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ABSTRACT: Arsenic (As) bioaccessibility is an important factor in estimating human health risk. Bioaccessibility of As in soils is primarily dependent on As adsorption, which varies with residence time. This study evaluated the effect of soil aging on potential lifetime cancer risk associated with chronic exposure to As contaminated soils. Four soils, chosen based on their differences in As reactivity, were amended with two arsenical pesticides - sodium arsenate, and dimethylarsinic acid (DMA) at two rates (675 and 1500mgkg(-1)). Rice was used as the test crop. Soil was sampled immediately after spiking, after 6 months, 1 year, and 3 years. Bioaccessible and total soil As concentrations were used to calculate lifetime excess cancer risk (ECR), which decreased significantly with soil-pesticide equilibration time. Immokalee soil, with the least As adsorption capacity, showed the highest decrease in ECR after 6 months resulting in values lower than the USEPA's cancer risk range of 1×10(-4) to 1×10(-6). For all other soils, the ECR was much higher than the target range even after 3 years. In the absence of significant changes in As bioaccessibility with time, the total soil As concentration more directly influenced the changes in ECR values with soil aging.
Journal of hazardous materials 10/2012; · 4.14 Impact Factor
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ABSTRACT: Although organoarsenical pesticides are being phased out, sites with high concentrations of organic arsenical residues still exist due to the long-term application of these pesticides. The biotic and abiotic speciation of dimethylarsinic acid (DMA) can result in the formation of inorganic arsenic (As) species. Oxidation state, retention, and thereby persistence, varies according to temporal changes, influencing the availability and toxicity of contaminants. The current greenhouse study aimed at evaluating temporal changes in the oxidation state of As, geochemical partitioning, and bioaccessibility. Four soils with varying physiochemical properties were contaminated with DMA at two concentrations (675 and 1,500 mg kg(-1) of As). Rice plants were grown for a 6 months period, following which, the soils were allowed to age. The operationally defined forms of As and its bioaccessibility was analyzed at 0, 6 months, 1 year, and 3 years. Changes in oxidation state of As were evaluated immediately after spiking and after 3 years of soil-pesticide equilibration. Results show that geochemical partitioning of As was affected significantly (P<0.05) by soil type, loading rates, and equilibration time. Arsenic was bound mainly to the poorly-crystalline Fe/Al-oxyhydroxides in the soil. However, these interactions did not affect As bioaccessibility, presumably due to the dissolution of the bound fractions of As in the acidic stomach. While 74-94% of the total bioaccessible As was transformed to As(V), 4-19% was transformed to the more toxic As(III). This study indicates that although aging affected the geochemical partitioning of As in the soil, bioaccesibility was controlled by the gastric pH.
Chemosphere 06/2011; 84(11):1563-71. · 3.21 Impact Factor
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ABSTRACT: Organoarsenical-containing animal feeds that promote growth and resistance to parasites are mostly excreted unchanged, ending up in nearby wastewater storage lagoons. Earlier work documented the partial transformation of organoarsenicals, such as, 3-nitro-4-hydroxyphenylarsonic acid (roxarsone) to the more toxic inorganic arsenate [As(V)] and 3-amino-4-hydroxyphenylarsonic acid (3-AHPAA). Unidentified roxarsone metabolites using liquid chromatography coupled to inductively coupled plasma mass spectrometry (LC/ICP-MS) were also inferred from the corresponding As mass balance. Earlier batch experiments in our laboratory suggested the presence of organometallic (Cu) complexes during relevant roxarsone degradation experiments. We hypothesized that organocopper compounds were complexed to roxarsone, mediating its degradation in field-collected swine wastewater samples from storage lagoons. The objective of this study was to investigate the role of organometallic (Cu) complexes during roxarsone degradation under aerobic conditions in swine wastewater suspensions, using electrospray ionization mass spectrometry (ES-MS).
Two swine wastewater samples differing in % solids content and total recoverable Cu concentrations were reacted with 500 ppb of roxarsone under aerobic conditions for 16 days. LC/ICP-MS and ES-MS were used for As speciation analyses, and characterization of metal-organoarsenical complexes in swine wastewater subsamples, respectively.
An organocopper roxarsone metabolite was found only in the high-Cu wastewater sample, suggesting the role of Cu in roxarsone degradation under aerobic conditions. The organocopper metabolite was not found in the low-Cu wastewater sample, because roxarsone did not undergo degradation under aerobic conditions even after 16 days.
Aerobic degradation of organoarsenicals (roxarsone) has not been documented before. Preliminary dataset from this study illustrates the direct and/or indirect association of particulate Cu in catalyzing roxarsone degradation under aerobic conditions in samples with high % solids content.
Concerns regarding the degradation of roxarsone in wastewater to the more toxic inorganic As may be partially linked to the presence of particulate Cu. The presence of Cu in wastewater-suspended particle surfaces has never been coupled before to organoarsenicals degradation reactions, thus, further studies are needed to elucidate the related reaction mechanisms and pathways. Water depth-dependent solid particle distribution profiles in wastewater storage lagoons could provide empirical evidence towards the design of effective degradation practices for nitrophenol-containing compounds, such as, organoarsenical-containing antibiotics, or explosive munitions compounds.
Environmental Science and Pollution Research 06/2010; 17(5):1167-73. · 2.65 Impact Factor
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ABSTRACT: There is a strong interest in developing an in vitro arsenic (As) model that satisfactorily estimates the variability in in vivo relative oral bioavailability (RBA) measurements. Several in vitro tests have been developed, but none is universally accepted due to their limited success in predicting soil As RBA. A suite of amorphous and crystalline solid As phases were chosen, utilizing a worst-case scenario (WCS) that simulated fasting children's gastric solution chemistry. The objectives of this study were to (i) determine the effects of residence time, pH, and solid-to-solution ratio on As bioaccessibility and speciation in the in vitro gastric test; (ii) provide the fundamental basis for an optimized in vitro model constrained by the WCS; and (iii) validate the optimized in vitro test with the in vivo RBA obtained with BALB/c mice. The gastric pH was the only significant (p < 0.05) factor influencing solid As bioaccessibility. Bioaccessible As retained the oxidation state after its release from the solid into the gastric solution. The optimized in vitro model adequately predicted RBA values for a suite of solid As phases typically encountered in soils, with the exception of aluminum-based solids. This study is an excellent starting point for developing an in vitro test applicable to different As-contaminated soils.
Environmental Science and Technology 08/2008; 42(16):6278-84. · 5.23 Impact Factor
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07/2005; , ISBN: 9780471478447
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ABSTRACT: Swine diets are often supplemented by organoarsenicals, such as 3-nitro-4-hydroxyphenylarsonic acid (roxarsone) to treat animal diseases and promote growth. Recent work reported roxarsone degradation under anaerobic conditions in poultry litter, but no such data exist for swine wastes typically stored in lagoons nearby concentrated animal feeding operations (CAFOs). The objectives of this study were to: (i) characterize a suite of swine wastes collected from 19 randomly selected CAFOs for soluble arsenate [As(V)], arsenite [As(III)], dimethylarsenic acid (DMA), monomethylarsonic acid (MMA), 3-amino-4-hydroxyphenylarsonic acid (3-HPPA), p-arsanilic acid, and roxarsone, and (ii) determine the geochemical fate of roxarsone in storage lagoons nearby CAFOs. Swine waste suspensions were spiked with roxarsone and incubated under dark/light and aerobic/anaerobic conditions to monitor roxarsone degradation kinetics. Arsenic speciation analysis using liquid chromatography and inductively coupled plasma mass spectrometry (LC-ICPMS) illustrated the prevalence of As(V) in swine waste suspensions. Roxarsone underwent degradation to either organoarsenicals (3-HPPA) or As(V) and a number of unidentified metabolites. Roxarsone degradation occurred under anaerobic conditions for suspensions low in solids content, but suspensions higher in solids content facilitated roxarsone degradation under both anaerobic and aerobic conditions. Increased solids content enhanced roxarsone degradation kinetics under aerobic conditions. According to current waste storage and sampling practices, arsenic in swine wastes stored in lagoons has been overlooked as a possible environmental health issue.
Journal of Environmental Quality 37(4):1626-33. · 2.32 Impact Factor
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ABSTRACT: A growing body of literature reports 3-nitro-4-hydroxyphenylarsonic acid (roxarsone) degradation in poultry litter (PL) to the more toxic inorganic arsenic (As). Aluminum-based drinking-water treatment residuals (WTR) present a low-cost amendment technology to reduce As availability in PL, similar to the use of alum to reduce phosphorus availability. Batch experiments investigated the effectiveness of WTR in removing roxarsone and inorganic As species from PL aqueous suspensions. Incubation experiments with WTR-amended PL evaluated the effects of WTR application rates (2.5-15% by weight) and incubation time (up to 32 d) at two incubation temperatures (23 and 35 degrees C) on As availability in PL. Batch PL aqueous experiments showed the high affinity of As(V), As(III), dimethylarsinic acid (DMA), monomethylarsonic acid (MMA), and roxarsone for the WTR. The 10% WTR amendment rate decreased As availability in PL by half of that of the unamended (no WTR) PL-incubated samples. The reduction in dissolved As concentrations during incubation of WTR-amended PL samples was kinetically limited, being complete within 13 d. Parallel reductions in roxarsone, As(V), and DMA concentrations were observed with liquid chromatography-inductively coupled plasma mass spectrometry, whereas As(III) and MMA concentrations were always <5% of dissolved As. Incubation temperature did not significantly (p > 0.05) influence dissolved As concentrations in the WTR-amended PL. Potential formation of a copper-containing roxarsone metabolite was considered in PL aqueous suspensions with the aid of electrospray mass spectrometry. Further experiments in the field are necessary to ensure that sorbed As is stable in WTR-amended PL.
Journal of Environmental Quality 37(3):963-71. · 2.32 Impact Factor
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ABSTRACT: Long-term application of arsenical pesticides in agricultural lands has resulted in high levels of arsenic (As) in certain soils. Conversion of former agricultural lands to residential areas has increased human contact with soil–As. Soil ingestion from incidental hand-to-mouth activity by children is now a very important issue in assessing human health risk associated with exposure to arsenical pesticide-applied former agricultural soils. Human health risk from exposure to soil–As is restricted only to those fractions of As in the soil that are available to the human gastrointestinal system. This study followed up on a static incubation experiment aimed at addressing the issue of soil variability on As bioaccessibility as a function of soil chemical properties, but in a greenhouse column system accounting for dynamic interactions between soils, water, plants, and pesticides. Two chemically variant soil types were chosen based on their potential differences with respect to As reactivity. The soils were amended with sodium arsenate pesticide at two high rates. Rice (Oryza sativa) was used as the test crop. A sequential extraction scheme was employed to identify the geochemical forms of As in soils (soluble, exchangeable, organic, Fe/Al-bound, Ca/Mg-bound, residual) immediately after spiking and after six months of equilibration. Concentrations of these As forms were correlated with the in-vitro fractions of As to identify those As species that are most likely to be bioaccessible in the human gastrointestinal system. Results from this study verified those obtained from the static incubation experiment, and demonstrated that As bioaccessibility is a function of soil speciation of As and that soil–As forms are a function of soil chemical properties.
Developments in Environmental Sciences.
