Arsenic is a metalloid present throughout the world, and the primary sources of exposure are through air, soil, and water. Arsenic is currently ranked as the most hazardous substance among environmental toxicants, and is well recognized as a human carcinogen, as well as a contributor to metabolic and cardiovascular diseases. However, cardiovascular effects have been mostly evaluated in epidemiological studies, and the direct mechanisms of pathogenesis remain largely unknown. The scope of studies described in this dissertation characterizes the cardiovascular pathophysiology associated with exposure to environmentally-relevant arsenic concentrations (100 µg/L), and attempts to elucidate the molecular mechanisms behind impaired vascular function. The effects of chronic arsenic exposure on blood pressure regulation were examined using a mouse model exposed to 100 µg/L for 22 weeks. Chronic exposure to arsenic results in the development of hypertension and concentric left ventricular hypertrophy. Furthermore, data presented here demonstrates that in utero exposure contributes to the development of metabolic syndrome throughout adulthood. Results indicate the development of hyperglycemia, hypercholesterolemia and nonalcoholic fatty liver disease. Mechanistic studies demonstrate the effects of arsenicals on endothelial nitric oxide synthase (eNOS) and its role in arsenic-induced vascular relaxation impairment. Biochemical assessment of eNOS conclude that decreased nitric oxide availability does not occur through alterations in protein levels or phosphorylation changes; however, decreased activity is likely a result of protein dimer stability through alterations in zinc tetrathiolate binding.

Arsenic is a naturally occurring contaminant in ground water. The link between human exposure to elevated levels of arsenic and the increase in cancerous and non-cancerous diseases is well documented. Consequently, arsenic removal from drinking water has been thoroughly investigated.Lowering the maximum contaminant limit of arsenic (from 50 to 10 ppb) will burden small water utilities, who either lack the financial or technical ability to comply. Adsorption onto solid media has been one of the most attractive options for small water utilities (EPA, 2001), but this process generates huge amounts of arsenic bearing solid residuals (ABSRs) complicating further this matter.Numerous studies have suggested that the Toxicity Characteristics Leaching Procedure (TCLP) does not properly reflect the actual leaching behavior of ASBRs under landfills (Ghosh et al., 2004). This work focuses on testing different arsenic iron- oxide and non- iron- based sorbents, likely to be used for arsenic removal, and assessing the long term behavior of these sorbents under landfill conditions. Our results indicate that microbial processes play a major role in the mobilization of As from granular ferric hydroxide (GFH). Long term operation of GFH sorbent showed that Fe (III) was reduced to Fe(II) and As(V) was reduced to As(III) under anaerobic/reducing conditions. Under semi batch landfill simulation experiments, our results show that non iron based media leached arsenic above the Toxicity Characteristics limit (TC) and it was observed that sorbate (As) might leach at a faster rate than the sorbent itself. It is thought that arsenic mobilization from iron-based sorbent occurs mostly due to iron reduction and its subsequent dissolution. However, measured arsenic leaching rates from the sorbents used in this study are comparable with that of the ferric hydroxide media, which indicates that the mechanism of arsenic mobilization might be independent of the possible dissolution of the sorbent. Despite the fact that non- iron based media may have a higher arsenic adsorption capacity, they leach arsenic at a higher rate than iron based media under our simulated landfill conditions.

Using Environmental Protection Agency occurrence and concentration data, it is estimated that about 6 million pounds of arsenic-bearing residuals (ABSR) will be generated annually in the United States when full compliance with the new standard for arsenic in drinking water (10 μg/L) is realized. Effective management of disposal of ABSR requires both a full characterization of the materials and an understanding of the environment in which the disposal will occur. Currently, there are different testing methods to evaluate the stability of ABSR, the principal of which is the EPA Toxicity Characteristics Leaching Procedure (TCLP). These tests indicate that common ABSRs may be disposed in mixed-solid waste landfills. However, this and previous work shows that these testing methods may significantly underestimate the degree and mechanism of arsenic mobilization from the residuals, because critical physical and chemical dissimilarities exist between the tests and landfill conditions. In addition, no current testing methods simulate the mineralogic aging in those ABSR, which exhibit further complexity. Landfill disposal involves liquid and solid residence times on the order of months and decades, respectively, whereas leaching tests are completed in two days or less. Consequently, time dependent re-mineralization of residuals that would be routinely expected in landfill time scales is not addressed by standard leaching tests. Treating arsenic brines by co-precipitation with iron oxyhydroxides is an established and effective remediation method for small quantities of highly concentrated liquid arsenic waste, such as brines derived from mine tailings, ion exchange resin regeneration, and reverse osmosis treatment of drinking water. However, amorphous ferric hydroxide (AFH) is expected to exhibit mineralogical aging analogous to the observed natural evolution of ferrihydrite to goethite and hematite. The aim of this research is to develop methods for characterization of AFH sludges precipitated from concentrated arsenic brines which exhibit mineralogical aging and to evaluate the impact of such aging on arsenic leachability. Overall, aging the sludge resulted in consistently higher arsenic release.

Potential arsenic toxicity in different geologic environments is dependent on total arsenic concentration and arsenic bioavailability. It is important to identify the geologic environments that may sequester arsenic because these systems can act as long-term sources for arsenic as well as retard transport and limit toxicity. Bioavailability is defined as the readiness of a compound or element to be taken up by organisms (Gregorich et al., 2001), while potential bioavailability is possible uptake of a compound or element by organisms. The objective of this research is to quantify the potential bioavailability of arsenic in laboratory microcosms and in different geologic environments in the Nueces and San Antonio River Watersheds, Texas, using a chelating resin as an infinite sink. To assess the applicability of chelating resins to estimate potential arsenic bioavailability in the field, iron-loaded DOWEX M4195 resin was used to extract arsenic from solutions and sediments (pond sediment, river sediment, and ephemeral stream sediment). The average percentage of arsenic sorbed from solution was 66% ± 0.16. Competition studies between arsenate, phosphate, and vanadate suggest there is moderate competition, reducing overall arsenic sorption to the resin in the presence of competing ions. Iron-loaded resin was then exposed to sediment samples spiked with increasing amounts of arsenic over 15, 30, 60 and 90 days. Results of the sediment study showed 1) increased arsenic sorption to the resin over time, 2) small variations of potential bioavailable arsenic among geologically different sediments, and 3) evidence of arsenic sequestration. Field devices that housed iron-loaded resin were used to extract potentially bioavailable arsenic from sediment in six different geologic environments (i.e. lake, river, perennial stream, ephemeral stream, pond, and wetland) in the watersheds over a twenty-eight day period. The wetland (15.7 mmol As/g wet resin) and perennial stream sediments (11.0 mmol As/g wet resin) represented the maximal and minimal calculated potential bioavailability, respectively. However, the potentially bioavailable index calculated from mmol As/g wet resin extracted from field environments and mmol As/ g sediment in digested samples showed sequestration would be high in the wetland environment and high bioavailability in the perennial stream and river environments.

Widespread arsenic contamination with adverse effects to human health is a global problem. Most previous studies on arsenic contamination in natural environments and those associated with mining and agricultural activities focused largely on arsenic-rich minerals such as arsenates, arsenites, sulfarsenides, and sulfides. Rock-forming minerals generally contain only minor or trace amounts of arsenic but, owing to their sheer abundances, are potentially important (and sometimes dominant) sources of this metalloid and can play significant roles in the attenuation and sequestration of arsenic in various environments. However, there remains a significant gap in my knowledge about the uptake and speciation of arsenic in rock-forming minerals. This thesis research is intended to bridge this gap by investigating the uptake and speciation of arsenic in selected rock-forming sulfate and phosphate minerals (i.e., gypsum, struvite and newberyite). Gypsum (CaSO4•2H2O) is a major by-product of mining and milling processes of borate, phosphate and uranium deposits worldwide and, therefore, potentially plays an important role in the stability and bioavailability of heavy metalloids, including As, in tailings and surrounding areas. Gypsum containing 1,900 and 185 ppm As, synthesized with Na2HAsO4•7H2O and NaAsO2 in the starting materials, respectively, has been investigated by synchrotron X-ray absorption spectroscopy (XAS), single-crystal electron paramagnetic resonance spectroscopy (EPR), and pulsed electron nuclear double resonance spectroscopy (ENDOR). Quantitative analyses of As K edge X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectra show that arsenic occurs in both +3 and +5 oxidation states and the As3+/As5+ value varies from 0.35 to 0.79. Single-crystal EPR spectra of gamma-ray-irradiated gypsum reveal two types of arsenic-associated oxyradicals: [AsO3]2− and an [AsO2]2−. The [AsO3]2− center is characterized by principal 75As hyperfine coupling constants of A1 = 1952.0(2) MHz, A2 = 1492.6(2) MHz and A3 = 1488.7(2) MHz, with the unique A axis along the S-O1 bond direction, and contains complex 1H superhyperfine structures that have been determined by pulsed ENDOR. These results suggest that the [AsO3]2− center formed from electron trapping on the central As5+ ion of a substitutional (AsO4)3− group after removal of an O1 atom. The [AsO2]2− center is characterized by its unique A(75As) axis approximately perpendicular to the O1-S-O2 plane and the A2 axis along the S-O2 bond direction, consistent with electron trapping on the central As3+ ion of a substitutional (AsO3)3− group after removal of an O2 atom. These results confirm lattice-bound As5+ and As3+ in gypsum and point to potential application of this mineral for immobilization and removal of arsenic pollution. EPR spectra show that another sulfate boussingaultite is also sequestering both As5+ and As3+ at its S site. Synthesis experiments at pH from 2 to 14 also show that arsenic uptake in gypsum is pH dependent. Struvite and newberyite, common biominerals and increasingly important green fertilizers recovered from wastewater treatment plants, are capable of sequestering a wide range of heavy metals and metalloids, including arsenic. Inductively coupled plasma mass spectrometric (ICPMS) analyses show that struvite formed under ambient conditions contains up to 547±15 ppm As and that the uptake of As is controlled by pH. Synchrotron As K-edge XANES spectra measured at 20 K show that As5+ is the predominant oxidation state in struvite, irrespective of Na2HAsO4•7H2O or NaAsO2 as the source for As. Modeling of As K-edge EXAFS data suggest that local structural distortion associated with the substitution of As5+ for P5+ in struvite reaches up to 3.75 Å. Single-crystal electron paramagnetic resonance (EPR) spectra of gamma-ray-irradiated struvite disclose five [AsO3]2- radicals and one [AsO4]2- radical. These arsenic-centered oxyradicals are all readily attributed to form from diamagnetic [AsO4]3- precursors during irradiation, providing further support for exclusive incorporation and local structural expansion beyond the first shell of As5+ at the P site in struvite. Arsenic doped newberyite (MgHPO4•3H2O) obtained from the gel diffusion method has investigated by synchrotron XAS at the As K-edge (11,867 eV) at 8 K and single-crystal EPR spectroscopy at room temperature. XANES data show that As5+ is dominant and EXAFS analysis reveals a local environment typical of the arsenate species as well. Single-crystal EPR spectra of gamma-ray-irradiated newberyite contain two arsenic-associated oxyradicals: [AsO3]2− and [AsO2]2− derived from As5+ and As3+, respectively, at the P site in the newberyite structure. Elevated concentrations of arsenic have also been observed in natural newberyite from guano deposits and reflect the accumulation of this metalloid in the food chain. Therefore, struvite and newberyite can both sequester significant amounts of arsenic, and their direct use as fertilizers (irrespective of origins from guano deposits or wastewaters) is a potential source of arsenic contamination. On the other hand, the capacities of struvite and newberyite for accommodating significant amounts of arsenic in crystal lattices coupled with their simple chemistry and crystallization under ambient conditions make them attractive materials for immobilization and removal of arsenic contamination in aqueous environments.

Nitrate, arsenic and vanadium are all potential groundwater contaminants. Traditional physical/chemical methodologies are often too technical or expensive for rural environments. Biofiltration has been shown to remove a wide range of contaminants depending on the operating parameters. This research examined the possibility of using the denitrifying bacteria, Paracoccus denitrificans, to remove nitrate, arsenic and vanadium simultaneously from groundwater with varying iron concentrations. During bench-scale testing nitrate concentrations were reduced by up to 73%, even with the metals present. Without iron, arsenic and vanadium removal was insignificant. Removal increased when iron was added as it was found that arsenic and vanadium could be removed adsorptively by iron hydroxides. With 1 mg/L of iron present, removal rates of 67% and 91% were achieved for arsenic and vanadium, respectively. When the iron was increased to 2 mg/L, the removal rates increased to 85% and 96%, respectively.

Arsenic taken up by plants and fungi from contaminated soils can subsequently be introduced into food chains. Given the toxic properties of some arsenic compounds, this may be a cause for concern. Much remains to be learned about how these compounds are transformed and distributed in terrestrial organisms. Radishes, white button mushrooms, fur, and feather samples were thus investigated to gain a better understanding of arsenic biotransformations in terrestrial organisms. In this study, we utilized two analytical techniques for the detection and identification of arsenic compounds (“arsenic speciation analysis”). High performance liquid chromatography inductively coupled plasma mass spectrometry (HPLC-ICP-MS) provided a highly sensitive method for detecting low levels (ng•g-1) of methanol:water extractable arsenic compounds. X-ray absorption spectroscopy (XAS) techniques provided direct arsenic speciation analysis of tissues, resulting in a more representative arsenic profile of the original organisms, without the need to extract arsenic first. Overall, the results for speciation analysis underline the complementary nature of the HPLC-ICP-MS and XAS techniques. Mushrooms contained organic arsenic compounds which were not identified in the radish. In particular arsenobetaine (AB), which is usually found as a minor constituent of terrestrial organisms, was a predominant arsenic compound found in mushroom extracts. How AB is synthesized in the environment remains unclear; however, results presented here suggest it was a product of fungal biotransformation and we speculate it may play a role in osmoregulation. In radish, fur and feather samples, direct analysis identified arsenic(III)-sulphur compounds not observed using HPLC-ICP-MS. In plants, these compounds are likely to be metal/metalloid binding phytochelatin proteins the formation of which has yet to be confirmed in planta. In radish plant vasculature, XAS imaging revealed segregation of pentavalent and trivalent arsenic compounds, suggesting differences in arsenic transport. In hair and feathers the formation of arsenic(III)-sulphur compounds may be evidence of arsenic binding to keratin proteins which has been hypothesized to occur, and may contribute to the observed reduction of exogenous arsenic contamination. / Thesis (Ph.D, Biology) -- Queen's University, 2007-05-30 11:55:40.157

The existence of small-scale gold mining in Nova Scotia between 1868 and 1942 has resulted in many high arsenic (As) tailings areas in the province, some of which are near rural/urban areas and are used for recreational activities such as dirt bike racing and all-terrain vehicle (ATV) riding. Because of the natural association of As with gold ore in the Meguma Terrane, processing of ore has resulted in As-rich mine waste that contains up to 2500 times more As than the Canadian soil quality guideline of 12 mg/kg. These high As concentrations in combination with the recreational use of these sites creates a risk of human exposure. The objective of this work was to investigate the effects of different cover options that might be used to mitigate the risk of human exposure. Four tailings samples were selected to represent the geochemical variability from two tailings areas: Montague gold mines and Goldenville. These samples were characterized and subjected to 29 weeks of column testing, in which each sample was leached with three different input solutions including synthetic rainwater (to simulate uncovered tailings exposed to natural acid rain), synthetic rainwater equilibrated with calcium carbonate (to simulate rainwater percolation through a crushed limestone cover), and a dilute organic acid solution (to simulate a vegetative cover). Results of acid base accounting (ABA) tests indicate that samples have the potential to generate acid in the future (ratio of neutralization potential to acid potential is less than 2), though surface water at the sites is currently circum-neutral. Acidic paste pH values (2.9) from a sample of As-rich hardpan indicate that a small volume of tailings at Montague are currently generating acid. Results of column testing indicate that the cover types simulated by the input solutions had less of an effect on the out-flowing leachate chemistry than did the small volume of secondary As phases in each sample (scorodite, yukonite, hydrous ferric arsenate and hydrous ferric oxides). For the majority of sample types, columns leached with an organic acid solution reported higher leachate As concentrations than were reported from columns leached with either the rainwater or carbonate-rainwater solutions. / Thesis (Master, Geological Sciences & Geological Engineering) -- Queen's University, 2010-10-27 14:26:06.13

Terra mine is an abandoned copper and silver mine in the Northwest Territories, Canada, from which mine tailings were deposited into Ho-Hum Lake, adjacent to the mine’s processing plant. The tailings contain elevated levels of arsenic (As), resulting in As levels exceeding Canadian sediment and water quality guidelines in the lake, and in downstream wetland water and sediment. This field and laboratory study focuses on the microbial ecology, and the reduction and oxidation of As, iron (Fe) and sulphur (S), in the wetland downstream from Ho-Hum Lake. This wetland is proposed as a passive remediation system for removal and storage of As. Using microcosm experiments, the stability of As-bearing sediments was compared in the upper, middle and lowestmost areas of the wetland over a 42-day period. Fresh sediments and sediments amended with a 10 mM acetate solution, both mixed with water, were compared. While no significant geochemical differences were found between acetate-amended and unamended microcosms, formation of inorganic As-S species was higher in amended microcosms, suggesting that micro-organisms were more active in the system because they were not carbon-limited. Formation of methylated-As species increased over time in all samples, including abiotic controls. Bacterial sulphate reduction occurred during the first 10 days of the experiment, perhaps resulting in precipitation of sulphide minerals. X-ray adsorption near edge spectroscopy was used to assess solid-state speciation of As in the sediments and indicated that pre-microcosm sediments from all sites showed high proportions of As(III)-S and As(III)-O speciation. Post-microcosm sediments revealed a 13% increase in the proportion of As(V)-O species, whereas abiotic controls showed only an 8% increase. DNA sequencing in post-microcosm sediments identified As, Fe and S reducing bacteria, and the geochemical patterns of As, Fe and S in the microcosms indicate the bacteria are likely active in the system. Microbial diversity and solid-state speciation of As in the sediments were assessed at varying depths at the microcosm sites, but correlation analysis revealed no significant relationship between As speciation and microbial diversity. A positive correlation between diversity and depth, and a negative relationship between As concentration and diversity, were found, perhaps indicating decreasing contamination with depth in the wetland. / Thesis (Master, Geological Sciences & Geological Engineering) -- Queen's University, 2011-07-03 23:27:44.373

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