Abstract The object of this study was to investigate the synthesis of a nanoscale zero-valent iron slurry (NZVIS) for use in Fenton-like reactions, and to evaluate its efficiency for As(III) oxidation to As(V) in spiked deionized water and simulated groundwater containing humic acid. Furthermore, this study used injection of the nanoiron slurry combined with electrokinetic processes to remediate As(III) in soil. NZVI was prepared by a chemical reduction process. The efficiency of using 3 wt% soluble starch (SS) to stabilize NZVI was also studied. It was found that the SS could keep the nanoparticles dispersed for over one day. The NZVI was characterized by XRD, FE-SEM, ESEM-EDS, and EDS-mapping, to observe its morphology and crystal structure. In this research the iron species observed took non-crystalline forms. In water batch tests, studies in deionized water were compared with those in simulated groundwater with humic acid, and dissolved oxygen content was adjusted. Injection of NZVIS oxidized As(III) to As(V) in all cases. In both deionized water and simulated groundwater, it was found that when the dissolved oxygen(DO) content was not increased, the NZVIS generated non-selective oxidant OH¡E, thus reducing the As(V) production rate. When dissolved oxygen content was increased, the DO oxidized organic matter present in the simulated groundwater, allowing the OH¡E to react further with As(III) and increasing the As(V) production rate. Finally, a test was performed in actual groundwater under optimal reaction conditions, without increasing the dissolved oxygen content, for comparison of As(V) yield. The concentration of As(V) was found to be higher in this test (As(V) Conc. = 17.55 £gg/L) than when using simulated groundwater (As(V) Conc. = 4.63 £gg/L). This study further examined NZVIS injection combined with electrokinetic (EK) technology for the remediation of soil columns containing a low concentration (initial conc. = 100 mg/kg) and a high concentration (initial conc. = 500 mg/kg) of As(III). EK alone without injection of NZVIS (Test E-1) resulted in a residual soil As(V) concentration of 24 mg/kg in the low-concentration test group. In Test E-2, where NZVIS was injected into the anode reservoir, and Test E-3, where NZVIS was injected into the cathode reservoir, residual soil As(V) concentrations were 2.3 mg/kg and 3.4 mg/kg, respectively. The high-concentration test group was comprised of Test E-4 (EK alone without injection of NZVIS), Test E-5 (NZVIS injected into anode reservoir), and Test E-6 (NZVIS injected into cathode reservoir). In these tests, only soil sections 0.2 and 0.4 (normalized distance from anode reservoir) met soil regulation standards. Residual As(V) concentrations in soil sections 0.6, 0.8, and 1.0 are much higher than the regulatory standard. In soil section 1.0, the residual As(V) concentration was less in Test E-6 than in Test E-5 (116.6 mg/kg and 183.5 mg/kg, respectively). This may be because at high pH values, the iron surface does not corrode, instead arsenic adsorption prevails. Only a fraction of negatively charged As(V) species will migrate towards the anode resulting in a relatively low soil As(V) concentration near the cathode.

Evaluating the ability of biosorbents to remove arsenic from water has global significance due to the widespread availability and low cost of biosorbent materials. In this study, the ability of coffee grounds and coconut substrate (two previously unreported biosorbents) to remove arsenic from water was compared against the performance of arsenic removal on rice husk (a recognized and widely tested biosorbent). The three biosorbents were individually screened for their ability to remove arsenite, As (III), and arsenate, As (V), from water. Batch reactors were employed to assess the percent removal, reaction kinetics, adsorption capacity, and desorption of each arsenic species onto/from biosorbents under pH buffered and non‐buffered conditions. The resulting experimental data was statistically interpreted using analysis of variance and ttesting of the means. The experimental results were also fit to existing kinetic and isotherm models to provide kinetic rate constants, the maximum adsorption capacity, and to help interpret the nature of the reactions on the biosorbent surface. While all three biosorbents removed arsenic with similar initial reaction kinetics (pseudo 1st order reaction rate constant for As (III) was 0.13 hr^‐1 for all three biosorbents and for As (V) was 0.17 hr^‐1 for coffee grounds and rice husk and 0.15 hr^‐1 for coconut substrate), the amount of arsenite and arsenate removed was highest for coffee grounds (84 and 91 percent, respectively), followed by rice husk (68 and 72 percent, respectively), and then coconut substrate (26 and 24 percent, respectively). The maximum adsorption capacity of arsenite and arsenate was determined for coffee grounds (0.66 and 0.70 mg/g, respectively) and rice husk (0.55 and 0.66 mg/g, respectively). While desorption was observed for both coffee grounds and rice husk, the total amount of desorption accounted for less than 15 percent of the total retained mass. The results of this thesis work reveal that coffee can be used as an effective biosorbent when compared to rice husk; however, coconut substrate is less effective than rice husk at removing As (III) and As (V).

Chapter 2: Germination and Growth of Radish (Raphanus sativus) and Lettuce (Lactuca sativus) Exposed to Arsenite and Arsenate in Hydroponic Growth Solution Little information is available on the survival, uptake, and dry mass production of vegetable seedlings and maturing plants in arsenic enriched environments. Such information is however very important to many vegetable growers in areas of subsistent agricultural like Bangladesh or home-gardeners in closer proximity of As sources such as metal smelters. Accordingly we conducted research investigating (i) the germination and radical formation of radish and lettuce seeds at varying As (V) and As (III) concentrations and (ii) radish and lettuce plants in solution culture. Seed germination studies demonstrated that 0.1mM and 0.025mM are toxic threshold levels of As (III and V) for radishes and lettuce, respectively, while As (V) is more toxic to radish seeds than As (III). Arsenic (III and V) impacted both germination and radical development in radish seeds. For lettuce we observed that As had no impact on germination but reduced radical length significantly (p < 0.01). At most equimolar concentrations, As (III) was more toxic than As (V) in lettuce seeds (0.025 - 0.10mM As), a result contrary to those obtained in radish seeds (0.05 - 0.5mM As). The hydroponic growth studies showed that losses and increases in dry weight are a function of absorbed As and are dependent on the source of As: As (V) or As (III). Moreover, the effect of absorbed As (V) or As (III) on dry weight reductions and increases differed between root and shoot portions of the plants and are crop dependent. Tissue-As (originally solution As (V)) was more toxic at the radish root level and tissue-As (originally solution As (III)) was more toxic at the radish shoot level. Conversely for lettuce, As (III) caused reductions in dry weight, while As (V) had a stimulating effect on biomass production. Lower As (V) concentrations in plant tissue throughout the lettuce study and at low As (V) concentrations (0.02mM) in the radish study may be explained by the molar ratio of P:As of approximately 5. From a food nutrition safety standpoint, studies need to concentrate on sub-lethal levels in order to ensure the proper formation of the harvestable portion of the plant. Chapter 3: Adsorption of Arsenate (V) and Arsenite (III) on Goethite in the Presence and Absence of Soluble Organic Carbon The environmental fate of arsenic is of utmost importance as the U.S. EPA has recently proposed to tighten the arsenic drinking water standard from 50 ppb to 5 ppb. In natural systems the presence of dissolved organic carbon (DOC) may compete with As for adsorption to mineral surfaces, hence increasing its potential bioavailability. Accordingly, the adsorption of arsenate As (V) and As (III) on goethite (α-FeOOH) was investigated in the presence of either a peat humic acid (Hap), a Suwannee River Fulvic Acid (FA) (IHSS) or citric acid (CA). Adsorption edges and kinetic experiments were used to examine the effects of equimolar concentrations of organic adsorbates on arsenic adsorption. Adsorption envelopes were conducted over a pH range of 11 to 3, while the kinetic studies were conducted at pH 6.5 for As (V) and pH 5.0 for As (III). Arsenate adsorption was inhibited in the order of Hap > FA > CA while arsenite adsorption was inhibited in the order of CA > FA > Hap. Humic acid reduces As V adsorption starting at pH 9, with a maximum reduction at pH 6.5. Fulvic acid slightly inhibited As (V) adsorption starting at pH 5, and this inhibition increased with a decrease in pH. No effect was observed in the presence of CA. Arsenite adsorption is inhibited by HA starting a pH 7 and increases with a decrease in pH, while FA and CA reduce As (III) adsorption beginning at pH 8, with a continuous reduction as the pH decreases. The differential extent of As V adsorption in the presence of the organic acids suggests that the distribution and the respective densities of the abundant functional groups (phenol/ catechol OH or COO⁻) are significant in the adsorption of As (V). Furthermore, larger organic acids may hydrophobically partition to surfaces via a more favorable entropy driven reaction mechanism which may influence As (V) diffusion and its subsequent adsorption to surfaces. The decrease in As (III) adsorption is caused by its reduced affinity for the surface at pH values lower than 9, and the simultaneous increase in surface activity by the organic substances' via their COO⁻ functional groups. The results of these experiments suggests that dissolved organic carbon substances are capable of increasing the bioavailability of As in soil and water systems in which the dominant solid phase is a crystalline iron oxide. Chapter 4: Adsorption of Arsenate and Arsenite on Ferrihydrite in the Presence and Absence of Dissolved Organic Carbon (DOC) The adsorption of As (V) and As (III) on synthetic 2-line ferrihydrite in the presence and absence of a peat humic acid (Hap), Suwannee River Fulvic Acid (FA) or citric acid (CA) was investigated. Previous work with goethite has demonstrated the ability of DOC materials to reduce As (V) and As (III) adsorption. In this study, a batch technique was used to examine the adsorption of arsenic (III and V) and DOCs on ferrihydrite in the pH range from 3 to 11. The results obtained demonstrated that As (V) adsorption on ferrihydrite was reduced only in the presence of CA. Arsenate reduced the adsorption of all organic acids except Hap. Both FA and CA reduced As (III) adsorption on ferrihydrite, while Hap had no effect. Fulvic and citric acid adsorption on ferrihydrite was reduced in the presence of As (III), however, adsorption increases of FA and CA were observed at lower pH, which is consistent with a decrease in As(III) adsorption. The peat humic acid had no effect on As (III) adsorption, and we believe that the adsorption process of Hap and As (III and V) on ferrihydrite are independent of each other. The observed differences between this study and the study on goethite are believed to be an intricate function of ferrihydrite's surface characteristics, which affects the mechanisms of surface adsorption and hence the affinity of organic acids such as Hap, FA, and CA for the ferrihydrite surface. As such, the adsorption of DOCs to ferrihydrite are assumed to be energetically less favorable and to occur with a fewer number of ligands, resulting in lower surface coverage of weaker bond strength. Additional factors for the observed differences are discussed. This work demonstrates the importance of the solid phase in adsorption processes and functional group composition, as noticeable differences are observed in comparison to a crystalline Fe-oxide solid phase. / Master of Science

Iron (Fe) speciation is important for many biogeochemical processes. The high abundance and limited solubility of Fe(III) are responsible for the widespread occurrence of Fe(III) minerals in the environment. Co-precipitation and adsorption onto mineral surfaces limits the free concentrations of compounds such as arsenate (As(V)), Fe(III) and, phosphate (P(V)). Mineral dissolution, on the other hand, might lead to elevated concentrations of these compounds. Fe speciation is strongly affected by natural organic matter (NOM), which suppresses hydrolysis of Fe(III) via complexation. It limits the formation of Fe(III) minerals and Fe(III) co-precipitation. This thesis is focused on interactions between Fe(III) and NOM as well as their impact on other elements (i.e. As(V) and P(V)). X-ray absorption spectroscopy (XAS) was used to obtain molecular scale information on Fe and As speciation. This was complemented with infrared spectroscopy, as well as traditional wet-chemical analysis, such as pH and total concentration determinations. Natural stream waters, soil solutions, ground water and soil samples from the Krycklan Catchment, in northern Sweden, were analyzed together with model compounds with different types of NOM. A protocol based on ion exchange resins was developed to concentrate Fe from dilute natural waters prior to XAS measurements. Iron speciation varied between the stream waters and was strongly affected by the surrounding landscape. Stream waters originating from forested or mixed sites contained both Fe(II, III)-NOM complexes and precipitated Fe(III) (hydr)oxides. The distribution between these two pools was influenced by pH, total concentrations and, properties of NOM. In contrast, stream waters from wetland sites and soil solutions from a forested site only contained organically complexed Fe. Furthermore, the soil solutions contained a significant fraction Fe(II)-NOM complexes. The soil samples were dominated by organically complexed Fe and a biotite-like phase. Two pools of Fe were also identified in the ternary systems with As(V) or P(V) mixed with Fe(III) and NOM: all Fe(III) was complexed with NOM at low total concentrations of Fe(III), As(V) and/or P(V). Hence, Fe(III) complexation by NOM reduced Fe(III)-As(V)/P(V) interactions at low Fe(III) concentrations, which led to higher bioavailability. Exceeding the Fe(III)-NOM complex equilibrium resulted in the occurrence of Fe(III)-As(V)/P(V) (co-)-precipitates.

Excessive concentrations of arsenic in soil- and groundwater constitute a global issue. The spread of arsenic is due to both natural and anthropogenic effects in the environment. Historically, the anthropogenic emissions have originated from several different industrial sectors e.g. wood impregnation. In Sweden, there are approximately 85 000 contaminated sites. Most of them are contaminated due to industrial activities. The emissions of arsenic in Sweden are mainly due to the wood impregnating agent CCA (copper, chromium and arsenic). Arsenic is a toxic metalloid that predominantly occurs as the inorganic compounds arsenite As[III] and arsenate As[V] in soil and groundwater. The mobilization of the arsenic compounds in soil water is affected by the redox conditions and by other conditions in the field, e.g. pH. Arsenate adsorbs stronger to iron- and aluminum hydroxides. Arsenite is the most toxic, mobile and soluble of the two compounds.   In a previously remediated impregnation plant in Hjältevad, Småland, arsenic has started to spread in the soil and groundwater. High dissolved concentrations of arsenic have been measured in the area. A hypothesis about the recent mobilization of arsenic is that pollutants below the groundwater table which were left behind after remediation started to dissolve due to changed redox conditions. This report aims to evaluate how the mobilization and adsorption of arsenic in Hjältevad is effected by pH and redox potential. This was addressed by leaching tests and geochemical modeling in Visual MINTEQ. Soil samples were collected during autumn 2017. Soil samples from seven different sampling points, taken from different depths were collected. Leaching tests were carried out for both dry and humid soil samples. Oxalate extractable arsenic was used together with measured dissolved concentrations of cat- and anions as input in Visual MINTEQ. The input data were used to evaluate the mobilization and adsorption of arsenite, arsenate and total arsenic due to pH, redox potential and the specific surface area of ferrihydrite. The modeling showed that the mobilization and adsorption of arsenic is dependent on pH, redox potential and reactive surfaces in the soil solution. Arsenate was adsorbed more strongly between pH 4.5 and 6.5 while arsenite was adsorbed at pH values greater than 7. The conclusion is that the mobilization and adsorption of arsenic were affected to some extent by the pH value. However the redox potential and the specific surface area of ferrihydrite were more influential. To verify the trends seen in the report, additional modeling is required. The report shows that most likely, arsenic started to mobilize in Hjältevad due to the changed redox conditions.

This study was conducted to determine how the structure and surface chemistry of bulk CaCO3 differs from that of nanometer-sized CaCO3 and then to determine rate, extent and mechanisms of As adsorption on various synthetic CaCO3 materials. Additionally, we sought to devise a chemical CaCO3 precipitate that approximates biogenic CaCO3. The bulk CaCO3 precipitation was performed by using a solution that was highly oversaturated so that large CaCO3 precipitates rapidly form. Two different methods were employed for the synthesis of nanometer size CaCO3 i) an in situ deposition technique and ii) an interfacial reaction (water in oil emulsion). Mineral characterization of all CaCO3 precipitates was done with Nitrogen Porosimetry (Brunauer Emmett Teller method), particle size analysis, X-ray diffraction and Fourier Transform Infrared/ Fourier Transform Raman spectroscopy. The principal objective of the research was to assess the overall reactivity of As(III) and As(V) with different synthetic CaCO3 minerals. This was accomplished by i) running adsorption isotherms (varying As concentration), ii) measuring pH envelopes (varying pH at a fixed concentration) and iii) kinetic experiments (varying reaction time). Also, electrophoretic mobility experiments were performed in the presence of As(III) and As(V), and these studies revealed that As(III) forms stronger inner-sphere complexes with CaCO3 than As(V). Also, it was found that nanometer-sized CaCO3 prepared via deposition formed stronger inner-sphere complexes with As oxyanions (q = 5.26 µmol/m2) compared to either nano-sized CaCO3 from interfacial reactions (q = 4.51 µmol/m2) or bulk CaCO3 (q = 4.39 µmol/m2).<p> The PEG-based nano CaCO3 prepared by an in-situ deposition technique presents a novel and readily available synthesis route that can be used as proxy for the biogenic CaCO3 known to be present in many different environmental conditions. The results of this study suggest that CaCO3 can be used as a sorbent for As in groundwater.

This study was conducted to determine how the structure and surface chemistry of bulk CaCO3 differs from that of nanometer-sized CaCO3 and then to determine rate, extent and mechanisms of As adsorption on various synthetic CaCO3 materials. Additionally, we sought to devise a chemical CaCO3 precipitate that approximates biogenic CaCO3. The bulk CaCO3 precipitation was performed by using a solution that was highly oversaturated so that large CaCO3 precipitates rapidly form. Two different methods were employed for the synthesis of nanometer size CaCO3 i) an in situ deposition technique and ii) an interfacial reaction (water in oil emulsion). Mineral characterization of all CaCO3 precipitates was done with Nitrogen Porosimetry (Brunauer Emmett Teller method), particle size analysis, X-ray diffraction and Fourier Transform Infrared/ Fourier Transform Raman spectroscopy. The principal objective of the research was to assess the overall reactivity of As(III) and As(V) with different synthetic CaCO3 minerals. This was accomplished by i) running adsorption isotherms (varying As concentration), ii) measuring pH envelopes (varying pH at a fixed concentration) and iii) kinetic experiments (varying reaction time). Also, electrophoretic mobility experiments were performed in the presence of As(III) and As(V), and these studies revealed that As(III) forms stronger inner-sphere complexes with CaCO3 than As(V). Also, it was found that nanometer-sized CaCO3 prepared via deposition formed stronger inner-sphere complexes with As oxyanions (q = 5.26 µmol/m2) compared to either nano-sized CaCO3 from interfacial reactions (q = 4.51 µmol/m2) or bulk CaCO3 (q = 4.39 µmol/m2).<p> The PEG-based nano CaCO3 prepared by an in-situ deposition technique presents a novel and readily available synthesis route that can be used as proxy for the biogenic CaCO3 known to be present in many different environmental conditions. The results of this study suggest that CaCO3 can be used as a sorbent for As in groundwater.