Arsenic is ubiquitous whether it is naturally occurring or produced by humans. It is found at sites on the National Priority List and at sites operated by DOE, where it is the second most commonly found contaminant. More wastes containing arsenic will be produced due to the lowering of the Maximum Contaminant Level (MCL) for arsenic in drinking water which will result in more treatment facilities for arsenic removal that will generate residuals. Furthermore, arsenic can be released from such wastes under the reduced conditions that are found in landfills. Pyrite (FeS2) is believed to be a compound that has a high affinity for arsenic and is stable under anoxic conditions. The first task of this research was to develop a method for making pyrite crystals of defined size with minimal reaction time and at high yield. Effects on the synthesis of pyrite particles of pH, the ratio of Fe/S, temperature and reaction time were investigated in batch reactor systems. Pyrite was synthesized within 24 hours at pH values ranging from pH 3.6 through pH 5.6, and at a ratio of Fe/S of 0.5. X-ray diffraction and scanning electron microscopy were used to size and characterize the pyrite particles. Experimental and analytical procedures developed for this work, included a hydride generation atomic absorption spectrometry method for measuring arsenic species (As(III), As(V)). The synthesized pyrite was applied to remove arsenic and its maximum capacity for arsenic removal was measured in batch adsorption experiments to be 3.23 μmol/g for As(III) and 113 μmol/g for As(V). Information obtained on the characteristics of chemical species before and after the reaction with arsenic showed that iron and sulfur were oxidized. Last, how strongly arsenic was bound to pyrite was investigated and it was determined that release of arsenic from As(III)-pyrite is not affected by pH, but release from As(V)-pyrite is affected by pH with minimum release in the range pH 5 to pH 8.

The waste water from the industrial production of the herbicide monosodium methyl arsenate was treated using coagulation. The coagulation process as developed in this research proved to be suitable for arsenic removal in aqueous media using chromium (III), calcium (II), and combination of calcium (II) and chromium (III), and magnesium (II). The results obtained suggest that the coagulation process can be used for the treatment of the waste water from the monosodium methyl arsenate production. Response surface methodology was used to study the effects of the various parameters, namely pH, mole ratios (Cr:As, Ca:As, and Mg:As), concentration of flocculent and initial arsenic concentration. To optimize the process conditions for the maximum removal of arsenic. Central composite and factorial designs were used to study the effects of these variables and to predict the effect of each. ANOVA was used to identify those factors which had significant effects on model quality and performance. The initial arsenic concentration appeared to be the only significant factor. These models were statistically tested and verified by confirmation experiments.

Arsenic is a prevalent contaminant at a large fraction of US Superfund sites. Therefore, establishing techniques for accelerating As remediation could benefit many contaminated sites. Remediation of As contaminated groundwater by conventional methods, i.e. pump and treat (P&T), can be impeded by slow desorption of As from Fe and Al (hydr)oxides in aquifer solids. Through experimentation at different physical scales (grain, bench, and field scale), the potential for chemical additions to increase As release from sediments and possibly accelerate P&T remediation is examined. The work described here focuses on As contamination and remediation at the Vineland Chemical Co. Superfund site in southern NJ. The site is extensively contaminated with As resulting from decades of poor chemical storage and disposal practices by the Vineland Chemical Co., which manufactured As-based biocides from 1949-1994. Despite significant intervention, including groundwater remediation by P&T and treatment of solids via soil washing, sufficient site clean up could require many decades with current technologies. Chemical amendments that either compete with As for sorption sites or dissolve Fe and Al (hydr)oxides can increase As mobility and potentially improve P&T remediation efficiency. Simple extrapolations from bench scale column experiments based on pore volumes suggest that treatment with 10 mM oxalic acid could lower the time necessary for clean up at the Vineland site from 600 years (with current techniques involving just groundwater) to potentially on the order of 4 years. Small scale (<1 mm2) X-ray fluorescence maps from columns performed within the synchrotron beamline showed As release during oxalic acid treatment that was consistent with the bulk column materials and suggested that microscale processes can be predictive of the larger system. Finally, during a 3-month pilot study at the Vineland site, oxalic acid was injected into a section of the aquifer via an injection manifold system that was designed and built for the experiment. Groundwater samples indicate that introduction of oxalic acid led to increased As release at a sampling well and pump and treat recovery well in the study area. Addition of oxalic acid shows promise for accelerating treatment of a highly contaminated site.

This research was directed at reducing arsenic levels in the effluents generated at the Canelands facility that manufactures monosodium methyl arsenate. Two effluent streams containing arsenic have to be considered, a raw water stream that is treated on site and a brine stream that is disposed of by sea outfall. Removal of arsenate from aqueous media by coagulation was investigated and models were developed describing selected variables that influence the removal of the arsenate. Three coagulant systems were investigated, namely aluminium(III) coagulation, iron(III) coagulation and binary mixtures of aluminium(III) and iron(III). Researchers have studied individual aluminium (III) sulphate and iron(III) chloride coagulation. No detailed research and modelling had, however, been carried out on the use of binary mixtures of aluminium (III) sulphate and iron (III) chloride coagulation of aqueous arsenate, nor had individual aluminium(III) sulphate and iron(III) chloride coagulation of arsenate been modelled at relatively high arsenate concentrations. The models that were generated were validated statistically and experimentally. The variables investigated in the aluminium(III) model included initial arsenate concentration, pH, polymeric flocculent concentration, aluminium(III) concentration and settling time. The variables modelled in the iron(III) coagulation were initial arsenate concentration, pH, polymeric flocculent concentration, and iron(III) to arsenic mole ratio. The modelling of the binary coagulant system included initial arsenate concentration, pH, iron (III) concentration, aluminium(III) concentration, and flocculent concentration as variables. The most efficient arsenic removal by coagulation was iron(III), followed by the binary mixture of aluminium(III) and iron(III) and the weakest coagulant was aluminium(III) sulphate. Scale-up coagulations performed on real raw water samples at a 50 litre volume showed that iron(III) was the most efficient coagulant (on a molar basis) followed closely by the binary mixture, while aluminium(III) coagulation was considerably weaker. The residual arsenic levels of the iron(III) and the binary coagulation systems met the effluent discharge criteria, but the aluminium coagulation system did not. Leaching tests showed that the iron(III) sludge was the most stable followed by the sludge of the binary mixture and the aluminium(III)-based sludge leached arsenic most readily. Settling rate studies showed that the flocs of the iron(III) coagulations settled the fastest, followed by binary mixture flocs and the aluminium flocs settled the slowest. The flocs of the binary mixture had the lowest volume, followed by the iron(III) flocs, while the aluminium(III) flocs were the most voluminous. Based on current operations of the raw water treatment plant the aluminium(III)-based coagulation is the most cost efficient. Given a relative costing of 1.00 for the aluminium(III) coagulation, the iron(III) chloride-based coagulation would be 2.67 times more expensive and the equimolar binary mixed aluminium(III)/iron(III) system would be 1.84 times the cost of aluminium(III) coagulation.

M.Sc. / Millions of inhabitants worldwide are exposed to arsenic contaminated drinking water as a result of natural and man-made processes. Arsenic especially its inorganic forms, arsenic (III) and arsenic (V) have negative effects on human health especially in developing countries. Therefore fabricating low cost and efficient adsorbents for arsenic (III) removal is of great importance. The aim of this study is to use magnetite (Fe3O4) as filler, incorporated into a polymer blend forming composites as adsorbents for arsenic (III) removal. This work presents the fabrication, characterization and application of Fe3O4-EVA/PCL composites for arsenic (III) removal from water. Fe3O4/Ethylene-vinyl acetate copolymer (EVA)/polyaniline (PANI) and Fe3O4/Ethylene-vinyl acetate copolymer (EVA)/polycaprolactone (PCL) nanocomposites have been successfully synthesized by melt blending technique using a laboratory mixer (Thermo Scientific Haake Rheomex OS). The composites were characterized using scanning electron microscopy (SEM) and x-ray diffraction (XRD) techniques. Thermal analysis was done by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and mechanical properties using INSTRON 4443 mechanical Tester. Ability of [EVA (70%) PCL (15%) Fe3O4 (15%)] composites to adsorbed As(III) from water has been investigated through batch experiments. The maximum adsorption was 2.83 mg/g of As(III) ions at 26 ±1°C and pH 8.6. Adsorption data were fitted to Langmuir, Freundlich and Dubinin-Radushkevich isotherms. The process fits well with the Langmuir isotherm. As(III) obeyed pseudo-second order kinetics. The nanocomposites investigated in this study showed good potential for As(III) removal from contaminated water may be due to the dispersion of the magnetite nanoparticles into the polymer blend composites which increases the surface area for the adsorption.

Groundwater arsenic contamination is currently a global problem, and also a concern at numerous former industrial sites, agricultural sites, landfill sites and mining operations in the U.S. This dissertation aims to develop improved strategies of remediating these arsenic contaminated aquifers. It focuses on two distinct approaches of remediation: (1) mobilizing arsenic from contaminated aquifer sediments to decrease the quantity of arsenic at the source of contamination; and (2) immobilizing arsenic in situ, to decrease the mobility and bioavailability of this arsenic. Optimal remediation may well involve combinations of these two approaches. Arsenic mobilization using oxalic acid is effective because oxalic acid dissolves arsenic host minerals and competes for sorption sites on those minerals. In this dissertation, oxalic acid treatment was tested using sediments with contrasting iron mineralogies and arsenic contents from the Dover Municipal Landfill and the Vineland Chemical Company Superfund sites. Oxalic acid mobilized arsenic from both sites and the residual sediment arsenic was less vulnerable to microbial reduction than before the treatment. Oxalic acid thus could improve the efficiency of widely used pump-and-treat remediation. Oxalic acid did not remove all of the reactive iron(III) minerals in Vineland sediment samples, and thus released significant quantities of arsenic into solution under reducing conditions than the Dover samples. Therefore, the efficacy of pump-and-treat must consider iron mineralogy when evaluating its overall potential for remediating groundwater arsenic. Arsenic immobilization occurs by changing the chemical state, or speciation, of arsenic and other elements in the system. Arsenic is often assumed to be immobile in sulfidic environments. In this dissertation, sulfate reduction was stimulated in sediments from the Vineland Superfund site and the Coeur d'Alene mining district. Sulfate reduction in the Coeur d'Alene sediments was more effective at removing arsenic from solution than the Vineland sediments. The Vineland sediments initially contained abundant reactive ferrihydrite, and underwent extensive sulfur cycling during incubation. As a result, arsenic in the Vineland sediments could not be effectively converted to immobile arsenic-bearing sulfides, but instead a part of the arsenic was probably converted to soluble thioarsenates. Therefore, coupling between the iron and sulfur redox cycles must be fully understood for arsenic immobilization by sulfate reduction to be successful. Arsenic can also be immobilized by retention on magnetite (Fe3O4). Magnetite is stable under a wide range of aquifer conditions including both oxic and iron(III)-reducing environments. In this dissertation, a series of experiments were performed with sediments from the Dover and Vineland Superfund sites, to examine the potential of magnetite for use in arsenic immobilization. Our data suggest that the formation of magnetite can be achieved by the microbial oxidation of ferrous iron with nitrate. Magnetite can incorporate arsenic into its structure during formation, forming a stable arsenic sink. Magnetite, once formed, can also immobilize arsenic by surface adsorption, and thus serve as a reactive filter when contaminated groundwater migrates through the treatment zone. Reactive transport modeling is used for investigating the magnetite based arsenic immobilization strategy and for scaling laboratory results to field environments. Such modeling suggests that the ratio between iron(II) and nitrate in the injectant regulates the formations of magnetite and ferrihydrite, and thus regulates the long-term evolution of the effectiveness of the strategy. The results from field-scale models favor scenarios that rely on the chromatographic mixing of iron(II) and nitrate after injection. The studies in this dissertation demonstrate that the environmental fate of arsenic depends on the biogeochemical cycling of arsenic, iron, and to a lesser extent, sulfur. The development of effective groundwater arsenic remediation strategies depends on a good understanding of each of the involved processes, and their combinations.

M.Sc. (Geology) / Most rural communities in developing countries rely on borehole water as their only source of water. Since borehole water comes from underground, it is often considered pure and clean, but this is frequently not the case. Groundwater contains certain amounts of trace elements that may become deleterious to human health. The objectives of this investigation were to assess the concentration levels of Potential Harmful Trace Elements (PHTEs) and their spatial distribution patterns in borehole water in the Greater Giyani area of Limpopo, South Africa, and the potential human health risks associated with this. The method of research comprised two phases: (I) In the first phase, I assessed the occurrence and distribution patterns of PHTEs in the boreholes of the Giyani area. A total of 29 water samples were collected from boreholes (including 15 community boreholes and 14 primary school boreholes) in the Greater Giyani area during the dry season (July/August 2012), and for comparison another 27 samples (including 15 community boreholes and 12 schools boreholes) from the same localities during the wet season (March 2013). The samples were analysed for the trace elements arsenic (As), cadmium (Cd), chromium (Cr), selenium (Se) and lead (Pb) using the Inductively Coupled Plasma Mass-Spectrometry (ICPMS) technique. In order to assess the groundwater quality, PHTEs concentrations were compared with the South African National Standard of Drinking water (SANS 241-1:2011). (II) In the second phase, I evaluated the geographic variation between PHTEs and associated human health effects. This involved acquisition of data on a total of 100 cancer cases recorded during the period 2011-2014 at Nkhensani Hospital. ArcGIS Spatial analyst tool was used to create thematic maps illustrating spatial distribution of clinical data and arsenic concentrations in boreholes.

Arsenic is found in drinking waters in many countries and since maximum allowable concentration is as low as 10 &micro / g/L, there are many research efforts to separate it from water. Membrane methods are used more and more widely in separation operations in recent years. Arsenic is mainly present in water as arsenite [As(III)] and arsenate [As(V)]. As pH of water changes, molecular formulas of As(III) and As(V) change. In this study, the performance of different ultrafiltration membranes for arsenic removal from water was investigated at different pH values, different feed concentrations and presence of other anions (SO42-, HPO42-, NO3-, Cl-). Donnan exclusion effect on separation was discussed since distribution of arsenite and arsenate anions change in water due to change in pH of the solution. Experiments were conducted via batch and continuous modes. For continuous ultrafiltration experiments, 30 kDa of polysulfone and 20 kDa of polyether sulfone membranes were used. Batch ultrafiltration experiments were performed with the usage of 3 kDa of regenerated cellulose membrane. Higher retention values for As(V) were obtained compared to retention values of As(III). When membranes&rsquo / performances were investigated, it was seen that highest As(V) removal was observed with the usage of polysulfone membrane. Increase in feed concentration and presence of other anions caused decrement in separation. Hydride Generation Atomic Absorption Spectrometry was used to perform analyses. Hydride generator part was designed, constructed and optimized to obtain reliable and accurate absorbance values.

In this thesis, the commercial viability of the aminolytic synthesis method is explored through robustness, versatility, and waste reduction studies. We report the preparation of metal precursors and the development of a synthetic approach using an aminolytic reaction of metal carboxylates in oleylamine and non-coordinating solvent. Manganese doping in the cobalt ferrites allows for the investigation of the couplings. All the compositions in the series Co1-xMnxFe2O4, 0.0  x  1.0 were synthesized via the aminolytic reaction. The coercivity decreases with increasing Mn2+ concentration due to reducing of high magnetic anisotropy ion (Co2+) content. To our knowledge, this work is the first completed series of Co1-xMnxFe2O4. The method is used to synthesize manganese ferrites dope with chromium. This allows for the investigation of the effects of orbital momentum quantum coupling. All the compositions of MnFe2-xCrxO4, x= 0.0, 0.05, 0.13, 0.25, 0.43, 0.62, and 0.85, were synthesized via the In-situ aminolytic method. Chromium concentration weakens the couplings resulting in the decrease in overall magnetic moment. All by-products can be recycled for re-utilization. The "mother" solution can be used for multiple batches without treatment. Our trials have shown that the reaction could undergo ten reactions using the same solution without scarifying the quality or yield of the product. Finally, an environmental application is explored through the use of iron oxides. Samples of goethite, maghemite, magnetite, and hematite were synthesized and characterized. These nanoparticles were exposed to arsenic and chromium solutions to measure the percent uptake of contaminant by each phase. Adsorption isotherms were plotted to obtain Freundlich parameters. The adsorption constant (K) averages over a 400% increase on literature values. We synthesized hematite and maghemite core-shell particles and exposed them to arsenite and maghemite core-shell particles have the higher removal affinity due to their smaller size.

Arsenic-based pesticide residues have been detected on Arizona State Museum’s (ASM) Diné (Navajo) textile collection using a handheld portable X-ray (pXRF) spectrometer. The removal of this toxic pesticide from historic textiles in museums and collections is necessary to reduce potential health risks to Native American communities, museum professionals, and visitors to these cultural institutions. A leader in engineering innovative pesticide removal methods, ASM received federal funding support to continue essential research in removing heavy metal pesticides from cultural property. The research objective was divided into three interconnected stages: (1) calibrate the pXRF instrument for arsenic contaminated cotton and wool textiles; (2) engineer a textile conservation aqueous washing treatment to remove arsenic from wool textiles; (3) demonstrate the aqueous washing treatment method on actual Navajo textiles known to have arsenic-based pesticide residues. The calibration process consisted of a dipping method to produce known homogenous arsenic cotton and wool test samples saturated with solutions of 100, 500, 1000, 2500, and 5000 parts per million (ppm). A linear correlation between observed pXRF test readings and formulated arsenic solutions corroborated the instruments range of detection for arsenic on specific textile materials. The calibration confirms that the pXRF is suitable instrument to measure the removal of arsenic from wool textiles. Wool test samples treated with solutions of an arsenic concentration of 1000ppm were used to develop an optimal aqueous washing treatment exploring the effects of time, temperature, agitation, and pH conditions to efficiently remove arsenic while minimizing damage to the structure and properties of the textile. Each conditional effect removed a certain percentage of arsenic, although the most efficient aqueous washing treatment consisted of submerging a wool textile in deionized water at room temperature for ten minutes with the greatest level of agitation within reason to minimize damage the textile. The final stage of the research applied the aqueous washing guidelines formulated from experimental research on three historic ASM Navajo textiles. Two textiles contained low arsenic concentrations (<100ppm), and one tested with a high arsenic concentration (~1000ppm). The aqueous washing treatment resulted in minimal change for low arsenic concentration textiles, and a 96% removal of arsenic on a high arsenic concentration textile. The preliminary success of removing arsenic-based pesticide residues from historic Navajo textiles greatly impacts the future management of historic textile collections, and also raises questions to further refine the research methodology or pursue alternative related research such as engineering a closed circulating arsenic removal system to limit the quantity of toxic water.