PhD (Environmental Sciences) / Department of Ecology and Resource Management / The presence of arsenic in groundwater has drawn worldwide attention from researchers and public health officials due to its effects on human health such as, cancer, skin thickening, neurological disorders, muscular weakness, loss of appetite and nausea. World Health Organisation (WHO) has set the limit of 10 μg/L for arsenic in drinking water in trying to reduce the effects of arsenic. This was further adopted by South African National Standard (SANS). The present study aims at evaluating arsenic concentration in selected groundwater sources around Greater Giyani Municipality in Limpopo Province and further synthesize clay based adsorbents for arsenic removal using Fe3+ and Mn2+ oxides and hexadecylammonium bromide (HDTMA-Br) cationic surfactant as modifying agents. The first section of the work presented the hydrogeochemical characteristics of groundwater in the Greater Giyani Municipality. The results showed that the pH of the samples ranges from neutral to weakly alkaline. The dominance of major anionic and cationic species was found to be in the order: HCO3 ->Cl->SO4 2->NO3 - and Na+>Mg2+>Ca2+>K+>Si4+, respectively. Hydrogeochemical facies identified in the study area include CaHCO3 (90%) and mixed CaNaHCO3 (10%) which shows the dominance of water-rock interaction. About 60% of the tested samples contains arsenic concentration above 10 μg/L as recommended by SANS and WHO. Concentration of arsenic was found to be ranging between 0.1 to 172.53 μg/L with the average of 32.21 μg/L. In the second part of this work, arsenic removal efficiency of locally available smectite rich and kaolin clay was evaluated. Results showed that the percentage As(V) removal by kaolin clay was optimum at pH 2 while the percentage As(III) removal was greater than 60% at pH 2 to 12. For smectite rich clay soils, the percentage of As(III) and As(V) removal was found to be optimum at pH between 6 and 8. The adsorption isotherm data for As(III) and As(V) removal by both clays fitted better to Freundlich isotherm. Adsorption of both species of arsenic onto the clay mineral occurred via electrostatic attraction and ion exchange mechanisms. Both clay soils could be regenerated twice using Na2CO3 as a regenerant. Kaolin clay showed a better performance and was selected for further modification. In the third section of this work, Fe-Mn bimetal oxide modified kaolin clay was successfully synthesized by precipitating Fe3+ and Mn2+ metal oxides to the interlayer surface of kaolin clay. Modification of kaolin clay increased the surface area from 19.2 m2/g to 29.8 m2/g and further v decreased the pore diameter from 9.54 to 8.5 nm. The adsorption data fitted to the pseudo second order of reaction kinetics indicating that adsorption of As(III) and As(V) occurred via chemisorption. The adsorption isotherm data was described by Langmuir isotherm models showing a maximum As(III) and As(V) adsorption capacities of 2.16 and 1.56 mg/g, respectively at a temperature of 289 K. Synthesized adsorbent was successfully reused for 6 adsorptiondesorption cycles using K2SO4 as a regenerant. Column experiments showed that maximum breakthrough volume of ≈2 L could be treated after 6 hours using 5 g adsorbent dosage. Furthermore, the concentration of Fe and Mn were within the WHO permissible limit. In the fourth part of the work kaolin clay was functionalized with hexadecyltrimethylamonium bromide (HDTMA-Br) cationic surfactant and its application in arsenic removal from groundwater was investigated. The results revealed that adsorption of As(III) and As(V) is optimum at pH range 4-8. The maximum As(III) and As(V) adsorption capacities were found 2.33 and 2.88 mg/g, respectively after 60 min contact time. Pseudo first order model of reaction kinetics described the adsorption data for As(V) better while pseudo second order model described As(III) adsorption data. The adsorption isotherm data for As(III) and As(V) fitted well to Langmuir model indicating that adsorption of both species occurred on a mono-layered surface. Adsorption thermodynamics model revealed that adsorption of As(III) and As(V) was spontaneous and exothermic. The As(III)/As(V) adsorption mechanism was ascribed to electrostatic attraction and ion exchange. The regeneration study showed that synthesized adsorbent can be used for up to 5 times. In the firth part of the work inorgano-organo modified kaolin clay was successfully synthesized through intercalation of Fe3+ and Mn2+ metal oxides and HDTMA-Br surfactant onto the interlayers of the clay mineral. The batch experiments showed that As(III) removal was optimum at pH range of 4-6, while the As(V) removal was optimum at pH range 4-8. The adsorption data for both species of arsenic showed a better fit to pseudo second order of reaction kinetics which suggest that the dominant mechanism of adsorption was chemisorption. The isotherm studies showed better fit to Langmuir isotherm model as compared to Freundlich model. The maximum adsorption capacity As(III) and As(V) at room temperature as determined by Langmuir model were found to be 7.99 mg/g and 7.32 mg/g, respectively. The thermodynamic studies for sorption of As(III) and As(V) showed negative value of ΔGᴼ and ΔHᴼ indicating that adsorption process occurred spontaneously and is exothermic in nature. The regeneration study showed that the vi inorgano-organo modified kaolin clay can be reused for up 7 adsorption-regeneration cycles using 0.01 M HCl as a regenerant. Thomas kinetic model and Yoon-Nelson model showed that the rate of adsorption increases with increasing flow rate and initial concentration and decreases with increasing of the bed mass. In conclusions, adsorbents synthesized from this work showed a better performance as compared to other adsorbents available in the literature. Among the synthesized adsorbents, inorgano-organo modified clay showed highest adsorption capacity as compared to surfactant functionalized and Fe-Mn bimetal oxides modified kaolin clay. However, all adsorbents were recommended for use in arsenic remediation from groundwater. The following recommendations were made following the findings from this study: 1) routine monitoring of arsenic in groundwater of Greater Giyani Municipality, 2) evaluating the possible link between arsenic exposure and arsenic related diseases within Giyani in order to find the extent of the problem in order to establish the population at risk, 3) The toxicity assessment for HDTMA-Br modified kaolin clay should be carried out, 4) Materials developed in the present study should be modeled and tested at the point of use for arsenic removal, and lastly, 5) this study further encourage the development of other arsenic removal materials that can be used at household level. / NRF

Die Arbeit besteht aus mehreren Studien zur Quantifizierung des Grundwasserstroms in Seen (Exfiltration; engl.: lacustrine groundwater discharge, LGD) und damit verbundener Nährstoffeinträge. In zwei einleitenden Kapiteln dieser Arbeit werden eine Gründe für die Vernachlässigung der Grundwasserexfiltration (LGD) in Seen und der daran gekoppelten Nährstoffeinträge identifiziert. Diese Literaturstudien fassen den aktuellen Kenntnisstand zum Einfluss des Grundwassers auf die Hydrologie von Seen und ihre Nährstoffhaushalte zusammen. Den Kern der vorliegenden Arbeit bilden zwei empirische Studien, die sich mit der Quantifizierung der grundwasserbürtigen Phosphor (P)-Fracht in den Arendsee in Deutschland befassen. Das Gesamtvolumen des Grundwasserzustroms wird basierend auf der Grundwasserneubildung im Einzugsgebiet des Sees ermittelt. Lokale Muster der Grundwasserexfiltration werden anhand von Temperaturtiefenprofilen des Seesediments bestimmt. Eine Kombination der Ergebnisse ermöglicht es, die quantitativen Daten mit lokalen Informationen zu unterstützen. Die Untersuchung der Grundwasserqualität zeigt, dass die P-Konzentrationen im Grundwasser im besiedelten Bereich teilweise stark erhöht sind. Als Konsequenz daraus haben die grundwasserbürtigen P-Frachten einen Anteil von mehr als 50% an der gesamten externen P-Last des Arendsees. Das Grundwasser ist damit eine maßgebliche Ursache für die Eutrophierung des Gewässers. Drei weitere Studien widmen sich der Entwicklung und Optimierung von Ansätzen zur qualitativen und quantitativen Bestimmung der Grundwasserexfiltration in Seen. Die kritische Auseinandersetzung mit den Ergebnissen der Studien zeigt die Notwendigkeit weiterer Forschung zur Verbesserung und Standardisierung der Methoden zur Bestimmung von LGD und damit verbundenen Stofftransporten auf. Der Fall des Arendsees sollte alle, Wissenschaftler und Praktiker, dazu motivieren, das Grundwasser als relevante Eutrophierungsquelle in Betracht zu ziehen. / The present work is a collection of studies on lacustrine groundwater discharge (LGD) and groundwater-borne phosphorus (P) loads. For a number of reasons, groundwater exfiltration (i.e., LGD) is often not considered in water and nutrient budgets of lakes. This is also and especially true for P which was often regarded to be immobile in groundwater until recently. Two chapters review the scientific literature regarding the impacts of groundwater on hydrology and nutrient budgets of lakes, respectively. They present mechanisms and processes of LGD as well as techniques and methods to measure LGD and related nutrient transports. Moreover, numbers of LGD volumes and loads reported in literature are presented. The core of the present work is represented by two case studies dealing with the quantification of P loads from LGD to a lake in Germany. A combination of different methods is applied to overcome the problem of quantitative large scale LGD determination without losing local spatial information. P concentrations in groundwater and LGD are investigated by detailed spatial water sampling. The results reveal that P is actually present in concentrations far above natural background concentrations in the urban groundwater. LGD-derived P loads account for more than 50% of the overall external P loads to the lake and by that contribute significantly to lake eutrophication. Three further studies are devoted to the development and improvement of approaches to determine LGD. Critical reviews of the above mentioned studies reveal the need for further research in order to standardize and improve methods for LGD and mass load determination. It is found that the appropriate method for LGD determination depends on the spatial scale of interest. The identification of P introduced by LGD as a main driver of lake eutrophication is an important finding which should encourage scientists, policy makers, and lake managers to consider groundwater as a relevant P source for lakes.

Indiana University-Purdue University Indianapolis (IUPUI) / Numerous studies have investigated the fate of pollutants in riparian buffers, but few studies have focused on the control of multiple contaminants simultaneously in riparian zones. To better understand what drives the biogeochemical cycles of multiple contaminants in riparian zones, a 19-month study was conducted in riparian buffers across a range of hydrogeomorphic (HGM) settings in the White River watershed in Indiana. Three research sites [Leary Webber Ditch (LWD), Scott Starling (SS) and White River (WR)] with contrasting hydro-geomorphology were selected. We monitored groundwater table depth, oxidation reduction potential (ORP), dissolved oxygen (DO), dissolved organic carbon (DOC), NO3-, NH4+, soluble reactive phosphorus (SRP), SO42- , total Hg and methylmercury (MeHg). Our results revealed that differences in HGM conditions translated into distinctive site hydrology, but significant differences in site hydrology did not lead to different biogeochemical conditions. Nitrate reduction and sulfate re-oxidation were likely associated with major hydrological events, while sulfate reduction, ammonia and methylmercury production were likely associated with seasonal changes in biogeochemical conditions. Results also suggest that the LWD site was a small sink for nitrate but a source for sulfate and MeHg, the SS site was a small sink for MeHg but had little effect on NO3-, SO42- and SRP, and the WR was an intermediate to a large sink for nitrate, an intermediate sink for SRP, and a small source for MeHg. Land use and point source appears to have played an important role in regulating solute concentrations (NO3-, SRP and THg). Thermodynamic theories probably oversimplify the complex patterns of solute dynamics which, at the sites monitored in the present study, were more strongly impacted by HGM settings, land use, and proximity to a point source.