabilization is a cost-effective long-term bioremediation technique for the immobilization of metalliferous mine tailings. However, the biogeochemical processes affecting metal(loid) molecular stabilization and mobility in the root zone remain poorly resolved. The roots of Prosopis juliflora grown for up to 36 months in compost-amended pyritic mine tailings from a federal Superfund site were investigated by microscale and bulk synchrotron X-ray absorption spectroscopy (XAS) and multiple energy micro-X-ray fluorescence imaging to determine iron, arsenic, and sulfur speciation, abundance, and spatial distribution. Whereas ferrihydrite-bound As(V) species predominated in the initial bulk mine tailings, the rhizosphere speciation of arsenic was distinctly different. Root-associated As(V) was immobilized on the root epidermis bound to ferric sulfate precipitates and within root vacuoles as trivalent As(III)-(SR) 3  tris-thiolate complexes. Molar Fe-to-As ratios of root epidermis tissue were two times higher than the 15% compost-amended bulk tailings growth medium. Rhizoplane-associated ferric sulfate phases that showed a high capacity to scavenge As(V) were dissimilar from the bulk-tailings mineralogy as shown by XAS and X-ray diffraction, indicating a root-surface mechanism for their formation or accumulation.

Arsenic uptake and speciation in vegetables grown under greenhouse conditions.

PubMed

Smith, E; Juhasz, A L; Weber, J

2009-04-01

The accumulation of arsenic (As) by vegetables is a potential human exposure pathway. The speciation of As in vegetables is an important consideration due to the varying toxicity of different As species. In this study, common Australian garden vegetables were hydroponically grown with As-contaminated irrigation water to determine the uptake and species of As present in vegetable tissue. The highest concentrations of total As were observed in the roots of all vegetables and declined in the aerial portions of the plants. Total As accumulation in the edible portions of the vegetables decreased in the order radish > mung bean > lettuce = chard. Arsenic was present in the roots of radish, chard, and lettuce as arsenate (As(V)) and comprised between 77 and 92% of the total As present, whereas in mung beans, arsenite (As(III)) comprised 90% of the total As present. In aerial portions of the vegetables, As was distributed equally between both As(V) and As(III) in radish and chard but was present mainly as As(V) in lettuce. The presence of elevated As in vegetable roots suggests that As species may be complexed by phytochelatins, which limits As translocation to aerial portions of the plant.

Analysis of maternal polymorphisms in arsenic (+3 oxidation state)-methyltransferase AS3MT and fetal sex in relation to arsenic metabolism and infant birth outcomes: Implications for risk analysis.

PubMed

Drobná, Zuzana; Martin, Elizabeth; Kim, Kyung Su; Smeester, Lisa; Bommarito, Paige; Rubio-Andrade, Marisela; García-Vargas, Gonzalo G; Stýblo, Miroslav; Zou, Fei; Fry, Rebecca C

2016-06-01

Arsenic (+3 oxidation state) methyltransferase (AS3MT) is the key enzyme in the metabolism of inorganic arsenic (iAs). Polymorphisms of AS3MT influence adverse health effects in adults, but little is known about their role in iAs metabolism in pregnant women and infants. The relationships between seven single nucleotide polymorphisms (SNPs) in AS3MT and urinary concentrations of iAs and its methylated metabolites were assessed in mother-infant pairs of the Biomarkers of Exposure to ARsenic (BEAR) cohort. Maternal alleles for five of the seven SNPs (rs7085104, rs3740400, rs3740393, rs3740390, and rs1046778) were associated with urinary concentrations of iAs metabolites, and alleles for one SNP (rs3740393) were associated with birth outcomes/measures. These associations were strongly dependent upon the male sex of the fetus but independent of fetal genotype for AS3MT. These data highlight a potential sex-dependence of the relationships among maternal genotype, iAs metabolism and infant health outcomes. Copyright © 2016 Elsevier Inc. All rights reserved.

Genetic polymorphisms of PPAR gamma, arsenic methylation capacity and breast cancer risk in Mexican women.

PubMed

Pineda-Belmontes, Cristina P; Hernández-Ramírez, Raúl U; Hernández-Alcaraz, César; Cebrián, Mariano E; López-Carrillo, Lizbeth

2016-04-01

To evaluate whether the presence of polymorphisms of peroxisome proliferator-activated receptor gamma PPARγ (Pro 1 2Ala) and PPARGC1B (Ala203Pro) modifies the association between the inorganic arsenic (iAs) methylation capacity and breast cancer (BC). Mexican women were interviewed, and blood and urine samples were collected from them (cases/controls= 197/220). The concentration of urinary arsenic species and the polymorphisms of interest were determined by high-performance liquid chromatography with inductively coupled plasma mass spectrometry (HPLC-ICP-MS) and polymerase chain reaction (PCR), respectively. In women with a high %MMA (urinary monomethyl arsenic) and high primary methylation ratio (PM = MMA/iAs), the risk of BC was increased (odds ratio [OR]%MMA T3 vs.T1= 3.60: 95% confidence interval [CI] 2.02-6.41, ORPMI T3 vs.T1= 3.47: 95%CI 1.95-6.17), which was maintained after adjusting for polymorphisms. No significant interactions were observed between the polymorphisms and the arsenic variables on the risk of BC. Pro 12Ala and Ala203Pro polymorphisms did not modify the association between the iAs methylation capacity and BC.

The microbial arsenic cycle in Mono Lake, California

USGS Publications Warehouse

Oremland, Ronald S.; Stolz, John F.; Hollibaugh, James T.

2004-01-01

Significant concentrations of dissolved inorganic arsenic can be found in the waters of a number of lakes located in the western USA and in other water bodies around the world. These lakes are often situated in arid, volcanic terrain. The highest concentrations of arsenic occur in hypersaline, closed basin soda lakes and their remnant brines. Although arsenic is a well-known toxicant to eukaryotes and prokaryotes alike, some prokaryotes have evolved biochemical mechanisms to exploit arsenic oxyanions (i.e., arsenate and arsenite); they can use them either as an electron acceptor for anaerobic respiration (arsenate), or as an electron donor (arsenite) to support chemoautotrophic fixation of CO2 into cell carbon. Unlike in freshwater or marine ecosystems, these processes may assume quantitative significance with respect to the carbon cycle in arsenic-rich soda lakes. For the past several years our research has focused on the occurrence and biogeochemical manifestations of these processes in Mono Lake, a particularly arsenic-rich environment. Herein we review some of our findings concerning the biogeochemical arsenic cycle in this lake, with the hope that it may broaden the understanding of the influence of microorganisms upon the speciation of arsenic in more common, less “extreme” environments, such as drinking water aquifers.

Lung inflammation biomarkers and lung function in children chronically exposed to arsenic

DOE Office of Scientific and Technical Information (OSTI.GOV)

Olivas-Calderón, Edgar, E-mail: edgar_olivascalderon@hotmail.com; School of Medicine, University Juarez of Durango, Gomez Palacio, Durango; Recio-Vega, Rogelio, E-mail: rrecio@yahoo.com

Evidence suggests that exposure to arsenic in drinking water during early childhood or in utero has been associated with an increase in respiratory symptoms or diseases in the adulthood, however only a few studies have been carried out during those sensitive windows of exposure. Recently our group demonstrated that the exposure to arsenic during early childhood or in utero in children was associated with impairment in the lung function and suggested that this adverse effect could be due to a chronic inflammation response to the metalloid. Therefore, we designed this cross-sectional study in a cohort of children associating lung inflammatorymore » biomarkers and lung function with urinary As levels. A total of 275 healthy children were partitioned into four study groups according with their arsenic urinary levels. Inflammation biomarkers were measured in sputum by ELISA and the lung function was evaluated by spirometry. Fifty eight percent of the studied children were found to have a restrictive spirometric pattern. In the two highest exposed groups, the soluble receptor for advanced glycation end products' (sRAGE) sputum level was significantly lower and matrix metalloproteinase-9 (MMP-9) concentration was higher. When the biomarkers were correlated to the urinary arsenic species, negative associations were found between dimethylarsinic (DMA), monomethylarsonic percentage (%MMA) and dimethylarsinic percentage (%DMA) with sRAGE and positive associations between %DMA with MMP-9 and with the MMP-9/tissue inhibitor of metalloproteinase (TIMP-1) ratio. In conclusion, chronic arsenic exposure of children negatively correlates with sRAGE, and positively correlated with MMP-9 and MMP-9/TIMP-1 levels, and increases the frequency of an abnormal spirometric pattern. Arsenic-induced alterations in inflammatory biomarkers may contribute to the development of restrictive lung diseases. - Highlights: • First study in children evaluating lung inflammatory biomarkers and As levels • In 275 children chronically exposed to As, 3 biomarkers were measured. • Negative associations were found between DMA, %MMA and %DMA with sRAGE. • Positive associations were found between %DMA with MMP-9 and with the MMP-9/TIMP-1 ratio. • Chronic arsenic exposure-induced alterations in lung inflammatory biomarkers in children.« less

Environmental exposure to arsenic and chromium in children is associated with kidney injury molecule-1

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cárdenas-González, M.

Environmental hazards from natural or anthropological sources are widespread, especially in the north-central region of Mexico. Children represent a susceptible population due to their unique routes of exposure and special vulnerabilities. In this study we evaluated the association of exposure to environmental kidney toxicants with kidney injury biomarkers in children living in San Luis Potosi (SLP), Mexico. A cross-sectional study was conducted with 83 children (5–12 years of age) residents of Villa de Reyes, SLP. Exposure to arsenic, cadmium, chromium, fluoride and lead was assessed in urine, blood and drinking water samples. Almost all tap and well water samples hadmore » levels of arsenic (81.5%) and fluoride (100%) above the permissible levels recommended by the World Health Organization. Mean urine arsenic (45.6 ppb) and chromium (61.7 ppb) were higher than the biological exposure index, a reference value in occupational settings. Using multivariate adjusted models, we found a dose-dependent association between kidney injury molecule-1 (KIM-1) across chromium exposure tertiles [(T1: reference, T2: 467 pg/mL; T3: 615 pg/mL) (p-trend=0.001)]. Chromium upper tertile was also associated with higher urinary miR-200c (500 copies/μl) and miR-423 (189 copies/μL). Arsenic upper tertile was also associated with higher urinary KIM-1 (372 pg/mL). Other kidney injury/functional biomarkers such as serum creatinine, glomerular filtration rate, albuminuria, neutrophil gelatinase-associated lipocalin and miR-21 did not show any association with arsenic, chromium or any of the other toxicants evaluated. We conclude that KIM-1 might serve as a sensitive biomarker to screen children for kidney damage induced by environmental toxic agents. - Highlights: • Children living in Mexico had exceedingly high arsenic and chromium exposure. • Arsenic and chromium exposure was significantly associated with urinary KIM-1. • KIM-1 might serve as a sensitive biomarker to evaluate kidney injury in children.« less

Establishment of a method for determination of arsenic species in seafood by LC-ICP-MS.

PubMed

Zmozinski, Ariane V; Llorente-Mirandes, Toni; López-Sánchez, José F; da Silva, Márcia M

2015-04-15

An analytical method for determination of arsenic species (inorganic arsenic (iAs), methylarsonic acid (MA), dimethylarsinic acid (DMA), arsenobetaine (AB), trimethylarsine oxide (TMAO) and arsenocholine (AC)) in Brazilian and Spanish seafood samples is reported. This study was focused on extraction and quantification of inorganic arsenic (iAs), the most toxic form. Arsenic speciation was carried out via LC with both anionic and cationic exchange with ICP-MS detection (LC-ICP-MS). The detection limits (LODs), quantification limits (LOQs), precision and accuracy for arsenic species were established. The proposed method was evaluated using eight reference materials (RMs). Arsenobetaine was the main species found in all samples. The total and iAs concentration in 22 seafood samples and RMs ranged between 0.27-35.2 and 0.02-0.71 mg As kg(-1), respectively. Recoveries ranging from 100% to 106% for iAs, based on spikes, were achieved. The proposed method provides reliable iAs data for future risk assessment analysis. Copyright © 2014 Elsevier Ltd. All rights reserved.

Leaching of Arsenic from Granular Ferric Hydroxide Residuals under Mature Landfill Conditions

PubMed Central

Ghosh, Amlan; Mukiibi, Muhammed; Sáez, A. Eduardo; Ela, Wendell P.

2008-01-01

Most arsenic bearing solid residuals (ABSR) from water treatment will be disposed in non-hazardous landfills. The lack of an appropriate leaching test to predict arsenic mobilization from ABSR creates a need to evaluate the magnitude and mechanisms of arsenic release under landfill conditions. This work studies the leaching of arsenic and iron from a common ABSR, granular ferric hydroxide, in a laboratory-scale column that simulates the biological and physicochemical conditions of a mature, mixed solid waste landfill. The column operated for approximately 900 days and the mode of transport as well as chemical speciation of iron and arsenic changed with column age. Both iron and arsenic were readily mobilized under the anaerobic, reducing conditions. During the early stages of operation, most arsenic and iron leaching (80% and 65%, respectively) was associated with suspended particulate matter and iron was lost proportionately faster than arsenic. In later stages, while the rate of iron leaching declined, the arsenic leaching rate increased greater than 7-fold. The final phase was characterized by dissolved species leaching. Future work on the development of standard batch leaching tests should take into account the dominant mobilization mechanisms identified in this work: solid associated transport, reductive sorbent dissolution, and microbially mediated arsenic reduction. PMID:17051802

Leaching of arsenic from granular ferric hydroxide residuals under mature landfill conditions.

PubMed

Ghosh, Amlan; Mukiibi, Muhammed; Sáez, A Eduardo; Ela, Wendell P

2006-10-01

Most arsenic bearing solid residuals (ABSR) from water treatment will be disposed in nonhazardous landfills. The lack of an appropriate leaching test to predict arsenic mobilization from ABSR creates a need to evaluate the magnitude and mechanisms of arsenic release under landfill conditions. This work studies the leaching of arsenic and iron from a common ABSR, granular ferric hydroxide, in a laboratory-scale column that simulates the biological and physicochemical conditions of a mature, mixed solid waste landfill. The column operated for approximately 900 days and the mode of transport as well as chemical speciation of iron and arsenic changed with column age. Both iron and arsenic were readily mobilized under the anaerobic, reducing conditions. During the early stages of operation, most arsenic and iron leaching (80% and 65%, respectively) was associated with suspended particulate matter, and iron was lost proportionately faster than arsenic. In later stages, while the rate of iron leaching declined, the arsenic leaching rate increased greater than 7-fold. The final phase was characterized by dissolved species leaching. Future work on the development of standard batch leaching tests should take into account the dominant mobilization mechanisms identified in this work: solid associated transport, reductive sorbent dissolution, and microbially mediated arsenic reduction.

Solid-phase arsenic speciation in aquifer sediments: A micro-X-ray absorption spectroscopy approach for quantifying trace-level speciation

DOE PAGES

Nicholas, Sarah L.; Erickson, Melinda L.; Woodruff, Laurel G.; ...

2017-05-19

Arsenic (As) is a geogenic contaminant affecting groundwater in geologically diverse systems globally. Arsenic release from aquifer sediments to groundwater is favored when biogeochemical conditions, especially oxidation-reduction (redox) potential, in aquifers fluctuate. The specific objective of this research is to identify the solid-phase sources and geochemical mechanisms of release of As in aquifers of the Des Moines Lobe glacial advance. The overarching concept is that conditions present at the aquifer-aquitard interfaces promote a suite of geochemical reactions leading to mineral alteration and release of As to groundwater. A microprobe X-ray absorption spectroscopy (μXAS) approach is developed and applied to rotosonicmore » drill core samples to identify the solid-phase speciation of As in aquifer, aquitard, and aquifer-aquitard interface sediments. This approach addresses the low solid-phase As concentrations, as well as the fine-scale physical and chemical heterogeneity of the sediments. The spectroscopy data are analyzed using novel cosine-distance and correlation-distance hierarchical clustering for Fe 1s and As 1s μXAS datasets. The solid-phase Fe and As speciation is then interpreted using sediment and well-water chemical data to propose solid-phase As reservoirs and release mechanisms. The results confirm that in two of the three locations studied, the glacial sediment forming the aquitard is the source of As to the aquifer sediments. The results are consistent with three different As release mechanisms: (1) desorption from Fe (oxyhydr)oxides, (2) reductive dissolution of Fe (oxyhydr)oxides, and (3) oxidative dissolution of Fe sulfides. The findings confirm that glacial sediments at the interface between aquifer and aquitard are geochemically active zones for As. The diversity of As release mechanisms is consistent with the geographic heterogeneity seen in the distribution of elevated-As wells.« less

Solid-phase arsenic speciation in aquifer sediments: A micro-X-ray absorption spectroscopy approach for quantifying trace-level speciation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nicholas, Sarah L.; Erickson, Melinda L.; Woodruff, Laurel G.

Arsenic (As) is a geogenic contaminant affecting groundwater in geologically diverse systems globally. Arsenic release from aquifer sediments to groundwater is favored when biogeochemical conditions, especially oxidation-reduction (redox) potential, in aquifers fluctuate. The specific objective of this research is to identify the solid-phase sources and geochemical mechanisms of release of As in aquifers of the Des Moines Lobe glacial advance. The overarching concept is that conditions present at the aquifer-aquitard interfaces promote a suite of geochemical reactions leading to mineral alteration and release of As to groundwater. A microprobe X-ray absorption spectroscopy (μXAS) approach is developed and applied to rotosonicmore » drill core samples to identify the solid-phase speciation of As in aquifer, aquitard, and aquifer-aquitard interface sediments. This approach addresses the low solid-phase As concentrations, as well as the fine-scale physical and chemical heterogeneity of the sediments. The spectroscopy data are analyzed using novel cosine-distance and correlation-distance hierarchical clustering for Fe 1s and As 1s μXAS datasets. The solid-phase Fe and As speciation is then interpreted using sediment and well-water chemical data to propose solid-phase As reservoirs and release mechanisms. The results confirm that in two of the three locations studied, the glacial sediment forming the aquitard is the source of As to the aquifer sediments. The results are consistent with three different As release mechanisms: (1) desorption from Fe (oxyhydr)oxides, (2) reductive dissolution of Fe (oxyhydr)oxides, and (3) oxidative dissolution of Fe sulfides. The findings confirm that glacial sediments at the interface between aquifer and aquitard are geochemically active zones for As. The diversity of As release mechanisms is consistent with the geographic heterogeneity seen in the distribution of elevated-As wells.« less

METABOLSM OF PENTAVALENT AND TRIVALENT DIMETHYLARSENIC ARSENIC IN THE MOUSE

EPA Science Inventory

Dimethylarsinic acid (DMA(V)) is a rat bladder carcinogen after chronic exposure in either drinking water or the diet. DMA(V) is also a major urinary metabolite of mammals exposed to inorganic arsenic. In mice, iv and po administration of [¹⁴C]-DMA(V) results in rapi...

Association between arsenic exposure from drinking water and hematuria: results from the Health Effects of Arsenic Longitudinal Study.

PubMed

McClintock, Tyler R; Chen, Yu; Parvez, Faruque; Makarov, Danil V; Ge, Wenzhen; Islam, Tariqul; Ahmed, Alauddin; Rakibuz-Zaman, Muhammad; Hasan, Rabiul; Sarwar, Golam; Slavkovich, Vesna; Bjurlin, Marc A; Graziano, Joseph H; Ahsan, Habibul

2014-04-01

Arsenic (As) exposure has been associated with both urologic malignancy and renal dysfunction; however, its association with hematuria is unknown. We evaluated the association between drinking water As exposure and hematuria in 7843 men enrolled in the Health Effects of Arsenic Longitudinal Study (HEALS). Cross-sectional analysis of baseline data was conducted with As exposure assessed in both well water and urinary As measurements, while hematuria was measured using urine dipstick. Prospective analyses with Cox proportional regression models were based on urinary As and dipstick measurements obtained biannually since baseline up to six years. At baseline, urinary As was significantly related to prevalence of hematuria (P-trend<0.01), with increasing quintiles of exposure corresponding with respective prevalence odds ratios of 1.00 (reference), 1.29 (95% CI: 1.04-1.59), 1.41 (95% CI: 1.15-1.74), 1.46 (95% CI: 1.19-1.79), and 1.56 (95% CI: 1.27-1.91). Compared to those with relatively little absolute urinary As change during follow-up (-10.40 to 41.17 μg/l), hazard ratios for hematuria were 0.99 (95% CI: 0.80-1.22) and 0.80 (95% CI: 0.65-0.99) for those whose urinary As decreased by >47.49 μg/l and 10.87 to 47.49 μg/l since last visit, respectively, and 1.17 (95% CI: 0.94-1.45) and 1.36 (95% CI: 1.10-1.66) for those with between-visit increases of 10.40 to 41.17 μg/l and >41.17 μg/l, respectively. These data indicate a positive association of As exposure with both prevalence and incidence of dipstick hematuria. This exposure effect appears modifiable by relatively short-term changes in drinking water As. Copyright © 2014 Elsevier Inc. All rights reserved.

Association between arsenic exposure from drinking water and hematuria: results from the Health Effects of Arsenic Longitudinal Study

PubMed Central

McClintock, Tyler R.; Chen, Yu; Parvez, Faruque; Makarov, Danil V.; Ge, Wenzhen; Islam, Tariqul; Ahmed, Alauddin; Rakibuz-Zaman, Muhammad; Hasan, Rabiul; Sarwar, Golam; Slavkovich, Vesna; Bjurlin, Marc A.; Graziano, Joseph H.; Ahsan, Habibul

2014-01-01

Arsenic (As) exposure has been associated with both urologic malignancy and renal dysfunction; however, its association with hematuria is unknown. We evaluated the association between drinking water As exposure and hematuria in 7,843 men enrolled in the Health Effects of Arsenic Longitudinal Study (HEALS). Cross-sectional analysis of baseline data was conducted with As exposure assessed in both well water and urinary As measurements, while hematuria was measured using urine dipstick. Prospective analyses with Cox proportional regression models were based on urinary As and dipstick measurements obtained biannually since baseline up to six years. At baseline, urinary As was significantly related to prevalence of hematuria (P-trend < 0.01), with increasing quintiles of exposure corresponding with respective prevalence odds ratios of 1.00 (reference), 1.29 (95% CI: 1.04–1.59), 1.41 (95% CI: 1.15–1.74), 1.46 (95% CI: 1.19–1.79), and 1.56 (95% CI: 1.27–1.91). Compared to those with relatively little absolute urinary As change during follow-up (−10.40 to 41.17 μg/l), hazard ratios for hematuria were 0.99 (95% CI: 0.80–1.22) and 0.80 (95% CI: 0.65–0.99) for those whose urinary As decreased by >47.49 μg/l and 10.87 to 47.49 μg/l since last visit, respectively, and 1.17 (95% CI: 0.94–1.45) and 1.36 (95% CI: 1.10–1.66) for those with between-visit increases of 10.40 to 41.17 μg/l and >41.17 μg/l, respectively. These data indicate a positive association of As exposure with both prevalence and incidence of dipstick hematuria. This exposure effect appears modifiable by short-term changes in drinking water As. PMID:24486435

Understanding Arsenic Dynamics in Agronomic Systems to ...

EPA Pesticide Factsheets

This review is on arsenic in agronomic systems, and covers processes that influence the entry of arsenic into the human food supply. The scope is from sources of arsenic (natural and anthropogenic) in soils, biogeochemical and rhizosphere processes that control arsenic speciation and availability, through to mechanisms of uptake by crop plants and potential mitigation strategies. This review makes a case for taking steps to prevent or limit crop uptake of arsenic, wherever possible, and to work toward a long-term solution to the presence of arsenic in agronomic systems. The past two decades have seen important advances in our understanding of how biogeochemical and physiological processes influence human exposure to soil arsenic, and thus must now prompt an informed reconsideration and unification of regulations to protect the quality of agricultural and residential soils. Consumption of staple foods such as rice, beverages such as apple juice, or vegetables grown in historically arsenic-contaminated soils is now recognized as a tangible route of arsenic exposure that, in many cases, is more significant than exposure from drinking water. Understanding the sources of arsenic to crop plants and the factors that influence them is key to reducing exposure now and preventing exposure in future. In addition to the abundant natural sources of arsenic, there are a large number of industrial and agricultural sources of arsenic to the soil; from mining wastes, coal fly

Linear combination fitting data

EPA Pesticide Factsheets

The dataset shows the weighted percentage of arsenic speciation for untreated and treated soil samples with amendments designed to immobilize arsenic in soils.This dataset is associated with the following publication:Mele, E., E. Donner, A. Juhasz, G. Brunetti, E. Smith, A. Betts , P. Castaldi, S. Deiana, K. Scheckel , and E. Lombi. In situ fixation of metal(loid)s in contaminated soils: a comparison of conventional, by product and engineered soil amendments. David L. Sedlak ENVIRONMENTAL SCIENCE & TECHNOLOGY. American Chemical Society, Washington, DC, USA, 49: 13501-13509, (2015).

Aquatic Humic Substances: Relationship Between Origin and Complexing Capacity.

PubMed

González-Guadarrama, María de Jesús; Armienta-Hernández, Ma Aurora; Rosa, André H

2018-05-01

Aiming to determine the relationship between source and complexing capacity, humic substances obtained from three sites (Sorocaba and Itapanhau Brasilian rivers, and Xochimilco Lake in Mexico) were studied. Copper, manganese, zinc and arsenic complexing capacity were determined for the three substances under various pH conditions. Results showed similar complexing capacity for the three elements depending on the chemistry of each one and on the physico-chemical conditions. Speciation diagrams showed that these conditions affect both, the humic substances, and the transition metals and arsenic.

Arsenic speciation in arsenic-rich Brazilian soils from gold mining sites under anaerobic incubation

USGS Publications Warehouse

De Mello, J. W. V.; Talbott, J.L.; Scott, J.; Roy, W.R.; Stucki, J.W.

2007-01-01

Background. Arsenic speciation in environmental samples is essential for studying toxicity, mobility and bio-transformation of As in aquatic and terrestrial environments. Although the inorganic species As(III) and As(V) have been considered dominant in soils and sediments, organisms are able to metabolize inorganic forms of arsenic into organo-arsenic compounds. Arsenosugars and methylated As compounds can be found in terrestrial organisms, but they generally occur only as minor constituents. We investigated the dynamics of arsenic species under anaerobic conditions in soils surrounding gold mining areas from Minas Gerais State, Brazil to elucidate the arsenic biogeochemical cycle and water contamination mechanisms. Methods. Surface soil samples were collected at those sites, namely Paracatu Formation, Banded Iron Formation and Riacho dos Machados Sequence, and incubated in CaCl2 2.5 mmol L-1 suspensions under anaerobic conditions for 1, 28, 56 and 112 days. After that, suspensions were centrifuged and supernatants analyzed for soluble As species by IC-ICPMS and HPLC-ICPMS. Results. Easily exchangeable As was mainly arsenite, except when reducible manganese was present. Arsenate was mainly responsible for the increase in soluble arsenic due to the reductive dissolution of either iron or manganese in samples from the Paracatu Formation and Riacho dos Machados Sequence. On the other hand, organic species of As dominated in samples from the Banded Iron Formation during anaerobic incubation. Discussion. Results are contrary to the expectation that, in anaerobic environments, As release due to the reductive dissolution of Fe is followed by As(V) reduction to As(III). The occurrence of organo-arsenic species was also found to be significant to the dynamics of soluble arsenic, mainly in soils from the Banded Iron Formation (BIF), under our experimental conditions. Conclusions. In general, As(V) and organic As were the dominant species in solution, which is surprising under anaerobic conditions in terrestrial environments. The unexpected occurrence of organic species of As was attributed to enrollment of ternary organic complexes or living organisms such as algae or cyanobacteria. Perspectives. These findings are believed to be useful for remediation strategies in mine-affected regions, as the organic As species are in general considered to be less toxic than inorganic ones and even As(V) is considered less mobile and toxic than As(III). ?? 2007 ecomed publishers (Verlagsgruppe Hu??thig Jehle Rehm GmbH).

Association between arsenic exposure from drinking water and proteinuria: results from the Health Effects of Arsenic Longitudinal Study

PubMed Central

Chen, Yu; Parvez, Faruque; Liu, Mengling; Pesola, Gene R; Gamble, Mary V; Slavkovich, Vesna; Islam, Tariqul; Ahmed, Alauddin; Hasan, Rabiul; Graziano, Joseph H; Ahsan, Habibul

2011-01-01

Background Proteinuria has been recognized as a marker for an increased risk of chronic renal disease. It is unclear whether arsenic (As) exposure from drinking water is associated with proteinuria. Methods We evaluated the association between As exposure from drinking water and proteinuria in 11 122 participants in the Health Effects of Arsenic Longitudinal Study (HEALS). Proteinuria was detected by urinary dipstick tests at baseline and at 2-year intervals. As exposure variables included baseline well As and changes in urinary As during follow-up modelled as time-dependent variables in the analyses. Results At baseline, well As was positively related to prevalence of proteinuria; prevalence odds ratios (PORs) for proteinuria in increasing quintiles of well As (≤7, 8–39, 40–91, 92–179 and 180–864 µg/l) were 1.00 (ref), POR 0.99 [95% confidence interval (CI) 0.77–1.27], POR 1.23 (95% CI 0.97–1.57), POR 1.50 (95% CI 1.18–1.89) and POR 1.59 (95% CI 1.26–2.00) (P for trend <0.01). Hazard ratios for incidence of proteinuria were POR 0.83 (95% CI 0.67–1.03) and POR 0.91 (95% CI 0.74–1.12) for participants with a decreasing level of >70 and 17–70 µg/l in urinary As over time, respectively, and were POR 1.17 (95% CI 0.97–1.42) and POR 1.42 (95% CI 1.16–1.73) for participants with an increasing level of 16–68 and >68 µg/l in urinary As over time, respectively, compared with the group with relatively little changes in urinary As as the reference group (urinary As −16 to 15 µg/l). Conclusion The findings suggest that there are adverse effects of As exposure on the risk of proteinuria and the effects are modifiable by recent changes in As exposure. PMID:21343184

Randomized placebo-controlled trial of 2,3-dimercapto-1-propanesulfonate (DMPS) in therapy of chronic arsenicosis due to drinking arsenic-contaminated water.

PubMed

Guha Mazumder, D N; De, B K; Santra, A; Ghosh, N; Das, S; Lahiri, S; Das, T

2001-01-01

Chronic arsenic toxicity, producing various clinical manifestations, is currently epidemic in West Bengal, India, Bangladesh, and other regions of the world. 2,3-Dimercapto-1-propanesulfonate, a chelating agent, increases excretion of arsenic in urine to several times the prechelation concentration but the therapeutic efficacy of 2,3-dimercapto-1-propanesulfonate in the management of chronic arsenic toxicity has been incompletely evaluated. We investigated the clinical use of 2,3-dmercapto-1-propanesulfonate in such patients. Twenty-one consecutive patients with chronic arsenicosis were individually randomized into 2 groups: 11 patients (9 males and 2 females, age 30.63+/-11.4 years) received 2,3-dimercapto-1-propanesulfonate 100-mg capsules 4 times a day for 1 week and repeated in the 3rd, 5th, and 7th week with no drug during the intervening period. The other 10 patients (5 males and 5 females, age 34.4+/-14.41 years) were given placebo capsules (resembling 2,3-dimercapto-1-propanesulfonate) in the same schedule. The consumption of arsenic-contaminated water was terminated by all 21 subjects. Initial and posttreatment urinary arsenic excretion was determined in all cases. Sequential excretion of urinary arsenic was determined during the treatment of 2 drug- and 1 placebo-treated cases. The clinical features were evaluated by an objective scoring system before and after treatment. Routine investigation including liver function test and skin biopsy were also done before and after the treatment. Drug-associated toxicity was tabulated. Therapy with 2,3-dimercapto-1-propanesulfonate caused significant improvement in the clinical condition of chronic arsenicosis patients as evidenced by significant reduction of total clinical scores from 8.90+/-2.84 to 3.27+/-1.73; p < 0.0001. Exposure cessation alone with placebo treatment also reduced clinical scores (8.50+/-1.96 to 5.40+/-2.12; p < 0.003), but the posttreatment total clinical score of 2,3-dimercapto-1-propanesulfonate-treated patients (3.27+/-1.73) was significantly lower than that of placebo-treated patients (5.40+/-2.12; p < 0.01). The most significant improvement was noted in regard to the clinical scores of weakness, pigmentation, and lung disease. No difference was noted between groups in the hematological and biochemical parameters (which were normal) and skin histology before and after treatment. No 2,3-dimercapto-1-propanesulfonate-related adverse effects were noted. Total urinary excretion of arsenic in 2,3-dimercapto-1-propanesulfonate-treated cases increased significantly following drug therapy, with no increase in placebo-treated cases. 2,3-Dimercapto-1-propanesulfonate treatment caused significant improvement in the clinical score of patients suffering from chronic arsenic toxicity. Increased urinary excretion of arsenic during the period of therapy is the possible cause of this improvement.

Change in Localizations of Arsenic in Rice Grains After Cooking with High Arsenic Waters - µXRF and XANES studies

NASA Astrophysics Data System (ADS)

Datta, S.; Ryan, B.; Kumar, N.; Bortz, T.; Bolen, Z. T.

2016-12-01

Threats of Arsenic (As) through food uptake, via consumption of rice, is a potential pathway that presents a concern not only for the millions of inhabitants who reside in river valleys and irrigate their soil with contaminated water, but the global rice market as well. This study focuses on high As rice from India and Bangladesh grown in such soils, and the effect of boiling rice with As-contaminated water in preparation for dietary intake. Husked and unhusked rice grains were boiled with >500 µg/L As-bearing water from the field to simulate local cooking methods. The resulting cooked water was analyzed using iCAP low limit detection via ICP-MS to understand the changes in dissolved elemental concentrations before and after cooking, and HPLC was introduced to measure for changes in As speciation in the waters. Using spectroscopic methods such as µXRF mapping associated with µXANES, distribution/localization and speciation changes of As in rice grains were identified. Further, with Linear Combination Fitting (LCF) of XANES spectra utilizing relevant reference compounds (As-S, AsIII, AsV, MMA and DMA), organic and inorganic As species were able to be mapped within rice grains. The results for uncooked/raw grains showed that predominantly As-S combined with AsIII and AsV accounted for 90% of speciation in most samples, localized in areas such as the outer aleurone layer. When analyzing cooked rice grains, the speciation appears to be an unidentified As species while the best LCF shows between 63-93% of As as MMA. Arsenic was found less localized throughout the cooked grains but rather heterogeneously distributed when compared to the uncooked/raw samples. The analyses of boiled/cooked water resulted in a significant decrease in dissolved As post-cooking (90%), but a subsequent increase in elements such as K, La, Li, Mo, Na, Ni, and Zr was observed; As-V was shown to be the main in-As species in the cooked water. The impact that this study portrays is consuming rice cooked by As-contaminated waters may not decrease the levels of As being consumed, but entitles further study on the specific health impacts that such cooked rice consumption could add to local population.

Low-level inorganic arsenic exposure and neuropsychological functioning in American Indian elders.

PubMed

Carroll, Clint R; Noonan, Carolyn; Garroutte, Eva M; Navas-Acien, Ana; Verney, Steven P; Buchwald, Dedra

2017-07-01

Inorganic arsenic at high and prolonged doses is highly neurotoxic. Few studies have evaluated whether long-term, low-level arsenic exposure is associated with neuropsychological functioning in adults. To investigate the association between long-term, low-level inorganic arsenic exposure and neuropsychological functioning among American Indians aged 64-95. We assessed 928 participants in the Strong Heart Study by using data on arsenic species in urine samples collected at baseline (1989-1991) and results of standardized tests of global cognition, executive functioning, verbal learning and memory, fine motor functioning, and speed of mental processing administered during comprehensive follow-up evaluations in 2009-2013. We calculated the difference in neuropsychological functioning for a 10% increase in urinary arsenic with adjustment for sex, age, education, and study site. The sum of inorganic and methylated arsenic species (∑As) in urine was associated with limited fine motor functioning and processing speed. A 10% increase in ∑As was associated with a .10 (95% CI -.20, -.01) decrease on the Finger Tapping Test for the dominant hand and a .13 decrease (95% CI -.21, -.04) for the non-dominant hand. Similarly, a 10% increase in ∑As was associated with a .15 (95% CI -.29, .00) decrease on the Wechsler Adult Intelligence Scale-Fourth Edition Coding Subtest. ∑As was not associated with other neuropsychological functions. Findings indicate an adverse association between increased urinary arsenic fine motor functioning and processing speed, but not with other neuropsychological functioning, among elderly American Indians. Copyright © 2017 Elsevier Inc. All rights reserved.

Association Between Variants in Arsenic (+3 Oxidation State) Methyltranserase (AS3MT) and Urinary Metabolites of Inorganic Arsenic: Role of Exposure Level

PubMed Central

Xu, Xiaofan; Drobná, Zuzana; Voruganti, V. Saroja; Barron, Keri; González-Horta, Carmen; Sánchez-Ramírez, Blanca; Ballinas-Casarrubias, Lourdes; Cerón, Roberto Hernández; Morales, Damián Viniegra; Terrazas, Francisco A. Baeza; Ishida, María C.; Gutiérrez-Torres, Daniela S.; Saunders, R. Jesse; Crandell, Jamie; Fry, Rebecca C.; Loomis, Dana; García-Vargas, Gonzalo G.; Del Razo, Luz M.; Stýblo, Miroslav; Mendez, Michelle A.

2016-01-01

Abstract Variants in AS3MT, the gene encoding arsenic (+3 oxidation state) methyltranserase, have been shown to influence patterns of inorganic arsenic (iAs) metabolism. Several studies have suggested that capacity to metabolize iAs may vary depending on levels of iAs exposure. However, it is not known whether the influence of variants in AS3MT on iAs metabolism also vary by level of exposure. We investigated, in a population of Mexican adults exposed to drinking water As, whether associations between 7 candidate variants in AS3MT and urinary iAs metabolites were consistent with prior studies, and whether these associations varied depending on the level of exposure. Overall, associations between urinary iAs metabolites and AS3MT variants were consistent with the literature. Referent genotypes, defined as the genotype previously associated with a higher percentage of urinary dimethylated As (DMAs%), were associated with significant increases in the DMAs% and ratio of DMAs to monomethylated As (MAs), and significant reductions in MAs% and iAs%. For 3 variants, associations between genotypes and iAs metabolism were significantly stronger among subjects exposed to water As >50 versus ≤50 ppb (water As X genotype interaction P < .05). In contrast, for 1 variant (rs17881215), associations were significantly stronger at exposures ≤50 ppb. Results suggest that iAs exposure may influence the extent to which several AS3MT variants affect iAs metabolism. The variants most strongly associated with iAs metabolism—and perhaps with susceptibility to iAs-associated disease—may vary in settings with exposure level. PMID:27370415

Stability of toxic arsenic species and arsenosugars found in the dry alga Hijiki and its water extracts.

PubMed

García-Salgado, Sara; Quijano, M Ángeles

2014-10-01

The achievement of reliable results in speciation analysis requires not only sensitive techniques but also sureness of species stability. Therefore, it is necessary to carry out stability studies because it is important to know with absolute certainty that there is not any species transformation during sample treatment and/or storage. Although several procedures have been recommended for the preservation of species integrity, there is no general agreement, as arsenic species stability depends on the sample matrix, the concentration level and the sample treatment procedure, so it is necessary to assess the arsenic species stability for each case. Thus, the present paper reports the stability tests of arsenic species carried out on the commercially available edible alga Hijiki (Hizikia fusiformis), from Japan, in both the dry sample and its water extracts, which were stored in amber glass and polystyrene containers at -18 and +4°C in the dark. Extractions were carried out with deionized water by microwave-assisted extraction, at a temperature of 90°C and three extraction steps of 5 min each, whereas arsenic speciation analysis was performed by anion exchange high performance liquid chromatography-photo-oxidation-hydride generation-atomic fluorescence spectrometry. The results obtained for the dry alga showed that the arsenic species present in it (arsenate (As(V)), dimethylarsinic acid (DMA) and the arsenosugars glycerol (Gly-sug), phosphate (PO4-sug), sulfonate (SO3-sug) and sulfate (SO4-sug)) were stable for at least 12 months when the sample was stored in polystyrene containers at +20°C in the dark. Regarding water extracts, the best storage conditions consisted of the use of polystyrene containers and a temperature of +4°C, for a maximum storage time of seven days. Therefore, the immediate analysis of Hijiki water extracts would not be necessary, and they could be stored for one week before analysis, ensuring arsenic species stability. This information about species integrity in extracts is especially useful when the sample treatment for arsenic species extraction is time-consuming. Copyright © 2014 Elsevier B.V. All rights reserved.

Health Risk Assessment and Urinary Excretion of Children Exposed to Arsenic through Drinking Water and Soils in Sonora, Mexico.

PubMed

García-Rico, Leticia; Meza-Figueroa, Diana; Jay Gandolfi, A; Del Rivero, Carlos Ibañez; Martínez-Cinco, Marco A; Meza-Montenegro, Maria M

2018-05-02

Environmental arsenic exposure is associated with increased risk of non-cancerous chronic diseases and a variety of cancers in humans. The aims of this study were to carry out for the first time a health risk assessment for two common arsenic exposure routes (drinking water and soil ingestion) in children living in the most important agricultural areas in the Yaqui and Mayo valleys in Sonora, Mexico. Drinking water sampling was conducted in the wells of 57 towns. A cross-sectional study was done in 306 children from 13 villages in the valleys. First morning void urine samples were analyzed for inorganic arsenic (InAs) and monomethyl and dimethyl arsenic (MMA and DMA) by HPLC/ICP-MS. The results showed a wide range of arsenic levels in drinking water between 2.7 and 98.7 μg As/L. Arsenic levels in agricultural and backyard soils were in the range of < 10-27 mg As/kg. The hazard index (HI) = ∑hazard quotient (HQ) for drinking water, agricultural soil, and backyard soil showed values > 1 in 100% of the study towns, and the carcinogenic risk (CR) was greater than 1E-04 in 85%. The average of arsenic excreted in urine was 31.7 μg As/L, and DMA had the highest proportion in urine, with averages of 77.8%, followed by InAs and MMA with 11.4 and 10.9%, respectively, percentages similar to those reported in the literature. Additionally, positive correlations between urinary arsenic levels and HI values were found (r = 0.59, P = 0.000). These results indicated that this population is at high risk of developing chronic diseases including cancer.

High levels of inorganic arsenic in rice in areas where arsenic-contaminated water is used for irrigation and cooking.

PubMed

Rahman, M Azizur; Hasegawa, H

2011-10-15

Rice is the staple food for the people of arsenic endemic South (S) and South-East (SE) Asian countries. In this region, arsenic contaminated groundwater has been used not only for drinking and cooking purposes but also for rice cultivation during dry season. Irrigation of arsenic-contaminated groundwater for rice cultivation has resulted high deposition of arsenic in topsoil and uptake in rice grain posing a serious threat to the sustainable agriculture in this region. In addition, cooking rice with arsenic-contaminated water also increases arsenic burden in cooked rice. Inorganic arsenic is the main species of S and SE Asian rice (80 to 91% of the total arsenic), and the concentration of this toxic species is increased in cooked rice from inorganic arsenic-rich cooking water. The people of Bangladesh and West Bengal (India), the arsenic hot spots in the world, eat an average of 450g rice a day. Therefore, in addition to drinking water, dietary intake of arsenic from rice is supposed to be another potential source of exposure, and to be a new disaster for the population of S and SE Asian countries. Arsenic speciation in raw and cooked rice, its bioavailability and the possible health hazard of inorganic arsenic in rice for the population of S and SE Asia have been discussed in this review. Copyright © 2011 Elsevier B.V. All rights reserved.

Dietary B Vitamin Intake Is Associated with Lower Urinary Monomethyl Arsenic and Oxidative Stress Marker 15-F2t-Isoprostane among New Hampshire Adults.

PubMed

Howe, Caitlin G; Li, Zhigang; Zens, Michael S; Palys, Thomas; Chen, Yu; Channon, Jacqueline Y; Karagas, Margaret R; Farzan, Shohreh F

2017-12-01

Background: Arsenic exposure has been associated with an increased risk of cardiovascular disease (CVD). Growing evidence suggests that B vitamins facilitate arsenic metabolism and may protect against arsenic toxicity. However, to our knowledge, few studies have evaluated this in US populations. Objective: Our objective was to examine whether higher B vitamin intake is associated with enhanced arsenic metabolism and lower concentrations of preclinical markers of CVD among New Hampshire adults. Methods: We used weighted quantile sum (WQS) regression to evaluate the collective impact of 6 dietary B vitamins (thiamin, riboflavin, folate, niacin, and vitamins B-6 and B-12) on 1 ) the proportion of arsenic metabolites in urine and 2 ) 6 CVD-related markers [including urinary 15-F 2t -isoprostane (15-F 2t -IsoP)] among 418 participants (26-75 y of age) from the New Hampshire Health Study. Contributions of arsenic metabolites to B vitamin-CVD marker associations were also explored in structural equation models. Results: In WQS models, the weighted sum of B vitamin intakes from food sources was inversely associated with the proportion of monomethyl arsenic species in urine (uMMA) (β: -1.03; 95% CI: -1.91, -0.15; P = 0.02). Thiamin and vitamins B-6 and B-12 contributed the most to this association, whereas riboflavin had a negligible effect. Higher overall B vitamin intake was also inversely associated with 15-F 2t -IsoP (β: -0.21; 95% CI: -0.32, -0.11; P < 0.01), with equal contributions from the 6 B vitamins, which was partially explained by differences in the proportion of uMMA (indirect effect β: -0.01; 95% CI: -0.04, -0.00). Conclusions: Among New Hampshire adults, higher intakes of certain B vitamins (particularly thiamin and vitamins B-6 and B-12 from food sources) may reduce the proportion of uMMA, an intermediate of arsenic metabolism that has been associated with an increased risk of CVD. Higher overall B vitamin intake may also reduce urinary 15-F 2t -IsoP, a marker of oxidative stress and potential risk factor for CVD, in part by reducing the proportion of uMMA. © 2017 American Society for Nutrition.

SNPs of GSTM1, T1, P1, epoxide hydrolase and DNA repair enzyme XRCC1 and risk of urinary transitional cell carcinoma in southwestern Taiwan

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hsu, L.-I; Chiu, Allen W.; Huan, Steven K.

A hospital-based case-control study was conducted near a former black-foot disease (BFD)-endemic area in southwestern Taiwan to examine the possible risk factors and genetic susceptibility for urinary transitional cell carcinoma (TCC). A total of 221 patients with pathologically confirmed TCC and 223 age-sex-matched control subjects from urology outpatient clinics were recruited between 1998 and 2002. The results showed that residency in the BFD area and consumption of well water for more than 10 years was a strong factor on urinary cancer risk (odds ratio [OR],8.16, 95% confidence interval [CI],3.34-19.90, p < 0.0001). Dose response relationship between average arsenic concentration inmore » well water and TCC risk was also observed. Cigarette smoking played a relatively minor role in urinary carcinogenesis in this study. The GSTP1 Ile105Val A {yields} G polymorphism was significantly associated with cancer risk (A/G + G/G: OR = 0.60, 95%CI = 0.39-0.94, p = 0.02), and the effect of Val105 allele was largely confined to the subjects diagnosed earlier than 55 years old (A/G + G/G: OR,0.29; 95% CI, 0.09-0.87, p = 0.03). The results suggest that GSTP1 is a candidate for susceptibility locus and Ile105 allele may predispose individuals to early-onset urinary TCC. The GSTM1 null genotype was associated with tumors of high-invasiveness (OR,2.21; 95% CI, 1.34-4.73) as well as with early-onset TCC risk (OR,2.53; 95% CI, 0.97-6.59). Our preliminary results showed the XRCC1 Arg194Trp were associated with arsenic-related urinary TCC and the interaction between the genotype and the exposure was statistically significant. The modulating effect of the GSTM1, GSTT1, GSTP1 Ile105Val, EPHX Tyr113His and XRCC1 Arg280His on arsenic-related TCC risk was also suggestive. These observations implied that impaired metabolism of carcinogenic exposure as well as impaired DNA repair function play an important role in arsenic-related urinary transitional cell carcinogenesis.« less

Arsenic methylation and lung and bladder cancer in a case-control study in northern Chile

DOE Office of Scientific and Technical Information (OSTI.GOV)

Melak, Dawit; Ferreccio, Catterina; Kalman, David

2014-01-15

In humans, ingested inorganic arsenic is metabolized to monomethylarsenic (MMA) then to dimethylarsenic (DMA), although this process is not complete in most people. The trivalent form of MMA is highly toxic in vitro and previous studies have identified associations between the proportion of urinary arsenic as MMA (%MMA) and several arsenic-related diseases. To date, however, relatively little is known about its role in lung cancer, the most common cause of arsenic-related death, or about its impacts on people drinking water with lower arsenic concentrations (e.g., < 200 μg/L). In this study, urinary arsenic metabolites were measured in 94 lung andmore » 117 bladder cancer cases and 347 population-based controls from areas in northern Chile with a wide range of drinking water arsenic concentrations. Lung cancer odds ratios adjusted for age, sex, and smoking by increasing tertiles of %MMA were 1.00, 1.91 (95% confidence interval (CI), 0.99–3.67), and 3.26 (1.76–6.04) (p-trend < 0.001). Corresponding odds ratios for bladder cancer were 1.00, 1.81 (1.06–3.11), and 2.02 (1.15–3.54) (p-trend < 0.001). In analyses confined to subjects only with arsenic water concentrations < 200 μg/L (median = 60 μg/L), lung and bladder cancer odds ratios for subjects in the upper tertile of %MMA compared to subjects in the lower two tertiles were 2.48 (1.08–5.68) and 2.37 (1.01–5.57), respectively. Overall, these findings provide evidence that inter-individual differences in arsenic metabolism may be an important risk factor for arsenic-related lung cancer, and may play a role in cancer risks among people exposed to relatively low arsenic water concentrations. - Highlights: • Urine arsenic metabolites were measured in cancer cases and controls from Chile. • Higher urine %MMA values were associated with increased lung and bladder cancer. • %MMA-cancer associations were seen at drinking water arsenic levels < 200 μg/L.« less

Associations between arsenic (+3 oxidation state) methyltransferase (AS3MT) and N-6 adenine-specific DNA methyltransferase 1 (N6AMT1) polymorphisms, arsenic metabolism, and cancer risk in a chilean population.

PubMed

de la Rosa, Rosemarie; Steinmaus, Craig; Akers, Nicholas K; Conde, Lucia; Ferreccio, Catterina; Kalman, David; Zhang, Kevin R; Skibola, Christine F; Smith, Allan H; Zhang, Luoping; Smith, Martyn T

2017-07-01

Inter-individual differences in arsenic metabolism have been linked to arsenic-related disease risks. Arsenic (+3) methyltransferase (AS3MT) is the primary enzyme involved in arsenic metabolism, and we previously demonstrated in vitro that N-6 adenine-specific DNA methyltransferase 1 (N6AMT1) also methylates the toxic inorganic arsenic (iAs) metabolite, monomethylarsonous acid (MMA), to the less toxic dimethylarsonic acid (DMA). Here, we evaluated whether AS3MT and N6AMT1 gene polymorphisms alter arsenic methylation and impact iAs-related cancer risks. We assessed AS3MT and N6AMT1 polymorphisms and urinary arsenic metabolites (%iAs, %MMA, %DMA) in 722 subjects from an arsenic-cancer case-control study in a uniquely exposed area in northern Chile. Polymorphisms were genotyped using a custom designed multiplex, ligation-dependent probe amplification (MLPA) assay for 6 AS3MT SNPs and 14 tag SNPs in the N6AMT1 gene. We found several AS3MT polymorphisms associated with both urinary arsenic metabolite profiles and cancer risk. For example, compared to wildtypes, individuals carrying minor alleles in AS3MT rs3740393 had lower %MMA (mean difference = -1.9%, 95% CI: -3.3, -0.4), higher %DMA (mean difference = 4.0%, 95% CI: 1.5, 6.5), and lower odds ratios for bladder (OR = 0.3; 95% CI: 0.1-0.6) and lung cancer (OR = 0.6; 95% CI: 0.2-1.1). Evidence of interaction was also observed for both lung and bladder cancer between these polymorphisms and elevated historical arsenic exposures. Clear associations were not seen for N6AMT1. These results are the first to demonstrate a direct association between AS3MT polymorphisms and arsenic-related internal cancer risk. This research could help identify subpopulations that are particularly vulnerable to arsenic-related disease. Environ. Mol. Mutagen. 58:411-422, 2017. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

Estimated Exposure to Arsenic in Breastfed and Formula-Fed Infants in a United States Cohort

PubMed Central

Carignan, Courtney C.; Jackson, Brian P.; Farzan, Shohreh F.; Gandolfi, A. Jay; Punshon, Tracy; Folt, Carol L.; Karagas, Margaret R.

2015-01-01

Background: Previous studies indicate that concentrations of arsenic in breast milk are relatively low even in areas with high drinking-water arsenic. However, it is uncertain whether breastfeeding leads to reduced infant exposure to arsenic in regions with lower arsenic concentrations. Objective: We estimated the relative contributions of breast milk and formula to arsenic exposure during early infancy in a U.S. population. Methods: We measured arsenic in home tap water (n = 874), urine from 6-week-old infants (n = 72), and breast milk from mothers (n = 9) enrolled in the New Hampshire Birth Cohort Study (NHBCS) using inductively coupled plasma mass spectrometry. Using data from a 3-day food diary, we compared urinary arsenic across infant feeding types and developed predictive exposure models to estimate daily arsenic intake from breast milk and formula. Results: Urinary arsenic concentrations were generally low (median, 0.17 μg/L; maximum, 2.9 μg/L) but 7.5 times higher for infants fed exclusively with formula than for infants fed exclusively with breast milk (β = 2.02; 95% CI: 1.21, 2.83; p < 0.0001, adjusted for specific gravity). Similarly, the median estimated daily arsenic intake by NHBCS infants was 5.5 times higher for formula-fed infants (0.22 μg/kg/day) than for breastfed infants (0.04 μg/kg/day). Given median arsenic concentrations measured in NHBCS tap water and previously published for formula powder, formula powder was estimated to account for ~ 70% of median exposure among formula-fed NHBCS infants. Conclusions: Our findings suggest that breastfed infants have lower arsenic exposure than formula-fed infants, and that both formula powder and drinking water can be sources of exposure for U.S. infants. Citation: Carignan CC, Cottingham KL, Jackson BP, Farzan SF, Gandolfi AJ, Punshon T, Folt CL, Karagas MR. 2015. Estimated exposure to arsenic in breastfed and formula-fed infants in a United States cohort. Environ Health Perspect 123:500–506; http://dx.doi.org/10.1289/ehp.1408789 PMID:25707031

The Use of ICP-MS and IC-ICP-MS in Environmental and Exposure Assesssment

EPA Science Inventory

OVERVIEW: Application of collision/reaction cell interference reduction technology for the minimization of polyatomic interferences in environmental matrices. Improved risk assessments through the use of arsenic speciation approaches that estimate the bio-accessibility asso...

Impact of lifestage and duration of exposure on arsenic-induced proliferative lesions and neoplasia in C3H mice.

EPA Science Inventory

Epidemiological studies suggest that chronic exposure to inorganic arsenic is associated with cancer of the skin, urinary bladder and lung as well as the kidney and liver. Previous experimental studies have demonstrated increased incidence of liver, lung, ovary, and uterine tumo...

CHARACTERIZATION OF HUMAN URINARY BLADDER CELL LINE UROTSA TRANSDUCED WITH RAT ASLLL-METHYLTRANSFERASE

EPA Science Inventory

In humans, the biomethylation of arsenic (As) is catalyzed by an As(III)-methyltransferase (Cyt19) and yields pentavalent and trivalent methylated arsenicals. Cyt19 activity and expression levels vary among tissues. For example, Cyt19 mRNA is not detected in UROtsa cells, a h...

Research on chromium and arsenic speciation in atmospheric particulate matter: short review

NASA Astrophysics Data System (ADS)

Nocoń, Katarzyna; Rogula-Kozłowska, Wioletta; Widziewicz, Kamila

2018-01-01

Atmospheric particulate matter (PM) plays an important role in the distribution of elements in the environment. The PM-bound elements penetrates into the other elements of the environment, in two basic forms - those dissolved in the atmospheric precipitation and those permanently bound to PM particles. Those forms differs greatly in their mobility, thus posing a potential threat to living organisms. They can also be an immediate threat, while being inhaled. Chromium (Cr) and arsenic (As) belong to the group of elements whose certain chemical states exhibit toxic properties, that is Cr(VI) and As(III). Thus, recognition of the actual threat posed by Cr and As in the environment, including those present in PM, is possible only through the in depth speciation analysis. Research on the Cr and As speciation in PM, more than the analogous studies of their presence in other compartments of the environment, have been undertaken quite rarely. Hence the knowledge on the speciation of PM-bound As and Cr is still limited. The state of knowledge in the field of PM-bound Cr and As is presented in the paper. The issues related to the characterization and occurrence of Cr and As species in PM, the share of Cr and As species mass in different PM size fractions, and in PM of different origin is also summarized. The analytical techniques used in the speciation analysis of PM-bound Cr and As are also discussed. In the existing literature there is no data on the physical characteristics of Cr and As (bound to a different PM size fractions), and thus it still lack of data needed for a comprehensive assessment of the actual environmental and health threat posed by airborne Cr and As.

Effects of water management on arsenic and cadmium speciation and accumulation in an upland rice cultivar.

PubMed

Hu, Pengjie; Ouyang, Younan; Wu, Longhua; Shen, Libo; Luo, Yongming; Christie, Peter

2015-01-01

Pot and field experiments were conducted to investigate the effects of water regimes on the speciation and accumulation of arsenic (As) and cadmium (Cd) in Brazilian upland rice growing in soils polluted with both As and Cd. In the pot experiment constant and intermittent flooding treatments gave 3-16 times higher As concentrations in soil solution than did aerobic conditions but Cd showed the opposite trend. Compared to arsenate, there were more marked changes in the arsenite concentrations in the soil solution as water management shifted, and therefore arsenite concentrations dominated the As speciation and bioavailability in the soil. In the field experiment As concentrations in the rice grains increased from 0.14 to 0.21 mg/kg while Cd concentrations decreased from 0.21 to 0.02 mg/kg with increasing irrigation ranging from aerobic to constantly flooding conditions. Among the various water regimes the conventional irrigation treatment produced the highest rice grain yield of 6.29 tons/ha. The As speciation analysis reveals that the accumulation of dimethylarsinic acid (from 11.3% to 61.7%) made a greater contribution to the increase in total As in brown rice in the intermittent and constant flooding treatments compared to the intermittent-aerobic treatment. Thus, water management exerted opposite effects on Cd and As speciation and bioavailability in the soil and consequently on their accumulation in the upland rice. Special care is required when irrigation regime methods are employed to mitigate the accumulation of metal(loid)s in the grain of rice grown in soils polluted with both As and Cd. Copyright © 2014. Published by Elsevier B.V.

Estimating Inorganic Arsenic Exposure from U.S. Rice and Total Water Intakes.

PubMed

Mantha, Madhavi; Yeary, Edward; Trent, John; Creed, Patricia A; Kubachka, Kevin; Hanley, Traci; Shockey, Nohora; Heitkemper, Douglas; Caruso, Joseph; Xue, Jianping; Rice, Glenn; Wymer, Larry; Creed, John T

2017-05-30

Among nonoccupationally exposed U.S. residents, drinking water and diet are considered primary exposure pathways for inorganic arsenic (iAs). In drinking water, iAs is the primary form of arsenic (As), while dietary As speciation techniques are used to differentiate iAs from less toxic arsenicals in food matrices. Our goal was to estimate the distribution of iAs exposure rates from drinking water intakes and rice consumption in the U.S. population and ethnic- and age-based subpopulations. The distribution of iAs in drinking water was estimated by population, weighting the iAs concentrations for each drinking water utility in the Second Six-Year Review data set. To estimate the distribution of iAs concentrations in rice ingested by U.S. consumers, 54 grain-specific, production-weighted composites of rice obtained from U.S. mills were extracted and speciated using both a quantitative dilute nitric acid extraction and speciation (DNAS) and an in vitro gastrointestinal assay to provide an upper bound and bioaccessible estimates, respectively. Daily drinking water intake and rice consumption rate distributions were developed using data from the What We Eat in America (WWEIA) study. Using these data sets, the Stochastic Human Exposure and Dose Simulation (SHEDS) model estimated mean iAs exposures from drinking water and rice were 4.2 μg/day and 1.4 μg/day, respectively, for the entire U.S. population. The Tribal, Asian, and Pacific population exhibited the highest mean daily exposure of iAs from cooked rice (2.8 μg/day); the mean exposure rate for children between ages 1 and 2 years in this population is 0.104 μg/kg body weight (BW)/day. An average consumer drinking 1.5 L of water daily that contains between 2 and 3 ng iAs/mL is exposed to approximately the same amount of iAs as a mean Tribal, Asian, and Pacific consumer is exposed to from rice. https://doi.org/10.1289/EHP418. Among nonoccupationally exposed U.S. residents, drinking water and diet are considered primary exposure pathways for inorganic arsenic (iAs). In drinking water, iAs is the primary form of arsenic (As), while dietary As speciation techniques are used to differentiate iAs from less toxic arsenicals in food matrices. Our goal was to estimate the distribution of iAs exposure rates from drinking water intakes and rice consumption in the U.S. population and ethnic- and age-based subpopulations. The distribution of iAs in drinking water was estimated by population, weighting the iAs concentrations for each drinking water utility in the Second Six-Year Review data set. To estimate the distribution of iAs concentrations in rice ingested by U.S. consumers, 54 grain-specific, production-weighted composites of rice obtained from U.S. mills were extracted and speciated using both a quantitative dilute nitric acid extraction and speciation (DNAS) and an in vitro gastrointestinal assay to provide an upper bound and bioaccessible estimates, respectively. Daily drinking water intake and rice consumption rate distributions were developed using data from the What We Eat in America (WWEIA) study. Using these data sets, the Stochastic Human Exposure and Dose Simulation (SHEDS) model estimated mean iAs exposures from drinking water and rice were [Formula: see text] and [Formula: see text], respectively, for the entire U.S. population. The Tribal, Asian, and Pacific population exhibited the highest mean daily exposure of iAs from cooked rice ([Formula: see text]); the mean exposure rate for children between ages 1 and 2 years in this population is [Formula: see text] body weight (BW)/day. An average consumer drinking 1.5 L of water daily that contains between 2 and [Formula: see text] is exposed to approximately the same amount of iAs as a mean Tribal, Asian, and Pacific consumer is exposed to from rice. https://doi.org/10.1289/EHP418.

Sea Level Rise Induced Arsenic Release from Historically Contaminated Coastal Soils.

PubMed

LeMonte, Joshua J; Stuckey, Jason W; Sanchez, Joshua Z; Tappero, Ryan; Rinklebe, Jörg; Sparks, Donald L

2017-06-06

Climate change-induced perturbations in the hydrologic regime are expected to impact biogeochemical processes, including contaminant mobility and cycling. Elevated levels of geogenic and anthropogenic arsenic are found along many coasts around the world, most notably in south and southeast Asia but also in the United States, particularly along the Mid-Atlantic coast. The mechanism by and the extent to which arsenic may be released in contaminated coastal soils due to sea level rise are unknown. Here we show a series of data from a coastal arsenic-contaminated soil exposed to sea and river waters in biogeochemical microcosm reactors across field-validated redox conditions. We find that reducing conditions lead to arsenic release from historically contaminated coastal soils through reductive dissolution of arsenic-bearing mineral oxides in both sea and river water inundations, with less arsenic release from seawater scenarios than river water due to inhibition of oxide dissolution. For the first time, we systematically display gradation of solid phase soil-arsenic speciation across defined redox windows from reducing to oxidizing conditions in natural waters by combining biogeochemical microcosm experiments and X-ray absorption spectroscopy. Our results demonstrate the threat of sea level rise stands to impact arsenic release from contaminated coastal soils by changing redox conditions.

Sea Level Rise Induced Arsenic Release from Historically Contaminated Coastal Soils

DOE PAGES

LeMonte, Joshua J.; Stuckey, Jason W.; Sanchez, Joshua Z.; ...

2017-05-04

Climate change-induced perturbations in the hydrologic regime are expected to impact biogeochemical processes, including contaminant mobility and cycling. Elevated levels of geogenic and anthropogenic arsenic are found along many coasts around the world, most notably in south and southeast Asia but also in the United States, particularly along the Mid-Atlantic coast. The mechanism by and the extent to which arsenic may be released in contaminated coastal soils due to sea level rise are unknown. Here we show a series of data from a coastal arsenic-contaminated soil exposed to sea and river waters in biogeochemical microcosm reactors across field-validated redox conditions.more » We find that reducing conditions lead to arsenic release from historically contaminated coastal soils through reductive dissolution of arsenic-bearing mineral oxides in both sea and river water inundations, with less arsenic release from seawater scenarios than river water due to inhibition of oxide dissolution. For the first time, we systematically display gradation of solid phase soil-arsenic speciation across defined redox windows from reducing to oxidizing conditions in natural waters by combining biogeochemical microcosm experiments and X-ray absorption spectroscopy. Here, our results demonstrate the threat of sea level rise stands to impact arsenic release from contaminated coastal soils by changing redox conditions.« less

Sea Level Rise Induced Arsenic Release from Historically Contaminated Coastal Soils

DOE Office of Scientific and Technical Information (OSTI.GOV)

LeMonte, Joshua J.; Stuckey, Jason W.; Sanchez, Joshua Z.

Climate change-induced perturbations in the hydrologic regime are expected to impact biogeochemical processes, including contaminant mobility and cycling. Elevated levels of geogenic and anthropogenic arsenic are found along many coasts around the world, most notably in south and southeast Asia but also in the United States, particularly along the Mid-Atlantic coast. The mechanism by and the extent to which arsenic may be released in contaminated coastal soils due to sea level rise are unknown. Here we show a series of data from a coastal arsenic-contaminated soil exposed to sea and river waters in biogeochemical microcosm reactors across field-validated redox conditions.more » We find that reducing conditions lead to arsenic release from historically contaminated coastal soils through reductive dissolution of arsenic-bearing mineral oxides in both sea and river water inundations, with less arsenic release from seawater scenarios than river water due to inhibition of oxide dissolution. For the first time, we systematically display gradation of solid phase soil-arsenic speciation across defined redox windows from reducing to oxidizing conditions in natural waters by combining biogeochemical microcosm experiments and X-ray absorption spectroscopy. Here, our results demonstrate the threat of sea level rise stands to impact arsenic release from contaminated coastal soils by changing redox conditions.« less

Lead and Arsenic Bioaccessibility and Speciation as a Function of Soil Particle Size

EPA Science Inventory

Bioavailability research of soil metals has advanced considerably from default values to validated in vitro bioaccessibility (IVBA) assays for site-specific risk assessment. Previously, USEPA determined that the soil-size fraction representative of dermal adherence and consequent...

PRINCIPLES OF SYNCHROTRON TECHNIQUES, POTENTIAL AND LIMITATIONS

EPA Science Inventory

Once environmental contaminants, such as arsenic, chromium, cadmium and lead, are detected, the problem becomes how to deal with them. For the past decade, researchers at the US EPA in Cincinnati have been employing synchrotron speciation methods to determine the exact chemical f...

Micron to Mine: Synchrotron Science for Mineral Exploration, Production, and Remediation

NASA Astrophysics Data System (ADS)

Banerjee, N.; Van Loon, L.; Flynn, T.

2017-12-01

Synchrotron science for mineral exploration, production, and remediation studies is a powerful tool that provides industry with relevant micron to macro geochemical information. Synchrotron micro X-ray fluorescence (SR-µXRF) offers a direct, high-resolution, rapid, and cost-effective chemical analysis while preserving the context of the sample by mapping ore minerals with ppm detection limits. Speciation of trace and deleterious elements can then be probed using X-ray absorption near-edge structure (XANES) spectroscopy. Large-scale (tens of cm) µXRF mapping and XANES analysis of samples collected at various mine locations have been undertaken to address questions regarding mineralization history to develop novel trace element exploration vectors. This information provides integral insights into trace element associations with ore minerals, local redox conditions responsible for mineralization, and mineralizing mechanisms. Gold is commonly intimately associated with sulfide mineralization (e.g., pyrite, arsenopyrite, etc.) and is present both as inclusions and filling fractures in sulfide grains. Gold may also occur as nanoparticles and/or in the sulfide mineral crystal lattice, known as "invisible gold". Understanding the nature and distribution of invisible gold in ore is integral to processing efficiency. The high flux and energy of a synchrotron light source allows for the detection of invisible gold by µXRF, and can probe its nature (metallic Au0 vs. lattice bound Au1+) using XANES spectroscopy. The long-term containment and management of arsenic is necessary to protect the health of both humans and the environment. Understanding the relationship of arsenic mineralization to gold deposits can lead to more sophisticated planning for mineral processing and the eventual storage of gangue materials. µXANES spectroscopy is an excellent tool for determining arsenic speciation within the context of the sample. Mineral phases such as arsenopyrite, scorodite, and arsenic trioxide can be accurately identified as well as relative amounts determined. With this information the oxidation-reduction of arsenic-bearing compounds can be monitored to optimize management practices for the long-term capture of arsenic contaminants.

Biochars mitigate greenhouse gas emissions and bioaccumulation of potentially toxic elements and arsenic speciation in Phaseolus vulgaris L.

PubMed

Ibrahim, Muhammad; Li, Gang; Khan, Sardar; Chi, Qiaoqiao; Xu, Yaoyang; Zhu, Yongguan

2017-08-01

Anthropogenic and natural activities can lead to increased greenhouse gas emissions and discharge of potentially toxic elements (PTEs) into soil environment. Biochar amendment to soils is a cost-effective technology and sustainable approach used to mitigate greenhouse gas emissions, improve phytoremediation, and minimize the health risks associated with consumption of PTE-contaminated vegetables. Greenhouse pot experiments were conducted to investigate the effects of peanut shell biochar (PNB) and sewage sludge biochar (SSB) on greenhouse gas (GHG) emissions, plant growth, PTE bioaccumulation, and arsenic (As) speciation in bean plants. Results indicated that amendments of PNB and SSB increased plant biomass production by increasing soil fertility and reducing bioavailability of PTEs. Addition of biochars also increased soil pH, total nitrogen (TN), total carbon (TC), dissolved organic carbon (DOC), and ammonium-nitrogen (NH 4 -N) but decreased available concentrations of PTEs such as cadmium (Cd), lead (Pb), and As. The concentration of nitrate-nitrogen (NO 3 - -N) was also decreased in biochar-amended soils. In addition, PNB and SSB amendments significantly (P < 0.01) reduced the bioaccumulation of chromium (Cr), As, Cd, Pb, and nickel (Ni) in stalks, leaves, and fruits of Phaseolus vulgaris L. Similarly, PNB and SSB amendments significantly (P ≤ 0.05) reduced inorganic As species like arsenite (As (III)) and arsenate (As (V)). Greenhouse gases such as carbon dioxide (CO 2 ) and methane (CH 4 ) emissions were significantly (P < 0.01) reduced but nitrous oxide (N 2 O) emissions first increased and then decreased amended with both biochars. Current findings demonstrate that SSB and PNB are two beneficial soil amendments simultaneous mitigating greenhouse gas emissions and PTE bioaccumulation as well as arsenic speciation in P. vulgaris L.

Mechanisms of Arsenic Hyperaccumulation in Pteris vittata. Uptake Kinetics, Interactions with Phosphate, and Arsenic Speciation1

PubMed Central

Wang, Junru; Zhao, Fang-Jie; Meharg, Andrew A.; Raab, Andrea; Feldmann, Joerg; McGrath, Steve P.

2002-01-01

The mechanisms of arsenic (As) hyperaccumulation in Pteris vittata, the first identified As hyperaccumulator, are unknown. We investigated the interactions of arsenate and phosphate on the uptake and distribution of As and phosphorus (P), and As speciation in P. vittata. In an 18-d hydroponic experiment with varying concentrations of arsenate and phosphate, P. vittata accumulated As in the fronds up to 27,000 mg As kg−1 dry weight, and the frond As to root As concentration ratio varied between 1.3 and 6.7. Increasing phosphate supply decreased As uptake markedly, with the effect being greater on root As concentration than on shoot As concentration. Increasing arsenate supply decreased the P concentration in the roots, but not in the fronds. Presence of phosphate in the uptake solution decreased arsenate influx markedly, whereas P starvation for 8 d increased the maximum net influx by 2.5-fold. The rate of arsenite uptake was 10% of that for arsenate in the absence of phosphate. Neither P starvation nor the presence of phosphate affected arsenite uptake. Within 8 h, 50% to 78% of the As taken up was distributed to the fronds, with a higher translocation efficiency for arsenite than for arsenate. In fronds, 49% to 94% of the As was extracted with a phosphate buffer (pH 5.6). Speciation analysis using high-performance liquid chromatography-inductively coupled plasma mass spectroscopy showed that >85% of the extracted As was in the form of arsenite, and the remaining mostly as arsenate. We conclude that arsenate is taken up by P. vittata via the phosphate transporters, reduced to arsenite, and sequestered in the fronds primarily as As(III). PMID:12428020

Influence of organic substrates on the kinetics of bacterial As(III) oxidation

NASA Astrophysics Data System (ADS)

Lescure, T.; Joulian, C.; Bauda, P.; Hénault, C.; Battaglia-Brunet, F.

2012-04-01

Soil microflora plays a major role on the behavior of metals and metalloids. Arsenic speciation, in particular, is related to the activity of bacteria able to oxidize, reduce or methylate this element, and determines mobility, bioavailability and toxicity of As. Arsenite (AsIII) is more toxic and more mobile than arsenate (AsV). Bacterial As(III)-oxidation tends to reduce the toxicity of arsenic in soils and the risk of transfer toward underlying aquifers, that would affect the quality of water resources. Previous results suggest that organic matter may affect kinetics or efficiency of bacterial As(III)-oxidation in presence of oxygen, thus in conventional physico-chemical conditions of a surface soil. Different hypothesis can be proposed to explain the influence of organic matter on As(III) oxidation. Arsenic is a potential energy source for bacteria. The presence of easily biodegradable organic matter may inhibit the As(III) oxidation process because bacteria would first metabolize these more energetic substrates. A second hypothesis would be that, in presence of organic matter, the Ars system involved in bacterial resistance to arsenic would be more active and would compete with the Aio system of arsenite oxidation, decreasing the global As(III) oxidation rate. In addition, organic matter influences the solubility of iron oxides which often act as the main pitfalls of arsenic in soils. The concentration and nature of organic matter could therefore have a significant influence on the bioavailability of arsenic and hence on its environmental impact. The influence of organic matter on biological As(III) oxidation has not yet been determined in natural soils. In this context, soil amendment with organic matter during operations of phytostabilization or, considering diffuse pollutions, through agricultural practices, may affect the mobility and bio-availability of the toxic metalloid. The objective of the present project is to quantify the influence of organic matter on the bacterial speciation of arsenic in contaminated soils. Moreover, the biogeochemical consequences of this phenomenon on the mobility and ecotoxicity of this metalloid will be studied. The first task of this program is the precise and systematic investigation of the influence of different types and concentrations of organic matters on the activity of As(III)-oxidizing pure strains. Influence of aspartate, succinate (simple substrates) and yeast extract (complex substrate) on As(III)-oxidation kinetics has been studied. For each experiment, the bacterial growth and the expression of genes involved in the speciation of arsenic, i.e. aio and ars genes, has been monitored. A direct perspective of this work will be to perform experiments with humic and fulvic acids (complex organic matter commonly found in soils), and with water-extracted organic matter from polluted soils. Then the As(III)-oxidation activity of bacterial communities extracted from contaminated soils will be followed. These assays should allow the screening of conditions which will be applied in subsequent experiments with several real contaminated soils, including a former mining site, impacted industrial sites, and a forest soil heavily contaminated after arsenical ammunitions storage. This work is co-funded by BRGM and ADEME (convention TEZ 11-16).

Transplacental Arsenic Carcinogenesis in Mice

PubMed Central

Waalkes, Michael P.; Liu, Jie; Diwan, Bhalchandra A.

2007-01-01

Our work has focused on the carcinogenic effects of in utero arsenic exposure in mice. Our data show a short period of maternal exposure to inorganic arsenic in the drinking water is an effective, multi-tissue carcinogen in the adult offspring. These studies have been reproduced in three temporally separate studies using two different mouse strains. In these studies pregnant mice were treated with drinking water containing sodium arsenite at up to 85 ppm arsenic from day 8 to 18 of gestation, and the offspring were observed for up to two years. The doses used in all these studies were well tolerated by both the dam and offspring. In C3H mice, two separate studies show male offspring exposed to arsenic in utero developed liver carcinoma and adrenal cortical adenoma in a dose-related fashion during adulthood. Prenatally exposed female C3H offspring show dose-related increases in ovarian tumors and lung carcinoma and in proliferative lesions (tumors plus preneoplastic hyperplasia) of the uterus and oviduct. In addition, prenatal arsenic plus postnatal exposure to the tumor promoter, 12-O-tetradecanoyl phorbol-13-acetate (TPA) in C3H mice produces excess lung tumors in both sexes and liver tumors in females. Male CD1 mice treated with arsenic in utero develop tumors of the liver and adrenal and renal hyperplasia while females develop tumors of urogenital system, ovary, uterus and adrenal and hyperplasia of the oviduct. Additional postnatal treatment with diethylstilbestrol or tamoxifen after prenatal arsenic in CD1 mice induces urinary bladder transitional cell proliferative lesions, including carcinoma and papilloma, and enhances the carcinogenic response in the liver of both sexes. Overall this model has provided convincing evidence that arsenic is a transplacental carcinogen in mice with the ability to target tissues of potential human relevance, such as the urinary bladder, lung and liver. Transplacental carcinogenesis clearly occurs with other agents in humans and investigating a potential transplacental component of the human carcinogenic response to arsenic should be a research priority. PMID:17306315

Ferric minerals and organic matter change arsenic speciation in copper mine tailings.

PubMed

Wang, Peng; Liu, Yunjia; Menzies, Neal W; Wehr, J Bernhard; de Jonge, Martin D; Howard, Daryl L; Kopittke, Peter M; Huang, Longbin

2016-11-01

Arsenic (As) is commonly associated with Cu ore minerals, with the resultant risk that As can be released offsite from mine tailings. We used synchrotron-based fluorescence X-ray absorption near-edge spectroscopy (XANES) imaging to provide in situ, laterally-resolved speciation of As within tailings which differed in magnetite content (5-12%) and organic matter content (0-5%). Although the total As content was lower in tailings with low magnetite (LM), the soluble (pore water) As was actually 7-times higher in LM tailings than in high magnetite (HM) tailings. Additionally, amendment with 5% sugarcane mulch residues (SMR) (for revegetation) further increased soluble As due to the dissolution and oxidation of arsenopyrite or orpiment. Indeed, in HM tailings, arsenopyrite and orpiment initially accounted for 88% of the total As, which decreased to 48% upon the addition of SMR - this being associated with an increase in As V -ferrihydrite from 12% to 52%. In LM tailings, the pattern of As distribution and speciation was similar, with As as As V -ferrihydrite increasing from 57% to 75% upon the addition of SMR. These findings indicate that changes in ore processing technology, such as the recovery of magnetite could have significant environmental consequences regarding the As mobilisation and transformation in mine tailings. Copyright © 2016 Elsevier Ltd. All rights reserved.

Localization and Speciation of Arsenic in Soil and Desert Plant Parkinsonia florida using μXRF and μXANES

PubMed Central

Castillo-Michel, Hiram; Hernandez-Viezcas, Jose; Dokken, Kenneth M.; Marcus, Matthew A.; Peralta-Videa, Jose R.; Gardea-Torresdey, Jorge L.

2011-01-01

Parkinsonia florida is a plant species native to the semi-desert regions of North America. The cultivation characteristics of this shrub/tree suggest that it could be used for phytoremediation purposes in semiarid regions. This work describes, through the use of synchrotron μXRF and μXANES techniques and ICP-OES, the arsenic (As) accumulation and distribution in P. florida plants grown in two soils spiked with As at 20 mg kg-1. Plants grown in a sandy soil accumulated at least twice more As in the roots compared to plants grown in a loamy soil. The lower As accumulation in plants grown in the loamy soil corresponded to a lower concentration of As in the water soluble fraction (WSF) of this soil. LC-ICP-MS speciation analysis showed only As(V) in the WSF from all treatments. In contrast, linear combination XANES speciation analysis from the root tissues showed As mainly present in the reduced As(III) form. Moreover, a fraction of the reduced As was found coordinating to S in a form consistent with As-Cys3. The percentage of As coordinated to sulfur was smaller for plants grown in the loamy soil when compared to the sandy soil. PMID:21842861

Localization and speciation of arsenic in soil and desert plant Parkinsonia florida using μXRF and μXANES.

PubMed

Castillo-Michel, Hiram; Hernandez-Viezcas, Jose; Dokken, Kenneth M; Marcus, Matthew A; Peralta-Videa, Jose R; Gardea-Torresdey, Jorge L

2011-09-15

Parkinsonia florida is a plant species native to the semidesert regions of North America. The cultivation characteristics of this shrub/tree suggest that it could be used for phytoremediation purposes in semiarid regions. This work describes, through the use of synchrotron μXRF and μXANES techniques and ICP-OES, the arsenic (As) accumulation and distribution in P. florida plants grown in two soils spiked with As at 20 mg kg(-1). Plants grown in a sandy soil accumulated at least twice more As in the roots compared to plants grown in a loamy soil. The lower As accumulation in plants grown in the loamy soil corresponded to a lower concentration of As in the water-soluble fraction (WSF) of this soil. LC-ICP-MS speciation analysis showed only As(V) in the WSF from all treatments. In contrast, linear combination XANES speciation analysis from the root tissues showed As mainly present in the reduced As(III) form. Moreover, a fraction of the reduced As was found coordinating to S in a form consistent with As-Cys(3). The percentage of As coordinated to sulfur was smaller for plants grown in the loamy soil when compared to the sandy soil.

Microbial Sulfate Reduction Enhances Arsenic Mobility Downstream of Zerovalent-Iron-Based Permeable Reactive Barrier.

PubMed

Kumar, Naresh; Couture, Raoul-Marie; Millot, Romain; Battaglia-Brunet, Fabienne; Rose, Jérôme

2016-07-19

We assessed the potential of zerovalent-iron- (Fe(0)) based permeable reactive barrier (PRB) systems for arsenic (As) remediation in the presence or absence of microbial sulfate reduction. We conducted long-term (200 day) flow-through column experiments to investigate the mechanisms of As transformation and mobility in aquifer sediment (in particular, the PRB downstream linkage). Changes in As speciation in the aqueous phase were monitored continuously. Speciation in the solid phase was determined at the end of the experiment using X-ray absorption near-edge structure (XANES) spectroscopy analysis. We identified thio-As species in solution and AsS in solid phase, which suggests that the As(V) was reduced to As(III) and precipitated as AsS under sulfate-reducing conditions and remained as As(V) under abiotic conditions, even with low redox potential and high Fe(II) content (4.5 mM). Our results suggest that the microbial sulfate reduction plays a key role in the mobilization of As from Fe-rich aquifer sediment under anoxic conditions. Furthermore, they illustrate that the upstream-downstream linkage of PRB affects the speciation and mobility of As in downstream aquifer sediment, where up to 47% of total As initially present in the sediment was leached out in the form of mobile thio-As species.

Concentrations and speciation of arsenic in New England seaweed species harvested for food and agriculture.

PubMed

Taylor, Vivien F; Jackson, Brian P

2016-11-01

A survey of arsenic (As) concentrations and speciation was conducted on 10 species of seaweed from commercial harvesters and from collection at two sites in New England. Concentrations of As ranged from 4 to 106 mg/kg, mostly in the form of arsenosugars, with the distribution of arsenosugar analogs varying between taxa. In brown algae, As levels were correlated with phosphate concentrations, and arsenosugar speciation reflected differences in sulfur and phosphate concentrations between taxa. Several samples of the brown algae species Laminaria digitata contained significant levels of inorganic As (2.8-20 mg/kg), the most toxic form of As. A weak acid extraction with microwave heating was compared with a weaker methanol: water extraction method, and found to give slightly higher extraction efficiency with comparable relative concentrations of inorganic As, supporting the use of this faster and simpler extraction method for monitoring. Seaweed is a niche dietary item in the U.S. but its popularity is increasing; it is also used in agriculture and livestock farming which provide potential indirect routes for human exposure. The presence of occasional high concentrations of iAs, as well as the lack of toxicity studies on organic As species, suggest that monitoring of these high As foods is warranted. Copyright © 2016 Elsevier Ltd. All rights reserved.

[Evaluation of compounding EDTA and citric acid on remediation of heavy metals contaminated soil].

PubMed

Yin, Xue; Chen, Jia-Jun; Cai, Wen-Min

2014-08-01

As commonly used eluents, Na2EDTA (EDTA) and citric acid (CA) have been widely applied in remediation of soil contaminated by heavy metals. In order to evaluate the removal of arsenic, cadmium, copper, and lead in the contaminated soil collected in a chemical plant by compounding EDTA and CA, a series of stirring experiments were conducted. Furthermore, the changes in speciation distribution of heavy metals before and after washing were studied. The results showed that, adopting the optimal molar ratio of EDTA/CA (1:1), when the pH of the solution was 3, the stirring time was 30 min, the stirring rate was 150 r x min(-1) and the L/S was 5:1, the removal rates of arsenic, cadmium, copper and lead could reach 11.72%, 43.39%, 24.36% and 27.17%, respectively. And it was found that after washing, for arsenic and copper, the content of acid dissolved fraction rose which increased the percentage of available contents. Fe-Mn oxide fraction mainly contributed to the removal of copper. As for cadmium, the percentages of acid dissolved fraction, Fe-Mn oxide fraction and organic fraction also decreased. In practical projects, speciation changes would pose certain environmental risk after soil washing, which should be taken into consideration.

Determination of arsenic species and arsenosugars in marine samples by HPLC-ICP-MS.

PubMed

Hirata, Shizuko; Toshimitsu, Hideki

2005-10-01

Arsenic-speciation analysis in marine samples was performed by high-pressure liquid chromatography (HPLC) with ICP-MS detection. Separation of eight arsenic species--As(III), MMA, DMA, As(V), AB, TMAO, AC and TeMAs(+)--was achieved on a C(18) column with isocratic elution (pH 3.0), under which conditions As(III) and MMA co-eluted. The entire separation was accomplished in 15 min. The HPLC-ICP-MS detection limits for the eight arsenic species were in the range 0.03-0.23 microg L(-1) based on 3 sigma for the blank response (n=5). The precision was calculated to be 2.4-8.0% (RSD) for the eight species. The method was successfully applied to several marine samples, e.g. oysters, fish, shrimps, and marine algae. Low-power microwave digestion was employed for extraction of arsenic from seafood products; ultrasonic extraction was employed for the extraction of arsenic from seaweeds. Separation of arsenosugars was achieved on an anion-exchange column. Concentrations of arsenosugars 2, 3, and 4 in marine algae were in the range 0.18-9.59 microg g(-1).

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yokohira, Masanao; Arnold, Lora L.; Pennington, Karen L.

Arsenic (+ 3 oxidation state) methyltransferase (As3mt) catalyzes reactions which convert inorganic arsenic to methylated metabolites. This study determined whether the As3mt null genotype in the mouse modifies cytotoxic and proliferative effects seen in urinary bladders of wild type mice after exposure to inorganic arsenic. Female wild type C57BL/6 mice and As3mt KO mice were divided into 3 groups each (n = 8) with free access to a diet containing 0, 100 or 150 ppm of arsenic as arsenite (As{sup III}). During the first week of As{sup III} exposure, As3mt KO mice exhibited severe and lethal systemic toxicity. At termination,more » urinary bladders of both As3mt KO and wild type mice showed hyperplasia by light microscopy. As expected, arsenic-containing granules were found in the superficial urothelial layer of wild type mice. In As3mt KO mice these granules were present in all layers of the bladder epithelium and were more abundant and larger than in wild type mice. Scanning electron microscopy of the bladder urothelium of As3mt KO mice treated with 100 ppm As{sup III} showed extensive superficial necrosis and hyperplastic changes. In As3mt KO mice, livers showed severe acute inflammatory changes and spleen size and lymphoid areas were decreased compared with wild type mice. Thus, diminished arsenic methylation in As3mt KO mice exacerbates systemic toxicity and the effects of As{sup III} on the bladder epithelium, showing that altered kinetic and dynamic behavior of arsenic can affect its toxicity.« less

Spatial and Temporal Variations in Arsenic Exposure via Drinking-water in Northern Argentina

PubMed Central

Concha, Gabriela; Nermell, Barbro

2006-01-01

This study evaluated the spatial, temporal and inter-individual variations in exposure to arsenic via drinking-water in Northern Argentina, based on measurements of arsenic in water, urine, and hair. Arsenic concentrations in drinking-water varied markedly among locations, from <1 to about 200 μg/L. Over a 10-year period, water from the same source in San Antonio de los Cobres fluctuated within 140 and 220 μg/L, with no trend of decreasing concentration. Arsenic concentrations in women's urine (3–900 μg/L, specific weight 1.018 g/mL) highly correlated with concentrations in water on a group level, but showed marked variations between individuals. Arsenic concentrations in hair (range 20–1,500 μg/kg) rather poorly correlated with urinary arsenic, possibly due to external contamination. Thus, arsenic concentration in urine seems to be a better marker of individual arsenic exposure than concentrations in drinking-water and hair. PMID:17366773

Influence of Organic Matter - Mineral Interfacial Reactions on Metal(loid) Speciation and Bioaccessibility

NASA Astrophysics Data System (ADS)

Chorover, J.; Kong, S.; Root, R. A.; Thomas, A.

2015-12-01

Bioaccessibility of contaminant metals in geomedia is often measured on the basis of kinetic release to solution during in vitro reaction with biofluid simulants. We postulate that development of a predictive-mechanistic understanding of bioaccessibility requires knowledge of metal(loid) molecular speciation upon sample introduction, as well as its change over the course of the in vitro reaction. Our results - including data from batch, column, mesocosm and field studies pertaining to arsenic, lead, and zinc contaminated materials - indicate the strong influence of organic matter and associated biological activity on metal(loid) speciation in mine tailings and related model systems. Furthermore, presence/absence of organic matter during bioassays affects the kinetics of metal(loid) release into biofluid simulants through multiple mechanisms.

Characterizing arsenic in preserved hair for assessing exposure potential and discriminating poisoning

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kempson, Ivan M.; Henry, Dermot; Francis, James

Advanced analytical techniques have been used to characterize arsenic in taxidermy specimens. Arsenic was examined to aid in discriminating its use as a preservative from that incorporated by ingestion and hence indicate poisoning (in the case of historical figures). The results are relevant to museum curators, occupational and environmental exposure concerns, toxicological and anthropological investigations. Hair samples were obtained from six taxidermy specimens preserved with arsenic in the late 1800s and early 1900s to investigate the arsenic incorporation. The presence of arsenic poses a potential hazard in museum and private collections. For one sample, arsenic was confirmed to be presentmore » on the hair with time-of-flight secondary ion mass spectrometry and then measured with neutron activation analysis to comprise 176 {mu}g g{sup -1}. The hair cross section was analysed with synchrotron micro-X-ray fluorescence to investigate the transverse distribution of topically applied arsenic. It was found that the arsenic had significantly penetrated all hair samples. Association with melanin clusters and the medulla was observed. Lead and mercury were also identified in one sample. X-ray absorption near-edge spectroscopy of the As K-edge indicated that an arsenate species predominantly existed in all samples; however, analysis was hindered by very rapid photoreduction of the arsenic. It would be difficult to discriminate arsenic consumption from topically applied arsenic based on the physical transverse distribution. Longitudinal distributions and chemical speciation may still allow differentiation.« less

ARSENIC IN DRINKING WATER SUPPLY WELLS: A MULTI ...

EPA Pesticide Factsheets

Studies have indicated that arsenic concentrations greater than the new U.S. Environmental Protection Agency (EPA) maximum contaminant level (MCL) concentration of 10 micrograms per liter (µg/L) occur in numerous aquifers around the United States. One such aquifer is the Central Oklahoma aquifer, which supplies drinking water to numerous communities in central Oklahoma. Concentrations as high as 230 µg/L have been reported in some drinking water supply wells from this aquifer. The city of Norman, like most other affected cities, is actively seeking a cost-effective solution to the arsenic problem. Only six of the city’s 32 wells exceeded the old MCL of 50 µg/L. With implementation of the new MCL this year, 18 of the 32 wells exceed the allowable concentration of arsenic. Arsenic-bearing shaly sandstones appear to be the source of the arsenic. It may be possible to isolate these arsenic-bearing zones from water supply wells, enabling production of water that complies with drinking water standards. It is hypothesized that geologic mapping together with detailed hydrogeochemical investigations will yield correlations which predict high arsenic occurrence for the siting of new drinking water production wells. More data and methods to assess the specific distribution, speciation, and mode of transport of arsenic in aquifers are needed to improve our predictions for arsenic occurrence in water supply wells. Research is also needed to assess whether we can ret

DOE Office of Scientific and Technical Information (OSTI.GOV)

Smith, Euan; Kempson, Ivan; Juhasz, Albert L.

The consumption of arsenic (As) contaminated rice is an important exposure route for humans in countries where rice cultivation employs As contaminated irrigation water. Arsenic toxicity and mobility are a function of its chemical-speciation. The distribution and identification of As in the rice plant are hence necessary to determine the uptake, transformation and potential risk posed by As contaminated rice. In this study we report on the distribution and chemical-speciation of As in rice (Oryza sativa Quest) by X-ray fluorescence (XRF) and X-ray absorption near edge structure (XANES) measurements of rice plants grown in As contaminated paddy water. Investigations ofmore » {mu}XRF images from rice tissues found that As was present in all rice tissues, and its presence correlated with the presence of iron at the root surface and copper in the rice leaf. X-ray absorption near edge structure analysis of rice tissues identified that inorganic As was the predominant form of As in all rice tissues studied, and that arsenite became increasingly dominant in the aerial portion of the rice plant.« less

Arsenic speciation and heavy metal distribution in polished rice grown in Guangdong Province, Southern China.

PubMed

Ma, Li; Wang, Lin; Tang, Jie; Yang, Zhaoguang

2017-10-15

Arsenic speciation and heavy metal distributions have been investigated in locally grown rice grains from Guangdong Province, Southern China. A total of 41 polished rice grain samples were collected throughout Guangdong Province. Arsenite (As(III)), as the predominant form found in the rice, was positively correlated (p<0.01) with total As (tAs) concentration. However, the percentage of As(III) reduced while tAs concentration increased (r=-0.361, p<0.05), due to restricted accumulation and translocation of As(III) in rice grains at high level of tAs. Statistical and geostatistical analyses were applied to investigate potential origins of heavy metals in rice. Only Cd, Cu and Ni were identified as influenced by anthropogenic sources such as industrial and commercial activities. As and Pb were primarily controlled by natural occurrence. The results of health risk assessment implied that continuous intake of rice grown in Guangdong Province could cause considerably non-carcinogenic and carcinogenic risk to local inhabitants. Copyright © 2017 Elsevier Ltd. All rights reserved.

Concentrations and speciation of arsenic along a groundwater flow-path in the Upper Floridan aquifer, Florida, USA

NASA Astrophysics Data System (ADS)

Haque, S. E.; Johannesson, K. H.

2006-05-01

Arsenic (As) concentrations and speciation were determined in groundwaters along a flow-path in the Upper Floridan aquifer (UFA) to investigate the biogeochemical “evolution“ of As in this relatively pristine aquifer. Dissolved inorganic As species were separated in the field using anion-exchange chromatography and subsequently analyzed by inductively coupled plasma mass spectrometry. Total As concentrations are higher in the recharge area groundwaters compared to down-gradient portions of UFA. Redox conditions vary from relatively oxic to anoxic along the flow-path. Mobilization of As species in UFA groundwaters is influenced by ferric iron reduction and subsequent dissolution, sulfate reduction, and probable pyrite precipitation that are inferred from the data to occur along distinct regions of the flow-path. In general, the distribution of As species are consistent with equilibrium thermodynamics, such that arsenate dominates in more oxidizing waters near the recharge area, and arsenite predominates in the progressively reducing groundwaters beyond the recharge area.

Oxidative DNA damage of peripheral blood polymorphonuclear leukocytes, selectively induced by chronic arsenic exposure, is associated with extent of arsenic-related skin lesions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pei, Qiuling, E-mail: 924969007@qq.com; Ma, Ning; Zhang, Jing

There is increasing evidence that oxidative stress is an important risk factor for arsenic-related diseases. Peripheral blood leukocytes constitute an important defense against microorganisms or pathogens, while the research on the impact of chronic arsenic exposure on peripheral blood leukocytes is much more limited, especially at low level arsenic exposure. The purpose of the present study was to explore whether chronic arsenic exposure affects oxidative stress of peripheral blood leukocytes and possible linkages between oxidative stress and arsenic-induced skin lesions. 75 male inhabitants recruited from an As-endemic region of China were investigated in the present study. The classification of arsenicosismore » was based on the degree of skin lesions. Arsenic levels were measured in drinking water and urine by Atomic Fluorescence Spectroscopy. Urinary 8-hydroxy-2′-deoxyguanosine (8-OHdG) was tested by Enzyme-Linked Immunosorbent Assay. 8-OHdG of peripheral blood leukocytes was evaluated using immunocytochemical staining. 8-OHdG-positive reactions were only present in polymorphonuclear leukocytes (PMNs), but not in monocytes (MNs). The 8-OHdG staining of PMN cytoplasm was observed in all investigated populations, while the 8-OHdG staining of PMN nuclei was frequently found along with the elevated amounts of cell debris in individuals with skin lesion. Urinary arsenic levels were increased in the severe skin lesion group compared with the normal group. No relationship was observed between drinking water arsenic or urine 8-OHdG and the degree of skin lesions. These findings indicated that the target and persistent oxidative stress in peripheral blood PMNs may be employed as a sensitive biomarker directly to assess adverse health effects caused by chronic exposure to lower levels of arsenic. -- Highlights: ► Male inhabitants were investigated from an As-endemic region of China. ► 8-OHdG-positive reactions were only present in polymorphonuclear leukocytes (PMNs). ► 8-OHdG staining of PMN nuclei was paralleled by increased debris of cells. ► Oxidative DNA damage of PMNs is associated with arsenic-related skin lesions.« less

How conservative is arsenic in coastal marine environments? A study in Irish coastal waters

NASA Astrophysics Data System (ADS)

Anninou, Pinelopi; Cave, Rachel R.

2009-04-01

The conservative potential of arsenic in the relatively pristine waters of Galway Bay, an estuarine system in the west of Ireland, is examined through the inter-seasonal variations in the distribution of its total, hydride and non-hydride fractions. The arsenic concentrations in Galway Bay and local fresh water sources at all seasons were lower than what is considered the natural seawater concentration of 2 μg L -1 (27 nM). The effects of physical mixing, biological uptake and regeneration of arsenic on its distribution are considered. The degree of biological uptake and regeneration of the element are determined by a first order speciation between total arsenic (a small part of which should be of organic origin) and hydride arsenic (mostly of inorganic origin). The structural similarity of arsenic species to phosphate in seawater causes arsenic to be taken up by biota, which then have to detoxify it, so results are presented against phosphate to determine the degree of biological transformation of arsenic at different seasons. An in-house, batch type system of hydride generation coupled to electro-thermal atomic absorption spectrometry is used for the analysis of arsenic; this is preceded by UV-digestion prior to the measurement of total arsenic. Results show only a small association of arsenic with phosphate but a near linear, positive distribution pattern between arsenic and salinity in Galway Bay ( R2 ˜ 0.6), which is reproducible among seasons, indicating that in this environment the biological uptake of arsenic is likely to be a much slower process than the physical mixing of the water masses.

Insights into arsenic multi-operons expression and resistance mechanisms in Rhodopseudomonas palustris CGA009

PubMed Central

Zhao, Chungui; Zhang, Yi; Chan, Zhuhua; Chen, Shicheng; Yang, Suping

2015-01-01

Arsenic (As) is widespread in the environment and causes numerous health problems. Rhodopseudomonas palustris has been regarded as a good model organism for studying arsenic detoxification since it was first demonstrated to methylate environmental arsenic by conversion to soluble or gaseous methylated species. However, the detailed arsenic resistance mechanisms remain unknown though there are at least three arsenic-resistance operons (ars1, ars2, and ars3) in R. palustris. In this study, we investigated how arsenic multi-operons contributed to arsenic detoxification in R. palustris. The expression of ars2 or ars3 operons increased with increasing environmental arsenite (As(III)) concentrations (up to 1.0 mM) while transcript of ars1 operon was not detected in the middle log-phase (55 h). ars2 operon was actively expressed even at the low concentration of As(III) (0.01 μM), whereas the ars3 operon was expressed at 1.0 μM of As(III), indicating that there was a differential regulation mechanism for the three arsenic operons. Furthermore, ars2 and ars3 operons were maximally transcribed in the early log-phase where ars2 operon was 5.4-fold higher than that of ars3 operon. A low level of ars1 transcript was only detected at 43 h (early log-phase). Arsenic speciation analysis demonstrated that R. palustris could reduce As(V) to As(III). Collectively, strain CGA009 detoxified arsenic by using arsenic reduction and methylating arsenic mechanism, while the latter might occur with the presence of higher concentrations of arsenic. PMID:26441915

THE URINARY BLADDER EXHIBITS A U-SHAPED GENOMIC DOSE-RESPONSE FOLLOWING SHORT- AND LONG-TERM EXPOSURE OF MICE TO ARSENATE IN DRINKING WATER

EPA Science Inventory

A number of studies have demonstrated increased urinary bladder tumor incidence in populations exposed to inorganic arsenic in drinking water at concentrations on the order of several hundred micrograms per liter, but experimental animal studies at much higher concentrations have...

Thioarsenates in geothermal waters of yellowstone National Park: Determination, preservation, and geochemical importance

USGS Publications Warehouse

Planer-Friedrich, B.; London, J.; McCleskey, R. Blaine; Nordstrom, D. Kirk; Wallschlager, D.

2007-01-01

Mono-, di-, tri-, and tetrathioarsenate, as well as methylated arsenic oxy- and thioanions, were determined besides arsenite and arsenate in geothermal waters of Yellowstone National Park using anion-exchange chromatography inductively coupled plasma mass spectrometry. Retention time match with synthetic standards, measured S:As ratios, and molecular electrospray mass spectra support the identification. Acidification was unsuitable for arsenic species preservation in sulfidic waters, with HCl addition causing loss of total dissolved arsenic, presumably by precipitation of arsenic-sulfides. Flash-freezing is preferred for the preservation of arsenic species for several weeks. After thawing, samples must be analyzed immediately. Thioarsenates occurred over a pH range of 2.1 to 9.3 in the geothermal waters. They clearly predominated under alkaline conditions (up to 83% of total arsenic), but monothioarsenate also was detected in acidic waters (up to 34%). Kinetic studies along a drainage channel showed the importance of thioarsenates for the fate of arsenic discharged from the sulfidic hot spring. The observed arsenic speciation changes suggest three separate reactions: the transformation of trithioarsenate to arsenite (major initial reaction), the stepwise ligand exchange from tri- via di- and monothioarsenate to arsenate (minor reaction), and the oxidation of arsenite to arsenate, which only becomes quantitatively important after thioarsenates have disappeared. ?? 2007 American Chemical Society.

GEOCHEMICAL MODELING OF ARSENIC SPECIATION AND MOBILIZATION: IMPLICATIONS FOR BIOREMEDIATION

EPA Science Inventory

Geochemical modeling techniques were used to examine the biogeochemical linkages between Fe, S, and As in shallow alluvial aquifers. We modeled: 1) the adsorption and desorption of As on the surface of hydrous ferric oxides (HFO’s) in stream beds under aerobic conditions; 2) red...

KINETICS OF ARSENATE REDUCTION BY DISSOLVED SULFIDE. (R825399)

EPA Science Inventory

Arsenic toxicity and mobility in soil and aquatic environments depends on its
speciation, with reducing environments generally leading to more hazardous
conditions with respect to this element. Aqueous sulfide (H₂S or
HS^-) is a strong reductan...

FIELD EVALUATION OF ARSENIC TRANSPORT: SPECIATION IN SEDIMENT MATERIAL

EPA Science Inventory

Fort Devens was established in 1917 as Camp Devens, a temporary training camp for soldiers from the New England area for WWI. Throughout its history, Fort Devens served as a training and induction center for military personnel, and as a unit mobilization and demobilization site....

Effect of sulfide on As(III) and As(V) sequestration by ferrihydrite.

PubMed

Zhao, Zhixi; Wang, Shaofeng; Jia, Yongfeng

2017-10-01

The sulfide-induced change in arsenic speciation is often coupled to iron geochemical processes, including redox reaction, adsorption/desorption and precipitation/dissolution. Knowledge about how sulfide influenced the coupled geochemistry of iron and arsenic was not explored well up to now. In this work, retention and mobilization of As(III) and As(V) on ferrihydrite in sulfide-rich environment was studied. The initial oxidation states of arsenic and the contact order of sulfide notably influenced arsenic sequestration on ferrihydrite. For As(III) systems, pre-sulfidation of As(III) decreased arsenic sequestration mostly. The arsenic adsorption capacity decreased about 50% in comparison with the system without sulfide addition. For As(V) systems, pre-sulfidation of ferrihydrite decreased 30% sequestration of arsenic on ferrihydrite. Reduction of ferrihydrite by sulfide in As(V) system was higher than that in As(III) system. Geochemical modeling calculations identified formation of thioarsenite in the pre-sulfidation of As(III) system. Formation of arsenic thioanions enhanced As solubility in the pre-sulfidation of As(III) system. The high concentration of sulfide and Fe(II) in pre-sulfidation of ferrihydrite system contributed to saturation of FeS. This supplied new solid phase to immobilize soluble arsenic in aqueous phase. X-ray absorption near edge spectroscopy (XANES) of sulfur K-edge, arsenic K-edge and iron L-edge analysis gave the consistent evidence for the sulfidation reaction of arsenic and ferrihydrite under specific geochemical settings. Copyright © 2017 Elsevier Ltd. All rights reserved.

Arsenic in the human food chain, biotransformation and toxicology--Review focusing on seafood arsenic.

PubMed

Molin, Marianne; Ulven, Stine Marie; Meltzer, Helle Margrete; Alexander, Jan

2015-01-01

Fish and seafood are main contributors of arsenic (As) in the diet. The dominating arsenical is the organoarsenical arsenobetaine (AB), found particularly in finfish. Algae, blue mussels and other filter feeders contain less AB, but more arsenosugars and relatively more inorganic arsenic (iAs), whereas fatty fish contain more arsenolipids. Other compounds present in smaller amounts in seafood include trimethylarsine oxide (TMAO), trimethylarsoniopropionate (TMAP), dimethylarsenate (DMA), methylarsenate (MA) and sulfur-containing arsenicals. The toxic and carcinogenic arsenical iAs is biotransformed in humans and excreted in urine as the carcinogens dimethylarsinate (DMA) and methylarsonate (MA), producing reactive intermediates in the process. Less is known about the biotransformation of organoarsenicals, but new insight indicates that bioconversion of arsenosugars and arsenolipids in seafood results in urinary excretion of DMA, possibly also producing reactive trivalent arsenic intermediates. Recent findings also indicate that the pre-systematic metabolism by colon microbiota play an important role for human metabolism of arsenicals. Processing of seafood may also result in transformation of arsenicals. Copyright © 2015 Elsevier GmbH. All rights reserved.

Estimating Inorganic Arsenic Exposure from U.S. Rice and Total Water Intakes

PubMed Central

Mantha, Madhavi; Yeary, Edward; Trent, John; Creed, Patricia A.; Kubachka, Kevin; Hanley, Traci; Shockey, Nohora; Heitkemper, Douglas; Caruso, Joseph; Xue, Jianping; Rice, Glenn; Wymer, Larry

2017-01-01

Background: Among nonoccupationally exposed U.S. residents, drinking water and diet are considered primary exposure pathways for inorganic arsenic (iAs). In drinking water, iAs is the primary form of arsenic (As), while dietary As speciation techniques are used to differentiate iAs from less toxic arsenicals in food matrices. Objectives: Our goal was to estimate the distribution of iAs exposure rates from drinking water intakes and rice consumption in the U.S. population and ethnic- and age-based subpopulations. Methods: The distribution of iAs in drinking water was estimated by population, weighting the iAs concentrations for each drinking water utility in the Second Six-Year Review data set. To estimate the distribution of iAs concentrations in rice ingested by U.S. consumers, 54 grain-specific, production-weighted composites of rice obtained from U.S. mills were extracted and speciated using both a quantitative dilute nitric acid extraction and speciation (DNAS) and an in vitro gastrointestinal assay to provide an upper bound and bioaccessible estimates, respectively. Daily drinking water intake and rice consumption rate distributions were developed using data from the What We Eat in America (WWEIA) study. Results: Using these data sets, the Stochastic Human Exposure and Dose Simulation (SHEDS) model estimated mean iAs exposures from drinking water and rice were 4.2μg/day and 1.4μg/day, respectively, for the entire U.S. population. The Tribal, Asian, and Pacific population exhibited the highest mean daily exposure of iAs from cooked rice (2.8μg/day); the mean exposure rate for children between ages 1 and 2 years in this population is 0.104μg/kg body weight (BW)/day. Conclusions: An average consumer drinking 1.5 L of water daily that contains between 2 and 3 ng iAs/mL is exposed to approximately the same amount of iAs as a mean Tribal, Asian, and Pacific consumer is exposed to from rice. https://doi.org/10.1289/EHP418 PMID:28572075

Linkage Analysis of Urine Arsenic Species Patterns in the Strong Heart Family Study

PubMed Central

Gribble, Matthew O.; Voruganti, Venkata Saroja; Cole, Shelley A.; Haack, Karin; Balakrishnan, Poojitha; Laston, Sandra L.; Tellez-Plaza, Maria; Francesconi, Kevin A.; Goessler, Walter; Umans, Jason G.; Thomas, Duncan C.; Gilliland, Frank; North, Kari E.; Franceschini, Nora; Navas-Acien, Ana

2015-01-01

Arsenic toxicokinetics are important for disease risks in exposed populations, but genetic determinants are not fully understood. We examined urine arsenic species patterns measured by HPLC-ICPMS among 2189 Strong Heart Study participants 18 years of age and older with data on ∼400 genome-wide microsatellite markers spaced ∼10 cM and arsenic speciation (683 participants from Arizona, 684 from Oklahoma, and 822 from North and South Dakota). We logit-transformed % arsenic species (% inorganic arsenic, %MMA, and %DMA) and also conducted principal component analyses of the logit % arsenic species. We used inverse-normalized residuals from multivariable-adjusted polygenic heritability analysis for multipoint variance components linkage analysis. We also examined the contribution of polymorphisms in the arsenic metabolism gene AS3MT via conditional linkage analysis. We localized a quantitative trait locus (QTL) on chromosome 10 (LOD 4.12 for %MMA, 4.65 for %DMA, and 4.84 for the first principal component of logit % arsenic species). This peak was partially but not fully explained by measured AS3MT variants. We also localized a QTL for the second principal component of logit % arsenic species on chromosome 5 (LOD 4.21) that was not evident from considering % arsenic species individually. Some other loci were suggestive or significant for 1 geographical area but not overall across all areas, indicating possible locus heterogeneity. This genome-wide linkage scan suggests genetic determinants of arsenic toxicokinetics to be identified by future fine-mapping, and illustrates the utility of principal component analysis as a novel approach that considers % arsenic species jointly. PMID:26209557

Blood Pressure Changes in Relation to Arsenic Exposure in a U.S. Pregnancy Cohort

PubMed Central

Farzan, Shohreh F.; Chen, Yu; Wu, Fen; Jiang, Jieying; Liu, Mengling; Baker, Emily; Korrick, Susan A.

2015-01-01

Background Inorganic arsenic exposure has been related to the risk of increased blood pressure based largely on cross-sectional studies conducted in highly exposed populations. Pregnancy is a period of particular vulnerability to environmental insults. However, little is known about the cardiovascular impacts of arsenic exposure during pregnancy. Objectives We evaluated the association between prenatal arsenic exposure and maternal blood pressure over the course of pregnancy in a U.S. population. Methods The New Hampshire Birth Cohort Study is an ongoing prospective cohort study in which > 10% of participant household wells exceed the arsenic maximum contaminant level of 10 μg/L established by the U.S. EPA. Total urinary arsenic measured at 24–28 weeks gestation was measured and used as a biomarker of exposure during pregnancy in 514 pregnant women, 18–45 years of age, who used a private well in their household. Outcomes were repeated blood pressure measurements (systolic, diastolic, and pulse pressure) recorded during pregnancy. Results Using linear mixed effects models, we estimated that, on average, each 5-μg/L increase in urinary arsenic was associated with a 0.15-mmHg (95% CI: 0.02, 0.29; p = 0.022) increase in systolic blood pressure per month and a 0.14-mmHg (95% CI: 0.02, 0.25; p = 0.021) increase in pulse pressure per month over the course of pregnancy. Conclusions In our U.S. cohort of pregnant women, arsenic exposure was associated with greater increases in blood pressure over the course of pregnancy. These findings may have important implications because even modest increases in blood pressure impact cardiovascular disease risk. Citation Farzan SF, Chen Y, Wu F, Jiang J, Liu M, Baker E, Korrick SA, Karagas MR. 2015. Blood pressure changes in relation to arsenic exposure in a U.S. pregnancy cohort. Environ Health Perspect 123:999–1006; http://dx.doi.org/10.1289/ehp.1408472 PMID:25793356

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fu, Songbo; Wu, Jie; Li, Yuanyuan

To investigate the differences in urinary arsenic metabolism patterns of individuals exposed to a high concentration of inorganic arsenic (iAs) in drinking water, an epidemiological investigation was conducted with 155 individuals living in a village where the arsenic concentration in the drinking water was 969 μg/L. Blood and urine samples were collected from 66 individuals including 51 cases with skin lesions and 15 controls without skin lesions. The results showed that monomethylated arsenic (MMA), the percentage of MMA (%MMA) and the ratio of MMA to iAs (MMA/iAs) were significantly increased in patients with skin lesions as compared to controls, whilemore » dimethylated arsenic (DMA), the percentage of DMA (%DMA) and the ratio of DMA to MMA (DMA/MMA) were significantly reduced. The percent DMA of individuals with the Ala/Asp genotype of glutathione S-transferase omega 1 (GSTO1) was significantly lower than those with Ala/Ala. The percent MMA of individuals with the A2B/A2B genotype of arsenic (+ 3 oxidation state) methyltransferase (AS3MT) was significantly lower than those with AB/A2B. The iAs and total arsenic (tAs) content in the urine of a Tibetan population were significantly higher than that of Han and Hui ethnicities, whereas MMA/iAs was significantly lower than that of Han and Hui ethnicities. Our results showed that when exposed to the same arsenic environment, different individuals exhibited different urinary arsenic metabolism patterns. Gender and ethnicity affect these differences and above polymorphisms may be effectors too. - Highlights: • We first survey a village with high iAs content in the drinking water (969 μg/L). • 90 villagers suffered typical skin lesions with a morbidity rate of 58%. • Cases exhibited higher %MMA and MMA/iAs, and lower %DMA and DMA/MMA than controls. • Gender and ethnicity affect the differences of iAs methylation metabolism levels. • GSTO1 and AS3MT gene polymorphisms may be factors too.« less

Arsenic exposure levels in relation to different working departments in a copper mining and smelting plant

NASA Astrophysics Data System (ADS)

Sun, Qingshan; Song, Yingli; Liu, Shengnan; Wang, Fei; Zhang, Lin; Xi, Shuhua; Sun, Guifan

2015-10-01

The investigation was carried out to evaluate arsenic exposure and the urine metabolite profiles of workers with different working departments, including administration (Group1), copper ore mining (Group2), copper ore grinding (Group3), electrolytic procession (Group4) and copper smelting (Group5) in a Copper mining and processing plant in China. Information about characteristics of each subject was obtained by questionnaire and inorganic arsenic (iAs), monomethylarsonic acid (MMA), dimethylarsinic acid (DMA) in urine were determined. The highest urinary levels of iAs, MMA and DMA all were found in the Group 5. Group 4 workers had a higher iAs% and a lower PMI compared to Group 3. The urinary total As (TAs) levels of 54.7% subjects exceeded 50 μg/g Cr, and the highest percentage (93.3%) was found in Group 5, smelters. The results of the present study indicate that workers in copper production plant indeed exposed to As, especially for smelters and workers of electrolytic process.

Speciation, Characterization, And Mobility Of As, Se and Hg In Flue Gas Desulphurization Residues

EPA Science Inventory

Flue gas from coal combustion contains significant amounts of volatile toxic trace elements such as arsenic (As), selenium (Se) and mercury (Hg). The capture of these elements in the flue gas desulphurization (FGD) scrubber unit has resulted in generation of a metal-laden residue...

Speciation, Characterization, And Mobility Of As, Se, and Hg In Flue Gas Desulphurization Residues

EPA Science Inventory

Flue gas from coal combustion contains significant amounts of volatile elements, such as arsenic (As), selenium (Se) and mercury (Hg), which could lead to serious environmental health risks. The capture of these toxic elements in the scrubber with a flue gas desulphurization (FGD...

SPECIATION OF ARSENIC ANIMAL FEED ADDITIVES BY MICROBORE HIGH-PERFORMANCE LIQUID CHROMATOGRAPHY WITH INDUCTIVELY COUPLED PLASMA MASS SPECTROMETRY

EPA Science Inventory

Phenylarsonic compounds have been used as poultry and swine feed additives for the purpose of growth promotion and disease prevention. Owing to the lack of suitable analytical methods, however, knowledge of their metabolism, environmental fate and impact remains incomplete. In or...

ASSESSING AS, HG AND SE SPECIATION AND TRANSPORT IN FLUE GAS DESULPHURIZATION MATERIAL AND DRYWALL

EPA Science Inventory

The risk associated with the reuse of flue gas desulphurization (FGD) material in drywall manufacture is largely determined by the distribution or mineralogical fractionation of mercury(Hg), arsenic (As) and selenium (Se). During coal combustion, FGD material is enriched in volat...

GREENHOUSE STUDY ON ARSENIC SPECIATION AND BIOAVAILABILITY IN TWO PESTICIDE-CONTAMINATED SOILS OF FLORIDA: PRELIMINARY RESULTS. (R830842)

EPA Science Inventory

The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

Arsenic mobilization and immobilization in paddy soils

NASA Astrophysics Data System (ADS)

Kappler, A.; Hohmann, C.; Zhu, Y. G.; Morin, G.

2010-05-01

Arsenic is oftentimes of geogenic origin and in many cases bound to iron(III) minerals. Iron(III)-reducing bacteria can harvest energy by coupling the oxidation of organic or inorganic electron donors to the reduction of Fe(III). This process leads either to dissolution of Fe(III)-containing minerals and thus to a release of the arsenic into the environment or to secondary Fe-mineral formation and immobilisation of arsenic. Additionally, aerobic and anaerobic iron(II)-oxidizing bacteria have the potential to co-precipitate or sorb arsenic during iron(II) oxidation at neutral pH that is usually followed by iron(III) mineral precipitation. We are currently investigating arsenic immobilization by Fe(III)-reducing bacteria and arsenic co-precipitation and immobilization by anaerobic iron(II)-oxidizing bacteria in batch, microcosm and rice pot experiments. Co-precipitation batch experiments with pure cultures of nitrate-dependent Fe(II)-oxidizing bacteria are used to quantify the amount of arsenic that can be immobilized during microbial iron mineral precipitation, to identify the minerals formed and to analyze the arsenic binding environment in the precipitates. Microcosm and rice pot experiments are set-up with arsenic-contaminated rice paddy soil. The microorganisms (either the native microbial population or the soil amended with the nitrate-dependent iron(II)-oxidizing Acidovorax sp. strain BoFeN1) are stimulated either with iron(II), nitrate, or oxygen. Dissolved and solid-phase arsenic and iron are quantified. Iron and arsenic speciation and redox state in batch and microcosm experiments are determined by LC-ICP-MS and synchrotron-based methods (EXAFS, XANES).

INDUCTION OF URINARY BLADDER PATHOLOGY IN MALE AND FEMALE C3H MICE EXPOSED TO SODIUM ARSENITE FROM GESTATION THROUGH YOUNG ADULTHOOD

EPA Science Inventory

Epidemiology studies suggest that chronic exposure to inorganic arsenic is associated with cancer of the skin, urinary bladder and lung as well as the kidney and liver. Recently, an in utero animal model was developed to characterize the carcinogenic properties of inorganic arsen...

Speciation and Attenuation of Arsenic and Selenium at Coal Combustion By-Product Management Facilities

DOE Office of Scientific and Technical Information (OSTI.GOV)

K. Ladwig; B. Hensel; D. Wallschlager

2005-10-18

Following completion of contracting activities, sites were identified for the field leachate characterization study. Sampling and Analyses Plans (SAPs) and Site Access Agreements (SAAs) were developed for each site. A total of ten sites were sampled during this reporting period. Among the trace constituents, boron, silicon, and strontium were present in highest concentrations, with median values above 1 mg/L (1,000 {micro}g/L). Work on the first of three sites for the detailed arsenic and selenium adsorption studies began in 2002, prior to completion of the final DOE award. Kd values ranged from 100 to 12,000 L/kg for arsenic (V), 15 tomore » 160 L.kg for As(III), and 5 to 25 L/kg for Se(VI).« less

Biomonitoring of urinary metals in a population living in the vicinity of industrial sources: a comparison with the general population of Andalusia, Spain.

PubMed

Aguilera, Inmaculada; Daponte, Antonio; Gil, Fernando; Hernández, Antonio F; Godoy, Patricia; Pla, Antonio; Ramos, Juan Luis

2008-12-15

The Ria of Huelva (south-west Spain) is one of the most polluted fluvial-estuarine systems in the world. Industrial activity delivers huge amounts of pollutants to the local environment, particularly heavy metals and arsenic. Here we aimed to determine urinary levels of As, Cd, Cr, Cu and Ni in a representative sample (n=857) of adults living in the Ria of Huelva. Levels were compared to those from a representative sample of 861 adults of the general urban population of Andalusia (southern Spain) and multiple regression models were developed to identify individual factors associated with urinary levels of these elements. Arsenic levels were significantly higher in the Ria of Huelva as compared to other Andalusian cities, whereas Cd and Ni levels were significantly lower. Despite these differences, levels in both groups were similar to the reference values reported in previous studies for general population. Age, gender, diet and lifestyle were the major factors contributing to the interindividual variation in urinary metals. In conclusion, despite living in a highly polluted area, the population of the Ria of Huelva failed to show higher urinary levels of the studied metals as compared to a reference urban population of the same region.

Preconcentration determination of arsenic species by sorption of As(V) on Amberlite IRA-410 coupled with fluorescence quenching of L-cysteine capped CdS nanoparticles.

PubMed

Hosseini, Mohammad Saeid; Nazemi, Sahar

2013-10-07

A simple and accurate method for arsenic speciation analysis in natural and drinking water samples is described in which preconcentration of arsenic as As(V) was coupled with spectrofluorometric determination. The extracted As(V) species with a column containing Amberlite IRA-410 were subjected to L-cysteine capped CdS quantum dots (QDs) and the fluorescence quenching of the QDs due to reduction of As(V) by L-cysteine was considered as a signal relevant to As(V) concentration. The As(III) species were also determined after oxidation of As(III) ions to As(V) with H2O2 and measurement of the total arsenic content. In treatment with 400 mL portions of water samples containing 30 μg L(-1) As(V), the relative standard deviation was 2.8%. The detection limit of arsenic was also found to be 0.75 μg L(-1) (1 × 10(-8) M). The reliability of proposed method was confirmed using certified reference materials. The trace amounts of arsenic species were then determined in different water samples, satisfactorily.

Simultaneous determination of arsenic and mercury species in rice by ion-pairing reversed phase chromatography with inductively coupled plasma mass spectrometry.

PubMed

Fang, Yong; Pan, Yushi; Li, Peng; Xue, Mei; Pei, Fei; Yang, Wenjian; Ma, Ning; Hu, Qiuhui

2016-12-15

An analytical method using reversed phase chromatography-inductively coupled plasma mass spectrometry for arsenic and mercury speciation analysis was described. The effect of ion-pairing reagent on simultaneous separation of four arsenic (arsenite, arsenate, monomethlyarsonate and dimethylarsinate) and three mercury species (inorganic mercury (Hg(II)), methylmecury and ethylmercury) was investigated. Parameters including concentrations and pH of the mobile phase were optimized. The separation and re-equilibration time was attained within 20min. Meanwhile, a sequential extraction method for arsenic and mercury in rice was tested. Subsequently, 1% HNO3 microwave-assisted extraction was chosen. Calibration curves based on peak area measurements were linear with correlation coefficient greater than 0.9958 for each species in the range studied. The detection limits of the species were in the range of 0.84-2.41μg/L for arsenic and 0.01-0.04μg/L for mercury, respectively. The proposed method was then successfully applied for the simultaneous determination of arsenic and mercury species in rice flour standard material and two kinds of rice from local markets. Copyright © 2016 Elsevier Ltd. All rights reserved.

Development and application of a robust speciation method for determination of six arsenic compounds present in human urine.

PubMed Central

Milstein, Lisa S; Essader, Amal; Pellizzari, Edo D; Fernando, Reshan A; Raymer, James H; Levine, Keith E; Akinbo, Olujide

2003-01-01

Six arsenic species [arsenate, arsenite, arsenocholine, arsenobetaine, monomethyl arsonic acid, and dimethyl arsinic acid] present in human urine were determined using ion-exchange chromatography combined with inductively coupled plasma mass spectrometry (IC-ICP-MS). Baseline separation was achieved for all six species as well as for the internal standard (potassium hexahydroxy antimonate V) in a single chromatographic run of less than 30 min, using an ammonium carbonate buffer gradient (between 10 and 50 mM) at ambient temperature, in conjunction with cation- and anion-exchange columns in series. The performance of the method was evaluated with respect to linearity, precision, accuracy, and detection limits. This method was applied to determine the concentration of these six arsenic species in human urine samples (n = 251) collected from a population-based exposure assessment survey. Method precision was demonstrated by the analysis of duplicate samples that were prepared over a 2-year analysis period. Total arsenic was also determined for the urine samples using flow injection analysis coupled to ICP-MS. The summed concentration of the arsenic species was compared with the measured arsenic total to demonstrate mass balance. PMID:12611657

Unraveling Health Risk and Speciation of Arsenic from Groundwater in Rural Areas of Punjab, Pakistan.

PubMed

Shakoor, Muhammad Bilal; Niazi, Nabeel Khan; Bibi, Irshad; Rahman, Mohammad Mahmudur; Naidu, Ravi; Dong, Zhaomin; Shahid, Muhammad; Arshad, Muhammad

2015-10-05

This study determined the total and speciated arsenic (As) concentrations and other health-related water quality parameters for unraveling the health risk of As from drinking water to humans. Groundwater samples (n = 62) were collected from three previously unexplored rural areas (Chichawatni, Vehari, Rahim Yar Khan) of Punjab in Pakistan. The mean and median As concentrations in groundwater were 37.9 and 12.7 µg·L(-1) (range = 1.5-201 µg·L(-1)). Fifty three percent groundwater samples showed higher As value than WHO safe limit of 10 µg·L(-1). Speciation of As in groundwater samples (n = 13) showed the presence of inorganic As only; arsenite (As(III)) constituted 13%-67% of total As and arsenate (As(V)) ranged from 33% to 100%. For As health risk assessment, the hazard quotient and cancer risk values were 11-18 and 46-600 times higher than the recommended values of US-EPA (i.e., 1.00 and 10(-6), respectively). In addition to As, various water quality parameters (e.g., electrical conductivity, Na, Ca, Cl(-), NO₃(-), SO₄(2-), Fe, Mn, Pb) also enhanced the health risk. The results show that consumption of As-contaminated groundwater poses an emerging health threat to the communities in the study area, and hence needs urgent remedial and management measures.

Water management impacts on arsenic speciation and iron-reducing bacteria in contrasting rice-rhizosphere compartments.

PubMed

Somenahally, Anil C; Hollister, Emily B; Yan, Wengui; Gentry, Terry J; Loeppert, Richard H

2011-10-01

Rice cultivated on arsenic (As) contaminated-soils will accumulate variable grain-As concentrations, as impacted by varietal differences, soil variables, and crop management. A field-scale experiment was conducted to study the impact of intermittent and continuous flooding on As speciation and microbial populations in rice rhizosphere compartments of soils that were either historically amended with As pesticide or unamended with As. Rhizosphere-soil, root-plaque, pore-water and grain As were quantified and speciated, and microbial populations in rhizosphere soil and root-plaque were characterized. Total-As concentrations in rhizosphere and grain were significantly lower in intermittently flooded compared to the continuously flooded plots (86% lower in pore-water, 55% lower in root-plaque and 41% lower in grain samples). iAs(V), iAs(III), and DMAs(V) were the predominant As species detected in rhizosphere-soil and root-plaque, pore-water and grain samples, respectively. Relative proportions of Archaea and iron-reducing bacteria (FeRB) were higher in rhizosphere soil compared to root-plaque. In rhizosphere soil, the relative abundance of FeRB was lower in intermittently flooded compared to continuously flooded plots, but there were no differences between root-plaque samples. This study has demonstrated that reductions in dissolved As concentrations in the rhizosphere and subsequent decreases in grain-As concentration can be attained through water management.

Unraveling Health Risk and Speciation of Arsenic from Groundwater in Rural Areas of Punjab, Pakistan

PubMed Central

Shakoor, Muhammad Bilal; Niazi, Nabeel Khan; Bibi, Irshad; Rahman, Mohammad Mahmudur; Naidu, Ravi; Dong, Zhaomin; Shahid, Muhammad; Arshad, Muhammad

2015-01-01

This study determined the total and speciated arsenic (As) concentrations and other health-related water quality parameters for unraveling the health risk of As from drinking water to humans. Groundwater samples (n = 62) were collected from three previously unexplored rural areas (Chichawatni, Vehari, Rahim Yar Khan) of Punjab in Pakistan. The mean and median As concentrations in groundwater were 37.9 and 12.7 µg·L−1 (range = 1.5–201 µg·L−1). Fifty three percent groundwater samples showed higher As value than WHO safe limit of 10 µg·L−1. Speciation of As in groundwater samples (n = 13) showed the presence of inorganic As only; arsenite (As(III)) constituted 13%–67% of total As and arsenate (As(V)) ranged from 33% to 100%. For As health risk assessment, the hazard quotient and cancer risk values were 11–18 and 46–600 times higher than the recommended values of US-EPA (i.e., 1.00 and 10−6, respectively). In addition to As, various water quality parameters (e.g., electrical conductivity, Na, Ca, Cl−, NO3−, SO42−, Fe, Mn, Pb) also enhanced the health risk. The results show that consumption of As-contaminated groundwater poses an emerging health threat to the communities in the study area, and hence needs urgent remedial and management measures. PMID:26445051

Arsenic bioaccessibility and speciation in the soils amended with organoarsenicals and drinking-water treatment residuals based on a long-term greenhouse study

NASA Astrophysics Data System (ADS)

Nagar, Rachana; Sarkar, Dibyendu; Makris, Konstantinos C.; Datta, Rupali

2014-10-01

SummaryAlthough organoarsenical pesticides are no longer applied to agricultural fields in the US, their widespread use until recently, toxicity, and potential transformation to inorganic arsenic has raised serious concern. Drinking-water treatment residuals (WTRs) have been proposed as a low-cost amendment for remediation of organoarsenical pesticide contaminated soils. A long-term greenhouse study was initiated to evaluate the effect WTR application on bioaccessibility, geochemical partitioning, and speciation of the Dimethylarsinic acid (DMA). Two soils (Immokalee and Orelia series) were spiked with DMA (1500 mg As kg-1) and amended with an Al- and Fe-based WTR at two rates (5% and 10% by wt.). Soil sampling was done immediately after spiking (time zero) and after 0.25, 0.5, 1, and 3 (time final) years of equilibration and subjected to bioaccessibility test and sequential extraction. Results showed that compared to the unamended (no WTR) control, As bioaccessibility in the WTR-amended soils significantly (p < 0.001) decreased by 40-70% in 3 years. The Fe-WTR was more effective than Al-WTR in decreasing soil As bioaccessibility. The in vitro and water-extracted samples were subjected to As speciation at time zero and time final. Results showed transformation of DMA into inorganic As, irrespective of WTR amendments. The Orelia soil showed significantly (p < 0.001) higher transformation than the Immokalee soil.

A simple method using on-line continuous leaching and ion exchange chromatography coupled to inductively coupled plasma mass spectrometry for the speciation analysis of bio-accessible arsenic in rice.

PubMed

Horner, Nolan S; Beauchemin, Diane

2012-03-02

A simple method for the speciation analysis of bio-accessible arsenic (As) in rice was developed using a continuous on-line leaching method to release the bio-accessible fraction. The continuous on-line leaching method has several advantages over commonly used batch methods including quicker and easier sample preparation, reduced risk of contamination and access to real time leaching data. The bio-accessibility of As in the samples was monitored using inductively coupled plasma mass spectrometry (ICP-MS). Results from a certified reference material as well as cooked and uncooked white rice showed that the majority of As was leached by saliva. Results obtained using the continuous on-line leaching method were comparable to those obtained using a batch method. Speciation analysis of the saliva leachate was performed using ion exchange chromatography coupled to ICP-MS. The four most toxic forms of As (As(III), monomethylarsonic acid (MMA), dimethylarsinic acid (DMA) and As(V)) were clearly separated within 5 min in a single chromatographic run. Over 92% of bio-accessible As in the certified reference material and uncooked white rice sample was in the form of DMA and As(V), whereas it was present as DMA and As(III) in the cooked white rice. Copyright © 2011 Elsevier B.V. All rights reserved.

Solid surface photochemistry of montmorillonite: mechanisms for the arsenite oxidation under UV-A irradiation.

PubMed

Yuan, Yanan; Wang, Yajie; Ding, Wei; Li, Jinjun; Wu, Feng

2016-01-01

Transformation of inorganic arsenic species has drawn great concern in recent decades because of worldwide and speciation-dependent pollution and the hazards that they pose to the environment and to human health. As(III) photooxidation in aquatic systems has received much attention, but little is known about photochemical transformation of arsenic species on top soil. As(III) photooxidation on natural montmorillonite under UV-A radiation was investigated by using a moisture- and temperature-controlled photochemical chamber with two black-light lamps. Initial As(III) concentration, pH, layer thickness, humic acid (HA) concentration, the presence of additional iron ions, and the contribution of reactive oxygen species (ROS) were examined. The results show that pH values of the clay layers greatly influenced As(III) photooxidation on montmorillonite. As(III) photooxidation followed the Langmuir-Hinshelwood model. HA and additional iron ions greatly promoted photooxidation, but excess Fe(II) competed with As(III) for oxidation by ROS. Scavenging experiments revealed that natural montmorillonite induced the conversion of As(III) to As(V) by generating ROS (mainly HO(•) and HO2(•)/O2(•-)) and that HO(•) radical was the predominant oxidant in this system. Our work demonstrates that photooxidation on the surface of natural clay minerals in top soil can be important to As(III) transformation. This allows understanding and predicting the speciation and behavior of arsenic on the soil surface.

Humans seem to produce arsenobetaine and dimethylarsinate after a bolus dose of seafood.

PubMed

Molin, M; Ulven, S M; Dahl, L; Telle-Hansen, V H; Holck, M; Skjegstad, G; Ledsaak, O; Sloth, J J; Goessler, W; Oshaug, A; Alexander, J; Fliegel, D; Ydersbond, T A; Meltzer, H M

2012-01-01

Seafood is the predominant food source of several organoarsenic compounds. Some seafood species, like crustaceans and seaweed, also contain inorganic arsenic (iAs), a well-known toxicant. It is unclear whether human biotransformation of ingested organoarsenicals from seafood result in formation of arsenicals of health concern. The present controlled dietary study examined the urinary excretion of arsenic compounds (total arsenic (tAs), iAs, AB (arsenobetaine), dimethylarsinate (DMA) and methylarsonate (MA)) following ingestion of a single test meal of seafood (cod, 780 μg tAs, farmed salmon, 290 μg tAs or blue mussel, 690 μg tAs or potato (control, 110 μg tAs)) in 38 volunteers. The amount of ingested tAs excreted via the urine within 0-72 h varied significantly among the groups: Cod, 74% (52-92%), salmon 56% (46-82%), blue mussel 49% (37-78%), control 45% (30-60%). The estimated total urinary excretion of AB was higher than the amount of ingested AB in the blue mussel group (112%) and also ingestion of cod seemed to result in more AB, indicating possible endogenous formation of AB from other organoarsenicals. Excretion of iAs was lower than ingested (13-22% of the ingested iAs was excreted in the different groups). Although the ingested amount of iAs+DMA+MA was low for all seafood groups (1.2-4.5% of tAs ingested), the urinary DMA excretion was high in the blue mussel and salmon groups, counting for 25% and 11% of the excreted tAs respectively. In conclusion our data indicate a possible formation of AB as a result of biotransformation of other organic arsenicals. The considerable amount of DMA excreted is probably not only due to methylation of ingested iAs, but due to biotransformation of organoarsenicals making it an inappropriate biomarker of iAs exposure in populations with a high seafood intake. Copyright © 2011 Elsevier Inc. All rights reserved.

Characterization of Arsenic Contamination on Rust from Ton Containers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gary S. Groenewold; Recep Avci; Robert V. Fox

The speciation and spatial distribution of arsenic on rusted steel surfaces affects both measurement and removal approaches. The chemistry of arsenic residing in the rust of ton containers that held the chemical warfare agents bis(2-chloroethyl)sulfide (sulfur mustard) and 2-chlorovinyldichloroarsine (Lewisite) is of particular interest, because while the agents have been decontaminated, residual arsenic could pose a health or environmental risk. The chemistry and distribution of arsenic in rust samples was probed using imaging secondary ion mass spectrometry (SIMS), X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy, and scanning electron microscopy/energy dispersive X-ray spectroscopy (SEM/EDX). Arsenic in the +3 and or +5more » oxidation state is homogeneously distributed at the very top-most layer of the rust samples, and is intimately associated with iron. Sputter depth profiling followed by SIMS and XPS shows As at a depth of several nm, in some cases in a reduced form. The SEM/EDX experiments show that As is present at a depth of several microns, but is inhomogeneously distributed; most locations contained oxidized As at concentrations of a few percent, however several locations showed very high As in a metallic form. These results indicate that the rust material must be removed if the steel containers are to be cleared of arsenic.« less

A need for determination of arsenic species at low levels in cereal-based food and infant cereals. Validation of a method by IC-ICPMS.

PubMed

Llorente-Mirandes, Toni; Calderón, Josep; Centrich, Francesc; Rubio, Roser; López-Sánchez, José Fermín

2014-03-15

The present study arose from the need to determine inorganic arsenic (iAs) at low levels in cereal-based food. Validated methods with a low limit of detection (LOD) are required to analyse these kinds of food. An analytical method for the determination of iAs, methylarsonic acid (MA) and dimethylarsinic acid (DMA) in cereal-based food and infant cereals is reported. The method was optimised and validated to achieve low LODs. Ion chromatography-inductively coupled plasma mass spectrometry (IC-ICPMS) was used for arsenic speciation. The main quality parameters were established. To expand the applicability of the method, different cereal products were analysed: bread, biscuits, breakfast cereals, wheat flour, corn snacks, pasta and infant cereals. The total and inorganic arsenic content of 29 cereal-based food samples ranged between 3.7-35.6 and 3.1-26.0 μg As kg(-1), respectively. The present method could be considered a valuable tool for assessing inorganic arsenic contents in cereal-based foods. Copyright © 2013 Elsevier Ltd. All rights reserved.

HPLC-HG-AFS determination of arsenic species in acute promyelocytic leukemia (APL) plasma and blood cells.

PubMed

Guo, Meihua; Wang, Wenjing; Hai, Xin; Zhou, Jin

2017-10-25

Arsenic trioxide (ATO) has been successfully used in the treatment of acute promyelocytic leukemia (APL). To clarify the arsenic species in APL patients, high performance liquid chromatography-hydride generation-atomic fluorescence spectrometry (HPLC-HG-AFS) and HG-AFS methods were developed and validated to quantify the plasma concentrations of inorganic arsenic (As(III) and As(V)) and methylated metabolites (MMA and DMA), and the total amounts of arsenic in blood cells and plasma. Blood cells and plasma were digested with mixtures of HNO 3 H 2 O 2 and analyzed by HG-AFS. For arsenic speciation, plasma samples were prepared with perchloric acid to precipitate protein. The supernatant was separated on an anion-exchange column within 6min with isocratic elution using 13mM CH 3 COONa, 3mM NaH 2 PO 4 , 4mM KNO 3 and 0.2mM EDTA-2Na. The methods provided linearity range of 0.2-20ng/mL for total arsenic and 2.0-50ng/mL for four arsenic species. The developed methods for total arsenic and arsenic species determination were precise and accurate. The spiked recoveries ranged from 81.2%-108.6% and the coefficients of variation for intra- and inter-batch precision were less than 9.3% and 12.5%, respectively. The developed methods were applied successfully for the assay of total arsenic and arsenic species in 5 APL patients. The HPLC-HG-AFS may be a good alternative for arsenic species determination in APL patients with its simplicity and low-cost in comparison with HPLC-ICP-MS. Copyright © 2017 Elsevier B.V. All rights reserved.

Relation between in Utero Arsenic Exposure and Birth Outcomes in a Cohort of Mothers and Their Newborns from New Hampshire

PubMed Central

Gilbert-Diamond, Diane; Emond, Jennifer A.; Baker, Emily R.; Korrick, Susan A.; Karagas, Margaret R.

2016-01-01

Background: Studies suggest that arsenic exposure influences birth outcomes; however, findings are mixed. Objective: We assessed in utero arsenic exposure in relation to birth outcomes and whether maternal prepregnancy weight and infant sex modified the associations. Methods: Among 706 mother–infant pairs exposed to low levels of arsenic through drinking water and diet, we assessed in utero arsenic exposure using maternal second-trimester urinary arsenic, maternal prepregnancy weight through self-report, and birth outcomes from medical records. Results: Median (interquartile range) of total urinary arsenic [tAs; inorganic arsenic (iAs) + monomethylarsonic acid (MMA) + dimethylarsinic acid (DMA)] was 3.4 μg/L (1.7–6.0). In adjusted linear models, each doubling of tAs was associated with a 0.10-cm decrease (95% CI: –0.19, –0.01) in head circumference. Results were similar for MMA and DMA. Ln(tAs) and ln(DMA) were positively associated with birth length in infant males only; among males, each doubling of tAs was associated with a 0.28-cm increase (95% CI: 0.09, 0.46) in birth length (pinteraction = 0.04). Results were similar for DMA. Additionally, arsenic exposure was inversely related to ponderal index, and associations differed by maternal weight. Each ln(tAs) doubling of tAs was associated with a 0.55-kg/m3 lower (95% CI: –0.82, –0.28, p < 0.001) ponderal index for infants of overweight/obese, but not normal-weight, mothers (pinteraction < 0.01). Finally, there was a significant interaction between maternal weight status, infant sex, and arsenic exposure on birth weight (pinteraction = 0.03). In girls born of overweight/obese mothers, each doubling of tAs was associated with a 62.9-g decrease (95% CI: –111.6, –14.2) in birth weight, though the association was null in the other strata. Conclusions: Low-level arsenic exposure may affect fetal growth, and the associations may be modified by maternal weight status and infant sex. Citation: Gilbert-Diamond D, Emond JA, Baker ER, Korrick SA, Karagas MR. 2016. Relation between in utero arsenic exposure and birth outcomes in a cohort of mothers and their newborns from New Hampshire. Environ Health Perspect 124:1299–1307; http://dx.doi.org/10.1289/ehp.1510065 PMID:26955061

Relation between in Utero Arsenic Exposure and Birth Outcomes in a Cohort of Mothers and Their Newborns from New Hampshire.

PubMed

Gilbert-Diamond, Diane; Emond, Jennifer A; Baker, Emily R; Korrick, Susan A; Karagas, Margaret R

2016-08-01

Studies suggest that arsenic exposure influences birth outcomes; however, findings are mixed. We assessed in utero arsenic exposure in relation to birth outcomes and whether maternal prepregnancy weight and infant sex modified the associations. Among 706 mother-infant pairs exposed to low levels of arsenic through drinking water and diet, we assessed in utero arsenic exposure using maternal second-trimester urinary arsenic, maternal prepregnancy weight through self-report, and birth outcomes from medical records. Median (interquartile range) of total urinary arsenic [tAs; inorganic arsenic (iAs) + monomethylarsonic acid (MMA) + dimethylarsinic acid (DMA)] was 3.4 μg/L (1.7-6.0). In adjusted linear models, each doubling of tAs was associated with a 0.10-cm decrease (95% CI: -0.19, -0.01) in head circumference. Results were similar for MMA and DMA. Ln(tAs) and ln(DMA) were positively associated with birth length in infant males only; among males, each doubling of tAs was associated with a 0.28-cm increase (95% CI: 0.09, 0.46) in birth length (pinteraction = 0.04). Results were similar for DMA. Additionally, arsenic exposure was inversely related to ponderal index, and associations differed by maternal weight. Each ln(tAs) doubling of tAs was associated with a 0.55-kg/m3 lower (95% CI: -0.82, -0.28, p < 0.001) ponderal index for infants of overweight/obese, but not normal-weight, mothers (pinteraction < 0.01). Finally, there was a significant interaction between maternal weight status, infant sex, and arsenic exposure on birth weight (pinteraction = 0.03). In girls born of overweight/obese mothers, each doubling of tAs was associated with a 62.9-g decrease (95% CI: -111.6, -14.2) in birth weight, though the association was null in the other strata. Low-level arsenic exposure may affect fetal growth, and the associations may be modified by maternal weight status and infant sex. Gilbert-Diamond D, Emond JA, Baker ER, Korrick SA, Karagas MR. 2016. Relation between in utero arsenic exposure and birth outcomes in a cohort of mothers and their newborns from New Hampshire. Environ Health Perspect 124:1299-1307; http://dx.doi.org/10.1289/ehp.1510065.

Determination of arsenic species in marine samples by HPLC-ICP-MS.

PubMed

Hirata, Shizuko; Toshimitsu, Hideki; Aihara, Masato

2006-01-01

Arsenic speciation analysis in marine samples was performed using high performance liquid chromatography (HPLC) with ICP-MS detection. The separation of eight arsenic species viz. arsenite (As(III)), monomethylarsonic acid (MMA), dimethylarsinic acid (DMA), arsenate (As(V)), arsenobetaine, trimethylarsine oxide (TMAO), arsenocholine and tetramethylarsonium ion (TeMAs) was achieved on a Shiseido Capcell Pak C18 column by using an isocratic eluent (pH 3.0), in which condition As(III) and MMA were co-eluted. The entire separation was accomplished in 15 min. The detection limits for 8 arsenic species by HPLC/ICP-MS were in the range of 0.02 - 0.10 microg L(-1) based on 3sigma of blank response (n=9). The precision was calculated to be 3.1-7.3% (RSD) for all eight species. The method then successfully applied to several marine samples e.g., oyster, scallop, fish, and shrimps. For the extraction of arsenic species from seafood products, the low power microwave digestion was employed. The extraction efficiency was in the range of 52.9 - 112.3%. Total arsenic concentrations were analyzed by using the microwave acid digestion. The total arsenics in the certified reference materials (DORM-2 and TORT-2) were analyzed and agreed with the certified values. The concentrations of arsenics in marine samples were in the range 6.6 - 35.1 microg g(-1).

Biological monitoring and the influence of genetic polymorphism of As3MT and GSTs on distribution of urinary arsenic species in occupational exposure workers.

PubMed

Janasik, Beata; Reszka, Edyta; Stanislawska, Magdalena; Wieczorek, Edyta; Fendler, Wojciech; Wasowicz, Wojciech

2015-08-01

To examine the differences in urinary arsenic metabolism patterns in men affected by occupational exposure, we performed a study on 149 participants—workers of a copper mill and 52 healthy controls without occupational exposure. To elucidate the role of genetic factors in arsenic (As) metabolism, we studied the associations of six polymorphisms: As3MT Met287Thr (T>C) in exon 9; As3MT A>G in 5'UTR; As3MT C>G in intron 6; As3MT T>G in intron 1; GSTP1 Ile105Val and GSTO2 T>C. Air samples were collected using individual samplers during work shift. Urine samples were analyzed for total arsenic and arsenic chemical forms (As(III); As(V), MMA, DMA, AsB) using HPLC-ICP-MS. A specific polymerase chain reaction was done for the amplification of exons and flanking regions of As3MT and GSTs. The geometric mean arsenic concentrations in the air were 27.6 ± 4.9 µg/m(3). A significant correlation (p < 0.05) was observed between arsenic in air and sum of iAs +MMA and iAs. As3MT (rs3740400) GG homozygotes showed significantly (p < 0.05) higher %iAs (21.8 ± 2.0) in urine than GC+CC heterozygotes (16.0 ± 2.1). A strong association between the gene variants and As species in urine was observed for GSTO2 (rs156697) polymorphism. The findings of the study point out that the concentration of iAs or the sum of iAs + MMA in urine can be a reliable biological indicator of occupational exposure to arsenic. This study demonstrates that As3MT and/or GSTs genotype may influence As metabolism. Nevertheless, further studies investigating genetic polymorphism in occupational conditions are required.

Selenium and arsenic in biology: their chemical forms and biological functions.

PubMed

Shibata, Y; Morita, M; Fuwa, K

1992-01-01

Based on the recent development of analytical methods, sensitive systems for the analysis and speciation of selenium and arsenic have been established. A palladium addition technique was developed for the accurate determination of selenium in biological samples using graphite furnace atomic absorption analysis. For the speciation of the elements, combined methods of HPLC either with ICP-AES or with ICP-MS were found to work well. These systems were applied to the elucidation of the chemical form of the elements in natural samples. Some chemical properties of the selenium-mercury complex in dolphin liver were elucidated: i.e., it was a cationic, water-soluble, low molecular weight compound containing selenium and mercury in a 1:1 molar ratio, and was shown to be different from a known selenium-mercury complex, bis(methylmercuric)selenide. The major selenium compound excreted in human urine was revealed to be other than any of those previously identified (TMSe, selenate, and selenite). TMSe, a suspected major metabolite in urine, was found, if at all, in low levels. The major water-soluble, and lipid-soluble arsenic compounds in a brown seaweed, U. pinnatifida (WAKAME), were rigorously identified, and the results were compared with other data on marine algae and animals. The major organic arsenic compounds (termed "arseno-sugars") in marine algae commonly contain 5-deoxy-5-dimethylarsinyl-ribofuranoside moiety. There are various kinds of arseno-sugar derivatives containing different side-chains attached to the anomeric position of the sugar, and the distribution of each arsenic species seems to be related to algal species. The arseno-sugar (A-XI) is present in every alga so far examined, is metabolized to lipids, and possibly may play some specific role in the algal cells. On the other hand, the major arsenic compound in fish, crustacea and molluscs has been identified as arsenobetaine, which is an arseno-analog of glycinebetaine, a very common osmo-regulator in living organisms. Arsenobetaine is not detected in marine algae while arseno-sugars are not present in marine animals except for some molluscs which contain both compounds in considerable amounts. Arsenobetaine is present in the urine of human beings who have eaten foods derived from marine animals.

Arsenic methylation capacity is associated with breast cancer in northern Mexico

DOE Office of Scientific and Technical Information (OSTI.GOV)

López-Carrillo, Lizbeth; Hernández-Ramírez, Raúl Ulises; Gandolfi, A. Jay

Exposure to environmental contaminants, dietary factors and lifestyles may explain worldwide different breast cancer (BC) incidence. Inorganic arsenic (iAs) in the drinking water is a concern in many regions, such as northern Mexico. Studies in several countries have associated the proportion of urinary monomethylarsenic (%MMA) with increased risks for many As-related diseases, including cancer. To investigate the potential relationships between the risk of BC and the capacity to methylate iAs, a hospital-based case–control study (1016 cases/1028 controls) was performed in northern Mexico. Women were directly interviewed about their reproductive histories. The profile of As metabolites in urine was determined bymore » HPLC-ICP-MS and methylation capacity was assessed by metabolite percentages and indexes. Total urinary As, excluding arsenobetaine (TAs-AsB), ranged from 0.26 to 303.29 μg/L. Most women (86%) had TAs-AsB levels below As biological exposure index (35 μg/L). Women with higher %MMA and/or primary methylation index (PMI) had an increased BC risk (%MMA OR{sub Q5vs.Q1} = 2.63; 95%CI 1.89,3.66; p for trend < 0.001; PMI OR{sub Q5vs.Q1} = 1.90; 95%CI 1.39,2.59, p for trend < 0.001). In contrast, women with higher proportion of urinary dimethylarsenic (%DMA) and/or secondary methylation index (SMI) had a reduced BC risk (%DMA OR{sub Q5vs.Q1} = 0.63; 95%CI 0.45,0.87, p for trend 0.006; SMI OR{sub Q5vsQ1} = 0.42, 95%CI 0.31,0.59, p for trend < 0.001). Neither %iAs nor total methylation index was associated to BC risk. Inter-individual variations in iAs metabolism may play a role in BC carcinogenesis. Women with higher capacity to methylate iAs to MMA and/or a lower capacity to further methylate MMA to DMA were at higher BC risk. - Highlights: • Arsenic methylation capacity is associated to an increased breast cancer (BC) risk. • Women with higher capacity to methylate arsenic to MMA were at higher BC risk. • Women with higher capacity to methylate arsenic to DMA were at lower BC risk. • Associations occurred at urinary As levels near the biological exposure index.« less

Determination of total arsenic using a novel Zn-ferrite binding gel for DGT techniques: Application to the redox speciation of arsenic in river sediments.

PubMed

Gorny, Josselin; Lesven, Ludovic; Billon, Gabriel; Dumoulin, David; Noiriel, Catherine; Pirovano, Caroline; Madé, Benoît

2015-11-01

A new laboratory-made Zn-ferrite (ZnFe2O4) binding gel is fully tested using Diffusive Gradient in Thin films (DGT) probes to measure total As [including inorganic As(III) and As(V), as well as MonoMethyl Arsenic Acid (MMAA(V)) and DiMethyl Arsenic Acid (DMAA(V))] in river waters and sediment pore waters. The synthesis of the binding gel is easy, cheap and its insertion into the acrylamide gel is not problematic. An important series of triplicate tests have been carried out to validate the use of the Zn-ferrite binding gel in routine for several environmental matrixes studies, in order to test: (i) the effect of pH on the accumulation efficiency of inorganic As species; (ii) the reproducibility of the results; (iii) the accumulation efficiency of As species; (iv) the effects of the ionic strength and possible competitive anions; and (v) the uptake and the elution efficiency of As species after accumulation in the binding gel. All experimental conditions have been reproduced using two other existing binding gels for comparison: ferrihydrite and Metsorb® HMRP 50. We clearly demonstrate that the Zn-ferrite binding gel is at least as good as the two other binding gels, especially for pH values higher than 8. In addition, by taking into consideration the diffusion rates of As(III) and As(V) in the gel, combining the 3-mercaptopropyl [accumulating only As(III)] with the Zn-ferrite binding gels allows for performing speciation studies. An environmental study along the Marque River finally illustrates the ability of the new binding gel to be used for field studies. Copyright © 2015. Published by Elsevier B.V.

Microscale speciation of arsenic and iron in ferric-based sorbents subjected to simulated landfill conditions

PubMed Central

Root, Robert A.; Fathordoobadi, Sahar; Alday, Fernando; Ela, Wendell; Chorover, Jon

2013-01-01

During treatment for potable use, water utilities generate arsenic-bearing ferric wastes that are subsequently dispatched to landfills. The biogeochemical weathering of these residuals in mature landfills affects the potential mobilization of sorbed arsenic species via desorption from solids subjected to phase transformations driven by abundant organic matter and bacterial activity. Such processes are not simulated with the Toxicity Characteristic Leaching Procedure (TCLP) currently used to characterize hazard. To examine the effect of sulfate on As retention in landfill leachate, columns of As(V) loaded amorphous ferric hydroxide were reacted biotically at two leachate sulfate concentrations (0.064 mM and 2.1 mM). After 300 d, ferric sorbents were reductively dissolved. Arsenic released to porewaters was partially co-precipitated in mixed-valent secondary iron phases whose speciation was dependent on sulfate concentration. As and Fe XAS showed that, in the low sulfate column, 75–81% of As(V) was reduced to As(III), and 53–68% of the Fe(III) sorbent was transformed, dominantly to siderite and green rust. In the high sulfate column, Fe(III) solids were reduced principally to FeS(am), whereas As(V) was reduced to a polymeric sulfide with local atomic structure of realgar. Multi-energy micro-X-ray fluorescence (ME-μXRF) imaging at Fe and As K-edges showed that As formed surface complexes with ferrihydrite > siderite > green rust in the low sulfate column; while discrete realgar-like phases formed in the high sulfate systems. Results indicate that landfill sulfur chemistry exerts strong control over the potential mobilization of As from ferric sorbent residuals by controlling secondary As and Fe sulfide co-precipitate formation. PMID:24102155

Use status and metabolism of realgar in Chinese patent medicine.

PubMed

Li, Yongfang; Wang, Da; Xu, Yuanyuan; Liu, Boying; Zheng, Yi; Yang, Boyi; Fan, Shujun; Zhi, Xueyuan; Zheng, Quanmei; Sun, Guifan

2015-04-08

Realgar is widely used in combination with other herbs as Chinese patent medicine to treat a wide range of diseases in China. It is also a well known arsenical toxicant. Chronic arsenic poisoning events caused by long-term usage of realgar-containing medicines have been reported in literatures. Given to the paradoxical role of realgar, comprehensive outline of its usage status in Chinese patent medicine might provide basal data for evaluating its toxicology risks in populations. Unfortunately, the relevant information is limited. Also, a metabolic process after intake of realgar-containing medicine in humans is poorly understood. The Traditional Chinese Patent Medicine Prescription Database was reviewed to get the information on the usage status of realgar. Realgar powder was dissolved in different pH-value solutions (1, 3, 5, 7, 9 and 11) to determine the soluble arsenic concentrations from realgar. Ten volunteers aged 24-26 years old were recruited to take four pills of Niu Huang Jie Du Pian (NHJDP), a very common Chinese patent medicine with realgar, to analyze the arsenic metabolism after exposure to realgar-containing medicine. The four pills were taken according to the medical instruction. Concentrations of soluble arsenic from realgar and urinary arsenic metabolites in humans were determined by hydride generation atomic absorption spectrometry. A total of 191 (2.25%) realgar-containing traditional Chinese patent medicines were obtained from the database, and almost 86.91% of them were for oral application. 73 (38.22%) medicines were found to be available for children. The mass fraction of arsenic in realgar-containing medicine ranged from 0.11% to 27.52%. According to medical instructions, the amount of average daily arsenic intake ranged from 0.47 to 2895.53mg. Nearly 86% medicines with daily intake of arsenic >10mg. Only inorganic arsenic (iAs) was detected from realgar in dissolution experiment and the levels of soluble iAs increased with pH values. After intake NHJDP, arsenic excretion in urine significantly increased, with a maximum excretion of iAs and monomethylarsonic acid at 6h post-ingestion and a peak excretion of dimethylarsinic acid at 9h post-ingestion. Arsenic methylation capacity was decreased after intake NHJDP. Females carried a more efficient arsenic methylation process than males. Realgar is widely used in traditional Chinese medicine. The arsenic solubility from realgar may be enhanced under alkaline conditions. The levels of urinary arsenic metabolites significantly increased while the arsenic methylation capacity significantly decreased after intaking realgar-containing medicine, which may suggest that a potential health hazard exists if people use arsenical medicines for long-term. Copyright © 2015. Published by Elsevier Ireland Ltd.

High-Iron Biosolids Compost-Induced Changes in Lead and Arsenic Speciation and Bioaccessibility in Co-contaminated Soils

EPA Science Inventory

The safety of urban farming has been questioned due to the potential for contamination in urban soils. A laboratory incubation, a field trial, and a second laboratory incubation were conducted to test the ability of high-Fe biosolids–based composts to reduce the bioaccessibil...

The Impact of Hazardous Chemicals on Macrophages

DTIC Science & Technology

2012-04-01

by inducing the activity of phase II detoxification enzymes in the urinary bladder. Arsenic {Ill) chloride [Ars(III)Cl]: Arsenic is one of the...agent used as raw materials for pharmaceuticals, analytical reagent as well as in organic synthesis and making iodine salts. 4,4’-Methylenebis ( 4𔃾...several factors. First, we sought to include hazardous chemicals with properties broadly representative of categories of TICs such as chlorides and

Arsenic uptake and speciation in the rootless duckweed Wolffia globosa.

PubMed

Zhang, Xin; Zhao, Fang-Jie; Huang, Qing; Williams, Paul N; Sun, Guo-Xin; Zhu, Yong-Guan

2009-01-01

Duckweeds are a common macrophyte in paddy and aquatic environments. Here, we investigated arsenic (As) accumulation, speciation and tolerance of the rootless duckweed Wolffia globosa and its potential for As phytofiltration. When grown with 1 microm arsenate, W. globosa accumulated two to 10 times more As than four other duckweed or Azolla species tested. W. globosa was able to accumulate > 1000 mg As kg(-1) in frond dry weight (DW), and tolerate up to 400 mg As kg(-1) DW. At the low concentration range, uptake rate was similar for arsenate and arsenite, but at the high concentration range, arsenite was taken up at a faster rate. Arsenite was the predominant As species (c. 90% of the total extractable As) in both arsenate- and arsenite-exposed duckweed. W. globosa was more resistant to external arsenate than arsenite, but showed a similar degree of tolerance internally. W. globosa decreased arsenate in solution rapidly, but also effluxed arsenite. Wolffia globosa is a strong As accumulator and an interesting model plant to study As uptake and metabolism because of the lack of a root-to-frond translocation barrier.

Arsenate reductase from Thermus thermophilus conjugated to polyethylene glycol-stabilized gold nanospheres allow trace sensing and speciation of arsenic ions.

PubMed

Politi, Jane; Spadavecchia, Jolanda; Fiorentino, Gabriella; Antonucci, Immacolata; De Stefano, Luca

2016-10-01

Water sources pollution by arsenic ions is a serious environmental problem all around the world. Arsenate reductase enzyme (TtArsC) from Thermus thermophilus extremophile bacterium, naturally binds arsenic ions, As(V) and As (III), in aqueous solutions. In this research, TtArsC enzyme adsorption onto hybrid polyethylene glycol-stabilized gold nanoparticles (AuNPs) was studied at different pH values as an innovative nanobiosystem for metal concentration monitoring. Characterizations were performed by UV/Vis and circular dichroism spectroscopies, TEM images and in terms of surface charge changes. The molecular interaction between arsenic ions and the TtArsC-AuNPs nanobiosystem was also monitored at all pH values considered by UV/Vis spectroscopy. Tests performed revealed high sensitivities and limits of detection equal to 10 ± 3 M -12 and 7.7 ± 0.3 M -12 for As(III) and As(V), respectively. © 2016 The Author(s).