Masters of Science / This study was conducted to investigate hydrogeochemical processes controlling the evolution of groundwater chemistry and their influence on water quality in the Heuningnes Catchment. The role or influence of hydrogeochemical processes in groundwater quality in aquifer systems remains poorly understood. One of the ways of improving such understanding is to employ different techniques to explore key processes that govern groundwater quality in aquifer systems. Therefore, the present study investigated hydrogeochemical processes of groundwater resources and identified key processes that explained its quality from a spatiotemporal perspective. The quantitative approach that provides the ability to assess relationships between variables both spatially and temporally was applied. Groundwater sampling was done on four occasions during July 2017, October 2017, March 2018, and July 2018. Identification of hydrogeochemical processes controlling the evolution of groundwater chemistry and quality was done using various complementary tools. These tools included classification of the main water types, evaluation of water-rock interaction by means of stoichiometry analysis and bivariate correlation plots, inverse geochemical modelling, and statistical analysis (hierarchical cluster analysis and factor analysis). Physical parameters were measured in situ, while water samples were collected from boreholes, piezometers, springs, and artesian boreholes for laboratory analysis for major ions analysis. Descriptive and bivariate statistical methods were used to summarise and evaluate the strength of the relationship between variables, while multivariate statistical methods were applied to group similar samples based on their chemical compositions. Tri linear Piper diagrams were generated to characterize water type based on double normalizing the proportions of cations and anions, while correlation and stoichiometric analysis were applied to identify hydrogeochemical processes influencing groundwater chemistry. The results generated from the trilinear Piper diagrams confirmed the dominance of sodium and chloride ions in waters of the Heuningnes Catchment. Groundwater of a Na/Cl type is typical for a coastal aquifer characterised by saline, deep ancient groundwater. The lower parts of the Catchment were characterised by saline groundwater. The results indicated that shallow groundwater samples within the study area were more mineralised as compared to deep groundwater with EC values ranging between 20.8 and 2990 mS/m, with waters within the Table Mountain Group region (TMG), recording the lowest values. Deep groundwater for boreholes and artesian boreholes located upstream in the Catchment was fresh and yielded some of the lowest EC values recorded with an EC value below 50 mS/m. Generally, EC values increased from the upper TMG region of the Catchment towards the Bokkeveld shale region downstream and were highest during the dry season of 2018. The results indicated strong geological influences on water chemistry. Bivariate correlation and stoichiometric analysis identified cation exchange, adsorption, evaporation, weathering of carbonates, sulphates and silicate minerals as processes influencing the chemistry of groundwater in the Heuningnes Catchment. The Saturation Index (SI) results showed a change of calcite, dolomite, aragonite, gypsum, anhydrite, halite, melantinterite, siderite and sylvite from being undersaturated to oversaturated at some areas for the different seasons along the flow path. The mass-balance modelling results indicated that ion exchange and reverse ion exchange processes were more dominant at low elevations along the same flow path during the dry periods. However, at high elevations along the flow path, silicate weathering was the dominant process taking place. The findings of this study demonstrated the influence of hydrogeochemical processes in changing the water chemistry along the flow paths. In conclusion, the study showed the value of utilising various assessment tools as complementary techniques to improve the understanding about hydrogeochemical processes, and its influence on evolution of groundwater chemistry and quality. Based on the findings of the study the following recommendations were made for future studies; the sample points or sample boreholes in the study Catchment should be increased; and to have more sampling trips to enable better comparison between the possible processes

Magister Scientiae (Integrated Water Resource Management) / River catchments in agricultural areas are strongly influenced by runoff from cultivated or grazed fields, and nutrient loading of these fields can result in large quantities of nitrates and phosphates being transported to rivers in surface runoff. In intensively farmed areas, nutrient loading is often so high that large quantities of nitrates and phosphates are transported to streams in surface runoff. Within these areas, strips of natural riparian vegetation and wetlands are critical in providing nutrient uptake functions that can reduce the load entering streams. A wetland can be a source, sink or transformer of nutrients, where fine sediments such as silt and clay have the ability to store and trap considerable amounts of phosphorus through adsorption and precipitation processes. Therefore, the determination of phosphorus adsorbed to fine sediment is important in understanding the role and value of wetlands in agricultural landscapes, and is the main focus of this study. The aim of the study is to evaluate an indicator-based approach, WET-EcoServices, to assess wetland sediment and phosphate trapping, through comparison with field survey data. The study focuses on spatial analysis and field survey of three Hydrogeomorphological (HGM) units classified for the Wiesdrift wetland on the Nuwejaars River, Cape Agulhas. The three HGM units are classified as: a floodplain wetland at the inlet of the system, a channelled valley-bottom wetland towards the middle part of the system and a floodplain wetland towards the outlet of the system. In-field observations were recorded for hydrogeomorphic and vegetation characteristics for each HGM Unit. AstroTurf mat sediment samples, grabbed channel bed and floodplain sediment samples were analysed for particle size and orthophosphate concentrations, while suspended sediment masses were recorded from three pairs of time-integrated sediment samplers located near the inlet, near the middle, and near the outlet of the wetland. Statistical analysis showed that orthophosphate concentrations are associated with fine sediment. Thus, the orthophosphate concentrations follow the distribution of silt on the Wiesdrift wetland. The dominant vegetation along transect 2, at which the highest concentrations of orthophosphate was found, is occupied by Typha capensis and Cyperus textilis. The percentage of fine sediment (silt) ranged between 0-37%, where the remaining percentage was sand. There was also a significant positive correlation between orthophosphate concentration and silt (Spearman’s rank-order correlation: rs = 0.692, N = 70, P < .001). The largest total sediment amount was found at Outlet 1 and Outlet 2 in the HGM unit 3 of the Wiesdrift wetland, with a value of 0.653 g. Overall, orthophosphate concentrations ranged between 0 mg/kg and 31320 mg/kg within the Wiesdrift wetland. WET-EcoServices determines an average score for phosphate trapping from on-site indicators such as hydrological zones, vegetation structure and soil texture/permeability. The dispersal of fine sediment and associated adsorbed phosphate is more complex than can be determined by a tool like WET-EcoServices because the tool captures the long-term mean conditions of a wetland system that determines the overall uptake of phosphates over extended time periods, thus future wetland assessments is recommended to take place over a longer period than this study. However, the field results of orthophosphate distribution are generally consistent with the findings from WET-EcoServices, further motivating for the use of the tool in wetland management applications.