Ferrihydrite in a suspension has been studied as a solution for purification of arsenic contaminated water. Many development countries, amongst them Burkina Faso, have arsenic in their groundwater and the current methods for purification are too expensive. Measurements have shown extremely high levels of arsenic in the groundwater in several places in Burkina Faso. Since the availability of surface water is limited, the groundwater is still used as drinking water.   A suspension of ferrihydrite has capacity to adsorb arsenic in water due to its chemical characteristics. Small-scale laboratory work with ferrihydrite suspensions has been performed in parallel in Uppsala, Sweden, and Ouagadougou, Burkina Faso. To purify the water with regard to the economical and practical circumstances in Burkina Faso, a column with safety filter was made out of simple materials such as plastic bottles, plastic tubes and glass wool. The contaminated water was flowing upwards through the column to prevent the filter from clogging.   In Uppsala it was discovered that a 1 L ferrihydrite suspension containing 10 g ferrihydrite can adsorb 0.7 g arsenic while it was shaken and centrifuged well. In Ouagadougou it was possible, in the setup, to clean 2 L arsenic contaminated water with the concentration of 100 µg/L. The conclusions from the experiments in this project are that ferrihydrite can adsorb arsenic in contaminated water but that the setup used needs to be further evaluated and developed

published_or_final_version / abstract / Medicine / Doctoral / Doctor of Philosophy

published_or_final_version / abstract / Paediatrics and Adolescent Medicine / Master / Master of Philosophy

published_or_final_version / Medicine / Master / Master of Philosophy

There is a continued interest in the properties of arsenic thiolate compounds for both industrial and biological uses. Recent discoveries in the medicinal properties of such compounds have resulted in a sustained need for the synthesis of new dithiarsolane compounds for research as anti-leukemic compounds. Close analogues of the 2-halo arsenic dithiolates, namely those with an arsenic-carbon bond instead of an arsenic-halide bond, have recently been shown to have some efficacy towards leukemia cells. Based on the hydrolytic character and the active role of glutathione with arsenic in vivo, the compounds reported here may also have such activity. Arsenic compounds have demonstrated biological activity in the literature, thus the hypothesis of this thesis is cyclized arsenic thiolates can be synthesized with the appropriate characteristics as to be potentially useful medicinal agents as well as provide new structural and reaction information. A series of arsenic and antimony di- and trithiolates has been synthesized and characterized. Those compounds include 2-chloro-1,3,2-dithiarsolane, 2-bromo- 1,3,2-dithiarsolane, 2-iodo-1,3,2-dithiarsolane, 2-chloro-1,3,2-dithiarsenane, 2-bromo- 1,3,2-dithiarsenane, 2-iodo-1,3,2-dithiarsenane, 3-chloro-4H,7H-5,6-benz-1,3,2- dithiarsepine, 2-chloro-benzo-1,3,2-dithiarsole, 1,2-bis-dithiarsolan-2-ylmercapto-ethane, tris-(pentafluorophenylthio)-arsen, bis(2-(1,3,2-benzodithiarsol-2ylsulfanyl)- benzenesulfide), 2-chloro-benzo-1,3,2-dithiastibole, and bis(2-(1,3,2-benzodithistibol)- 1,2-benzenedithiol. Elucidation of the pH characteristics of arsenic dithiolates within the human toxicity reaction pathway is an area of interest. It has been shown that the aqueous arsenic dithiolate stability depends on the size of the ring. 2-Chloro-1,3,2-dithiarsolane has been shown to be somewhat stable at both low and high pH as well as neutral pH. 1,2-bis- Dithiarsolan-2-ylmercapto-ethane is completely stable in a neutral aqueous solution. Glutathione does not permanently bind to arsenic even in overwhelming excess. In particular, these fully characterized compounds determine how reactive the AsS and AsCl linkages are under environmental and biological conditions, and provide a source of new reagents to examine in medical applications. Future applications may include the incorporation of the reported compounds in filtration and remediation technologies with further modification.

Arsenic is a highly toxic, easily transportable and widespread contaminant in groundwater throughout the world. Arsenic causes acute toxicity by disrupting biological functions. In groundwater arsenic concentrations can reach up to a few milligrams per liter. Current regulations on arsenic content in drinking water are becoming more stringent and require the standard to be reduced to a few parts per billion. Arsenic exists as oxyanions in aqueous solution in either trivalent or pentavalent oxidation states depending on the oxidation-reduction potential and pH of the medium. Several treatment methods are available for removing arsenic from water. However, cost, operational complexity of the technology, skill required to operate the technology and disposal of arsenic bearing residual are factors that should be considered before the selection of any treatment method. Most of these techniques are also effective only in removing As(V) and not As(III). N,N’-bis(2-mercaptoethyl)isophthalamide), abbreviated BDTH2, is known to effectively precipitate soft heavy metals from water. A solid-supported reagent with the metal capture ability of BDTH2 would be ideal to use as a filtration column packing material for removal of aqueous As(III). In order to attain this objective, a new dithiol compound, 2,2'-(isophthaloylbis(azanediyl))bis(3-mercaptopropanoic acid) (abbreviated ABDTH2) has been synthesized and immobilized on silica beads. Silica-supported reagent ABDTH2 (SiABDTH2) thus prepared, completely removed As(III) from water by forming As-S bonds. In batch study, SiABDTH2 reduced the concentration of As(III) in aqueous solutions from 200 ppb to below 5 ppb at pH 5, 7 and 9. XAFS study of ABDT-As(III) and SiABDT-As(III) indicated that arsenic was present in +3 oxidation state as well as As(III) was only bonded to sulfur atom of ABDT unit. When SiABDTH2 was used as filtration column material, only 3% of ABDTH2 was leached out from the column. However, 100% As(III) was removed from 20 L of 200 ppb As(III) aqueous solution at a flow rate of 20 mL/min.

Mercury and arsenic are widespread contaminants in aqueous environments throughout the world. The elements arise from multiple sources including mercury from coal-fired power plants and wells placed in natural geological deposits of arseniccontaining minerals. Both elements have significant negative health impacts on humans as they are cumulative toxins that bind to the sulfhydryl groups in proteins, disrupting many biological functions. There are currently no effective, economical techniques for removing either mercury or arsenic from aqueous sources. This thesis will demonstrate a superior removal method for both elements by formation of covalent bonds with the sulfur atoms in N,N’-Bis(2-mercaptoethyl)isophthalamide (commonly called “B9”). That B9 can precipitate both elements from water is unusual since aqueous mercury exists primarily as a metal(II) dication while aqueous arsenic exists as As(III) and As(V) oxyanions.

Arsenic (As) is a common occurring environmental pollutant. The USEPA has a stricter regulation for arsenic in drinking water (10 ug/L). Small drinking water suppliers from regions with high arsenic backgrounds levels, will need to remove arsenic from drinking water in order to meet the new standard. The proposed treatment by the USEPA is the oxidation of arsenite (AsIII) to arsenate (AsV) followed by the adsorption onto metal oxides (e.g. granular ferrihydrite (GFH)). Large amounts of arsenic-bearing solid waste will be generated and disposed in municipal landfills based on EPA's recommendation. The alkaline and anaerobic conditions prevailing in mature landfills combined with the high content of organic matter and the microbial activity prevailing in landfill could play an important role in the biotransformation and mobilization of sorbed arsenic in landfills. The extensive use of organo arsenical compounds such as pesticides in agriculture has become an emerging source of arsenic contamination in the environment. Roxarsone (4-hydroxy-3-nitrophenylarsonic acid) is a compound supplemented in the poultry feed to enhance growth by controlling coccidian parasites. Chickens excrete the roxarsone without changes in its chemical structure. Land application of chicken manure in agricultural fields is a common practice. Approximately 900 metric tons of roxarsone is estimated to be released into environment in the U.S. annually. The environmental impact is significant when considering that these quantities of arsenic are spread onto relative small land areas in the direct vicinity of poultry houses. The aim of this study is to evaluate the role of anaerobic bioconversion on the fate and mobility of inorganic and organic arsenic compounds. The results taken as a whole suggest that arsenic in drinking water residuals is susceptible to enhanced mobilization due to anaerobic microbial activity, and therefore As mobilization should be expected in mature landfills. Roxarsone was readily biotransformed by a methanogenic consortium to its corresponding amino compound, 4-hydroxy-3-aminophenylarsonic acid (HAPA). A fraction of the HAPA went on to be converted to AsIII after long term incubations. Therefore, land application of roxarsone-containing wastes could potentially lead to the formation of more toxic and mobile forms of arsenic which will have negative impact on the environment.

The recent lowering of the arsenic MCL from 50 ppb to 10 ppb in 2006 will cause many utilities to implement new technologies for arsenic removal. Most of the affected utilities are expected to use adsorption onto solid sorbents for arsenic removal, especially in the arid Southwest, where conserving and re-using water is of utmost importance. This would cause the generation of more than 6 million pounds of arsenic residuals every year, which then would be disposed of in landfills. This thesis effort focuses on the testing of different aluminum and iron (hydr)-oxide based sorbents that are likely to be used for arsenic removal and assessing the behavior of these Arsenic Bearing Solid Residuals (ABSRs) under landfill conditions. It was demonstrated that the Toxicity Characteristic Leaching Procedure (TCLP) test underestimates the arsenic mobilization in landfills. Desorption of arsenic from ABSRs was quantified as a function of the range of pH and concentrations of competitive anions like phosphate, bicarbonate, sulfate and silicate and NOM found in landfills. The effect of pH is much more significant than the anions and NOM. Arsenic release due to competition of different anions is neither additive nor purely competitive. Landfill conditions were simulated inside long-term, continuous flow-through column reactors, and arsenic mobilization from sorbents was measured under those conditions. The results indicate that under reducing conditions, and in the presence of other competitive anions and high organics, microbes reduce arsenate to arsenite, which is a much more mobile species. Fe(III) is also reduced to Fe(II) under these conditions. Arsenic is transported in the particulate phase, associated with the iron, much more than in the dissolved phase. It was also observed that the sorbent itself might leach away at a faster rate than the arsenic sorbate causing a depletion of surface sites and a sudden spike in the release rate of arsenic, after a long residence time. Finally, investigation of different solid sorbents indicate, that the rate of leaching and the form of arsenic released varies widely and is independent of the respective adsorption capacities, even under similar leaching conditions.

Introduction: It has been reported that the principal source of exposure for humans to inorganic arsenic (As) comes from drinking water. It is known that selenium (Se) competes with the reductive metabolism and methylation of As and Se compete for the availability of glutathione. The overarching goal of this dissertation research is to assess relationships between arsenic intake from water and other fluids with urinary arsenic output and then to assess how urinary arsenic output is modified by selenium exposure. Methods: Households in the Binational Arsenic Exposure Survey (BAsES) were selected for their varying groundwater arsenic concentrations. A first morning urine void and water samples from all household drinking sources were collected for As quantification. Relationships were examined between various urinary arsenic biomarkers and estimated arsenic exposures. The association between urinary arsenic biomarkers and dietary intake and urinary output of selenium was also evaluated. Results: Arizonans reported consuming 18.5 mL/kg-day of water and 34.3 mL/kg-day from all fluids. In contrast, participants from Mexico reported 3.5 mL/kg-day of water and 12.3 mL/kg-day from all fluids. Median urinary inorganic As concentration among Arizona participants (ranging from 1.2 to 2.0 µg/L) was lower than among participants from Mexico (range 2.5 to 6.2 µg/L). 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. No statistically significant relationships were seen between urinary methylated arsenic biomarkers with either dietary intake of selenium or the urinary selenium concentration. Conclusion: Water was the primary contributor to total fluid intake among Arizonans while Mexico participants primarily consumed carbonated beverages. Arsenic intake from water was significantly associated with urinary arsenic output; however, the concentration of arsenic consumed explained a small fraction of urinary arsenic levels. While selenium can biologically interact with arsenic in the liver, no relationship between urinary arsenic biomarkers were identified with either dietary intake of selenium or urinary output of selenium.