Arsenic contamination in drinking water has been a cause of serious concerns across the United States as well as throughout the world. Over 70 million people in Eastern India, Bangladesh, Vietnam, Taiwan, and Northern China have been victims of arsenic poisoning. The USEPA has classified arsenic as a Class A carcinogen and recently reduced the Maximum Contaminant Level (MCL) in drinking water from 50ppb to 10ppb. The deadline for all the water utilities to meet this level is 23rd January 2006. To meet those drinking water standards, small water utilities need low cost and effective arsenic removal techniques. Natural zeolites such as Chabazite are excellent sorbents for several metallic and radioactive cations. Modifying the zeolite structure can effectively enhance the adsorption capacities of these zeolites for removal of heavy metals. The present work investigates the adsorption capacities of Cuprous and Ferrous treated Chabazite for removal of arsenic. This investigation is a part of a broader project directed at developing an effective pretreatment process that uses modified Chabazite in conjugation with Microfiltration (MF) or Ultrafiltration (UF) for removal of organic and inorganic contaminants. The goal of this research is to determine how well Cuprous and Ferrous treated Chabazite sorbs arsenic in its trivalent and pentavalent state. The other objectives of this research are to examine which modification of the chabazite has the higher removal efficiency of arsenic. This study will also compare arsenic adsorption on the modified zeolites in response to competitive adsorption of various anions present in natural source waters such as sulfates, hydroxides, and chlorides. The potential benefit of this study is to find the most effective treatment of for removal of arsenic species from aqueous solutions. This investigation may provide small water utilities, with a cost effective way for removal of arsenic and thus meet the recommended new regulatory maximum contaminant level (MCL).

Neural tube defects (NTDs) are malformations affecting about 2.6/1000 births worldwide, and 1/1000 in the United States. Their etiology remains unknown, and is likely due to interaction of genetic susceptibility factors with environmental exposure. Of the many environmental agents considered to potentially contribute to NTD risk, arsenic is one that is surrounded in controversy. We have developed a model system utilizing maternal intraperitoneal (I.P.) exposure on E7.5 and E8.5 to As 9.6 mg/kg (as sodium arsenate) in a normal inbred mouse strain, LM/Bc/Fnn, that is sensitive to arsenate-induced exencephaly. We investigated arsenate induced gene expression changes using DNA microarrays of embryonic anterior neural tube tissue, as well as monitoring of metabolic function in conjunction with the administration of select compounds to rescue the normal phenotype. Finally, to address questions concerning the importance of route of administration and potential maternal toxicity, a teratology study was performed using three arsenate doses administered orally. Regarding the gene expression study, we identified several candidate genes and ontology groups that may be responsible for arsenate’s teratogenicity. Genes include: engrailed 1 (En-1), platelet derived growth factor receptor alpha (Pdgfrα) and ephrinA7 (EphA7). Gene ontology groups identified include oxidative phosphorylation, redox response, and regulation of I-kappaB kinase/NF-kappaB cascade. Acute arsenate exposure induced disruption of mitochondrial function and dependent glucose homeostasis: subsequent hyperglycemia was teratogenic. Maternal treatment with insulin or n-acetyl cysteine, an antioxidant and precursor of glutathione synthesis, proved highly successful in rescuing both the normal phenotype, and to differing degree, the maternal hyperglycemia. Maternal oral arsenate administration also resulted in exencephaly, with exposed embryos exhibiting a positive linear trend with arsenate dosage. There were also linear trends in the relationships between arsenate dose and anomalies involving several components of the axial skeleton: the vertebrae and calvarium. There was no evidence of maternal toxicity as shown by lack of differences in maternal body weight gain, liver, and kidney weights. In conclusion, maternal arsenate exposure (regardless of exposure route) was teratogenic in our model, primarily causing NTDs. Responsible mechanisms may involve disruption of redox and glucose homeostasis as well as expression of established NTD candidate genes.

Neural tube defects (NTDs) are malformations affecting about 2.6/1000 births worldwide, and 1/1000 in the United States. Their etiology remains unknown, and is likely due to interaction of genetic susceptibility factors with environmental exposure. Of the many environmental agents considered to potentially contribute to NTD risk, arsenic is one that is surrounded in controversy. We have developed a model system utilizing maternal intraperitoneal (I.P.) exposure on E7.5 and E8.5 to As 9.6 mg/kg (as sodium arsenate) in a normal inbred mouse strain, LM/Bc/Fnn, that is sensitive to arsenate-induced exencephaly. We investigated arsenate induced gene expression changes using DNA microarrays of embryonic anterior neural tube tissue, as well as monitoring of metabolic function in conjunction with the administration of select compounds to rescue the normal phenotype. Finally, to address questions concerning the importance of route of administration and potential maternal toxicity, a teratology study was performed using three arsenate doses administered orally. Regarding the gene expression study, we identified several candidate genes and ontology groups that may be responsible for arsenate’s teratogenicity. Genes include: engrailed 1 (En-1), platelet derived growth factor receptor alpha (Pdgfrα) and ephrinA7 (EphA7). Gene ontology groups identified include oxidative phosphorylation, redox response, and regulation of I-kappaB kinase/NF-kappaB cascade. Acute arsenate exposure induced disruption of mitochondrial function and dependent glucose homeostasis: subsequent hyperglycemia was teratogenic. Maternal treatment with insulin or n-acetyl cysteine, an antioxidant and precursor of glutathione synthesis, proved highly successful in rescuing both the normal phenotype, and to differing degree, the maternal hyperglycemia. Maternal oral arsenate administration also resulted in exencephaly, with exposed embryos exhibiting a positive linear trend with arsenate dosage. There were also linear trends in the relationships between arsenate dose and anomalies involving several components of the axial skeleton: the vertebrae and calvarium. There was no evidence of maternal toxicity as shown by lack of differences in maternal body weight gain, liver, and kidney weights. In conclusion, maternal arsenate exposure (regardless of exposure route) was teratogenic in our model, primarily causing NTDs. Responsible mechanisms may involve disruption of redox and glucose homeostasis as well as expression of established NTD candidate genes.

The maximum contaminant level (MCL) for arsenic in drinking water was reduced to 10 parts per billion in 2006 by the USEPA. As a result, approximately 10,000 tons of arsenic-bearing residuals (ABSRs) are estimated to be generated every year from water treatment processes. It has also been established that the standard Toxicity Characteristic Leaching Procedure (TCLP), underestimates arsenic leaching from ABSRs, particularly under mature, mixed solid waste landfill conditions. This makes it critical to investigate stabilization technologies that would ensure long-term stability of arsenic residuals after disposal. Arsenic is ubiquitously associated with iron oxides in natural environments as well as water treatment residuals. Hence, knowledge of iron oxide transformations under landfill conditions is critical to understanding the fate and mobility of the associated arsenic. In this work, the effect of high local Fe(II) concentrations on ferrihydrite transformation pathways was studied. Magnetite was the sole transformation product in the presence of high local Fe(II) concentrations. In the absence of high Fe(II) concentrations, goethite was the major transformation product along with minor quantities of magnetite. These results have implications for arsenic mobility from ABSRs since goethite and magnetite have different arsenic sorption capacities and mechanisms. Two technologies were investigated for the stabilization of ABSRs - Arsenic Crystallization Technology (ACT) and Microencapsulation. The strategy for ACT was to convert ABSRs into minerals with a high arsenic capacity and long-term stability under landfill conditions. Scorodite, arsenate hydroxyapatites, ferrous arsenate, arsenated schwertmannite, tooeleite and silica-amended tooeleite, were synthesized and evaluated for their potential to serve as arsenic sinks using TCLP and a simulated landfill leachate test. Ferrous arsenate type solids and arsenated schwertmannite showed most promise in terms of low arsenic leachability and favorable synthesis conditions. Microencapsulation involved coating arsenic-loaded ferrihydrite with a mineral having high stability under landfill conditions. Based on results from a previous study, vivianite was investigated as a potential encapsulant for ABSRs. A modified version of the TCLP was used to evaluate the effectiveness of microencapsulation. Although vivianite did not prove to be a promising encapsulant, our efforts offer useful insights for the development of a successful microencapsulation technology for arsenic stabilization.

Arsenic (As) is a highly toxic chemical that is widely distributed in groundwater around the world. As-bearing sulfide minerals (ASM) are known to contribute to high background concentrations of As in groundwater in regions where the geochemistry of the parent material is dominated by sulfide minerals. The fate of As in groundwater depends on the activity of microorganisms which can oxidize arsenite (Asᴵᴵᴵ), or reduce arsenate (Asᵛ). In oxidizing environments, Asᵛ is the predominant species, and the accumulation of As is limited by the sorption of As onto iron (Fe) oxides and hydroxides. Under reducing environments, Asᴵᴵᴵ is the predominant specie, and while the sorption strength of Asᴵᴵᴵ on the Fe-surface of Fe (oxy)hydroxides is weaker, the accumulation of As in water can be limited by the precipitation of As as part of an ASM. The main aim of this research is to study the impact of microbial activity on the mobilization and immobilization of As in the environment. The first objective of this research was to characterize the metabolic activity of three Asᴵᴵᴵ-oxidizing bacteria, Azoarcus sp. pb-1 strain EC1, Azoarcus sp. pb-1 strain EC3 and Diaphorobacter sp. pb-1 strain MC, isolated from a non-contaminated, pristine environment. These Asᴵᴵᴵ-oxidizing bacteria demonstrated a great metabolic flexibility to use oxygen and nitrate to oxidize Asᴵᴵᴵ as well as organic and inorganic substrates as alternative electron donors (e-donors) explains their presence in non-As-contaminated environments. The findings suggest that at least some Asᴵᴵᴵ-oxidizing bacteria are flexible with respect to electron-acceptors and e-donors and that they are potentially widespread in low As concentration environments. The second objective of this research was to investigate the stability of orpiment (As₂S₃) and arsenopyrite (FeAsS), at circumneutral pH and 30°C, under aerobic- and or anoxic conditions (nitrate amended as electron acceptor (e-acceptor)), in order to assess the feasibility of immobilizing As by formation of ASM as a long-term option for the bioremediation of As contamination. The percentage of As released from the minerals ranged from zero when FeAsS was biologically incubated to 87% for As₂S₃(s) under anoxic abiotic conditions. While the dissolution of ASM was greater in biological conditions, the presence of inoculum provided as sludge served as a sink for As, limiting the mobilization of As into aqueous phase. Thus, the mobilization of As from ASM can be controlled by altering the environmental conditions such as the redox conditions or by stimulating microbial activity. Further research investigated the formation of ASM catalyzed by biological reduction of Asᵛ and sulfate (SO₄²⁻). In particular, the third objective of this research was to study the effect of the pH on the removal of As due to the biological-mediated formation of ASM in an iron-poor system. A series of batch experiments were performed to study the reduction of SO₄²⁻ and Asᵛ by an anaerobic mixed culture in a range of pH conditions (6.1-7.2), using ethanol as the e-donor. A marked decrease of the total aqueous concentrations of As and S and the formation of a yellow precipitate was observed in the inoculated treatments amended with ethanol, but not in the non-inoculated controls, indicating that the As-removal was biologically mediated. The pH dramatically affected the extent and rate of As removal, as well as the stoichiometric composition of the precipitate. The precipitate was composed of a mixture of orpiment and realgar, and the proportion of orpiment in the sample increased with increasing pH. The results suggest that ASM formation is greatly enhanced at mildly acidic pH conditions. The fourth objective was to investigate the biomineralization of As through simultaneous Asᵛ and SO₄²⁻ reduction in a minimal iron environment for the As-contaminated groundwater bioremediation. A continuous bioreactor, inoculated with an anaerobic sludge was maintained at circumneutral pH (6.25-6.50) and fed with Asᵛ and SO₄²⁻, utilizing ethanol as an e-donor for over 250 d. A second bioreactor running under the same conditions but lacking SO₄²⁻ was operated as a control to study the fate of As removal. The reactor fed with both Asᵛ and SO₄²⁻ removed on the average 91.2% of the total soluble As, while less than 5% removal was observed in the control bioreactor without S. The biomineralization of As in the bioreactor was also evident from the formation of a yellow precipitate made of a mixture of As₂S₃ and AsS minerals. These results taken as a whole indicate that a bioremediation process relying on the addition of a simple, low-cost e-donor offers potential to promote the removal of As from groundwater by precipitation of ASM. The fifth objective was to evaluate the toxic impact that the exposure to soluble As or the formation of ASM could have on the anaerobic mixed culture used as inocula. The methanogenic community on the reactors was impacted by addition of As. The biogenic ASM inhibited the acetoclastic methanogens causing an accumulation of acetate. In the SO₄²⁻-free bioreactor, the methanogens were initially highly sensitive to Asᴵᴵᴵ (formed from Asᵛ reduction) but quickly adapted to its toxicity. Consequently, the formation of ASM would impact the methanogenic activity of an anaerobic biofilm, while the exposure to Asᴵᴵᴵ would not have a negative impact if the biofilm undergoes adaptation. The sixth and final objective was to study the stability of a biogenic ASM at two different pH values (6.5 and 7.5) and under different redox conditions. The long-term stability was evaluated in three different bioreactors that operated for 145 d: aerobic (R1), anoxic (nitrate as alternative e-acceptor (R2) and anaerobic (R3). The dissolution of ASM was greatly affected by the pH, and slightly by the presence and nature of the e-acceptor. The ASM was very stable at pH 6.5, however, the As mobilization rate was up to 7-fold higher at pH 7.5, likely due to the formation of thioarsenic species. The stability of ASM was also impacted by the e-acceptor present. The As mobilization rate was 77% higher under anaerobic conditions than under aerobic conditions, most likely due to the formation of secondary As-bearing minerals. Therefore, the stability of ASM depends on the conditions of the operation, and it can be controlled by altering the environmental conditions, such as the pH or the presence of the e-acceptor.

Thesis (M.S.)--Montana State University--Bozeman, 2007. / Typescript. Chairperson, Graduate Committee: William P. Inskeep. Includes bibliographical references (leaves 86-94).

No description available.

Inorganic pesticides including natural chemicals such as arsenic, copper, lead, and sulfur have been used extensively to control pests in agriculture. Lead arsenate (PbHAsO4) was first used in apple orchards in the late 1890's to combat the codling moth, Cydia pomonella (Linnaeus). The affordable and persistent pesticide was applied in ever increasing amounts for the next half century. The persistence in the environment in addition to the heavy applications during the early 1900's may have led to many of the current and former orchards in this country being contaminated. In this study, soil samples were taken from several apple orchards across the state, ranging from Southwest to Northern Virginia and were analyzed for arsenic and lead. Based on naturally occurring background levels and standards set by other states, two orchards sampled in this study were found to have very high levels of arsenic and lead in the soil, Snead Farm and Mint Spring Recreational Park. Average arsenic levels at Mint Spring Recreational Park and Snead Farm were found to be 65.2 ppm and 107.6 ppm, respectively. Average lead levels were found to be 354.5 ppm and 442.3 ppm, respectively. Based on these results, Virginia needs to look at setting standards for lead and arsenic in soil to determine if cleanup of former agricultural lands will be necessary. / Master of Science

Structures made of chromated copper arsenic (CCA) have been shown to leach arsenic into the surrounding soil. Soil cores were taken adjacent to six CCA decks at 0, 15, 60 and 300 cm from the deck at depths of 0–10, 10–20, and 20–30 cm, and were analyzed for soil arsenic concentrations. Median soil arsenic concentrations ranged from 1.8 μg/g at a depth of 10–20 cm and a distance of 300 cm to 34.5 μg/g at a depth of 0–10 cm and a distance of 30 cm. Soil arsenic concentrations taken at depths of 0–10 and 10–20 cm decreased as distance from the deck increased. Soil arsenic concentrations close to the deck were higher at lower soil depths and at homes with greater deck wipe arsenic concentrations. Age of deck and slope of land had significant effects on the differences in arsenic concentrations between samples taken at different distances when evaluated in models by themselves, but not in models adjusting for deck wipe concentrations. Size of deck and bulk density of soil did not have significant effects on soil arsenic concentrations.

Human exposure to arsenic in groundwater is a global concern, and arsenic mobility in groundwater is often controlled by Fe mineral dissolution and precipitation. Additionally, Fe(II)-catalyzed recrystallization of Fe oxides has been shown to enable trace element release from and incorporation into Fe oxides. However, the effect of As(V) on the Fe(II)-catalyzed recrystallization of Fe oxides such as goethite, magnetite, and ferrihydrite remains unclear. Here, we measured the extent of Fe atom exchange between aqueous Fe(II) and magnetite, goethite, or ferrihydrite in the presence of As(V) by reacting isotopically "normal" Fe oxides with 57Fe-enriched aqueous Fe(II). At lower levels of adsorption (≤13.3 μM), As(V) had little influence on the rate or extent of Fe(II)-catalyzed Fe atom exchange in goethite or magnetite. However, Fe atom exchange was increasingly inhibited as As(V) concentration increased above 100 μM. Additionally, adsorbed As(V) may be incorporated into magnetite over time in the presence and absence of added aqueous Fe(II) as indicated by X-ray absorption spectroscopy (XAS) and chemical extraction data, with more rapid incorporation in the absence of added Fe(II). XAS and chemical extraction data are also consistent with the incorporation of As(V) during goethite and magnetite precipitation. Additionally, atom exchange data indicated that low levels of As(V) coprecipitation (As:Fe = 0.0005-0.0155) had little influence on the rate or extent of Fe(II)-catalyzed Fe atom exchange in goethite or magnetite. Atom exchange data indicated that ferrihydrite likely transforms via a dissolution-reprecipitation mechanism both to lepidocrocite at 0.2 mM Fe(II) and to magnetite at 5 mM Fe(II). The presence of 206 μM As(V) slowed the transformation of ferrihydrite to more crystalline iron minerals and slowed the rate of atom exchange between aqueous Fe(II) and ferrihydrite. However, the degree of atom exchange did not directly correlate with the amount of ferrihydrite transformed. In summary, Fe oxide recrystallization processes may affect As(V) uptake and release in the environment, and As(V) may inhibit Fe(II)-catalyzed Fe oxide recrystallization.