The Hydrochemical and Isotopic Characterization of GROUNDWATER in Southern Mozambique
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THE HYDROCHEMICAL AND ISOTOPIC CHARACTERIZATION OF GROUNDWATER TownIN SOUTHERN MOZAMBIQUE Sabine Henry | HNRSAB003Cape University ofof Cape Town February 2020 Report Ti University The copyright of this thesis vests in theTown author. No quotation from it or information derived from it is to be published without full acknowledgement of the source. The thesis is to be used for private study or non- commercial research purposes only.Cape Published by the Universityof of Cape Town (UCT) in terms of the non-exclusive license granted to UCT by the author. University Declaration I am presenting this dissertation in FULL fulfilment of the requirements for my degree. I know the meaning of plagiarism and declare that all of the work in the dissertation, save for that which is properly acknowledged, is my own. I hereby grant the University of Cape Town free license to reproduce for the purpose of research either the whole or any portion of the contents in any manner whatsoever of the above dissertation. Abstract A groundwater chemistry sampling campaign was run over two sampling seasons in 2018. Groundwater samples were taken across the region of southern Mozambique, between the towns of Namaacha, Catuane, Ponta do Ouro and Marracuene. Major anions and cations were analyzed by two labs at Stellenbosch University, and stable isotopes of oxygen and hydrogen, and radiogenic isotopes of strontium were analyzed at the Department of Geological Sciences at the University of Cape Town. The aim of this study was to characterize the isotopic and hydrochemical composition of groundwater in the southern Mozambique study area, using major ions and stable isotopes. Samples were categorized into different zones based on the underlying geology in which the borehole was sited. Overall, the dominant anions and cations are: Cl>HCO3>SO4 and Na> Ca=Mg>K. 68% of samples plotted in the Na-Cl water type, whilst 30% plotted in the Na-HCO3 water type of the Piper and Chadha diagrams. Salinization is the mechanism controlling the Na-Cl water types, whilst recharge is mechanism controlling the Na-HCO3 water types. Saturation indices of calcite, dolomite, halite, and gypsum. Saturation indices were calculated using the thermodynamic software PHREEQC. All samples were undersaturated with respect to gypsum and halite, suggesting that the conditions were thermodynamically favored for their dissolution. Samples that were from boreholes that plotted in the limestone layers and >40m depth in basalts, and quaternary sediments were oversaturated with respect to calcite and dolomite, indicating that the conditions were thermodynamically favored for their precipitation out of solution. Samples that plotted in the rhyolite, shallow basalts and quaternary sediments were undersaturated with respect to calcite and dolomite, suggesting dissolution into solution. Sixty-two percent of sample had an NA/Cl ration greater than one, indicating silicate weathering as a major process affecting the chemical character of the water. Samples in the basalts however had Na/Cl ratios less than one, and δ2H and δ18O values out of the range of seawater, suggesting ion exchange as a process affecting the chemistry of groundwater in these areas. Since there is no established Local Meteoric Water Line (LMWL) in the area, LMWL from Pretoria and Durban were used as proxies, and the Global Meteoric Water Line (GMWL) was also plotted. Samples in the rhyolites, basalts and quaternary sediments has high d-excess values, and showed a strong evaporation trend. The mechanisms for groundwater salinization in these areas is strongly influenced by evapoconcentaion effects. Geographical features such as seasonal variation, latitude, elevation and distance from coast do not appear to be a major factor affecting the isotopic composition of the groundwaters. The strontium isotopes and elemental strontium concentrations indicate that groundwater mixing likely occurred in each zone, however no end-members were established. Acknowledgments • Prof. Chris Harris, for all the guidance, supervision and advice; • Prof. Jodie Miller, for co-supervision and providing the opportunity and funding to do this Masters; • Conseng Engineering (Mozambique), Oscar and Claudio for taking us around to collect samples; • Jared van Rooyen, for being an excellent field assistant and providing lots of wisdom; • To Sherissa Roopnarain and Warrick Joe for isotope analysis at UCT stable isotope laboratory at UCT; • The Central Analytical Facility at Stellenbosch University; • My family for all their support and guidance; • Félicie, Katie and Claire for their friendship and support;. • WE-consult Uganda and Umvoto Africa for the opportunity to broaden my understanding of hydrogeology. Description Table of Contents Chapter Description Page ABSTRACT .................................................................................................................................................................. 3 Table of Contents ....................................................................................................................................i List of Tables .........................................................................................................................................iii List of Figures ........................................................................................................................................iii List of Abbreviations ................................................................................. Error! Bookmark not defined. 1. INTRODUCTION ................................................................................................................................................ 1 1.1. Stable Isotopes in the Hydrological Cycle ..............................................................................2 1.1.1. The Hydrological Cycle ................................................................................................2 1.1.2. Reference Standards and Measurement of delta 18O and 2H ...................................3 1.1.3. Fractionation Processes ..............................................................................................3 1.1.4. Meteoric Water Lines ....................................................................................................5 1.1.5. Evaporation, Deuterium Excess ‘d’ and its effects on the GMWL ...........................5 1.2. Hydrochemical Processes ........................................................................................................6 1.2.1. Ion Exchange Processes .............................................................................................8 1.2.2. Saturation Indices .........................................................................................................9 1.2.3. Oxidation-Reduction Reactions ..................................................................................9 1.2.4. Salinization Processes .............................................................................................. 10 1.3. Study Area ............................................................................................................................... 11 1.3.1. Geology ....................................................................................................................... 12 1.4. Hydrology ................................................................................................................................ 16 1.4.1. Precipitation and Climate .......................................................................................... 16 1.4.2. Drainage Basins and River Systems ....................................................................... 16 1.4.3. Groundwater Occurrences and Estimated Yields .................................................. 18 2. METHODOLOGY ............................................................................................................................................. 21 2.1. In-Field Sampling Procedure ................................................................................................. 21 2.2. Analytical Techniques ............................................................................................................ 22 2.2.1. Major Cations ............................................................................................................. 22 2.2.2. Bicarbonate ................................................................................................................ 22 2.2.3. Chloride and Sulphate ............................................................................................... 22 2.2.4. Oxygen (δ18O) and Hydrogen (δ2H) .......................................................................... 23 2.2.5. Strontium Isotopes .................................................................................................... 23 3. RESULTS ......................................................................................................................................................... 25 3.1. Physiochemical Parameters .................................................................................................. 30 i 3.2. Major Ions ................................................................................................................................ 31 3.3. Isotopes δ18O, δ2H and d-excess ......................................................................................... 39 4. DISCUSSION ..................................................................................................................................................