1. Hydrogeochemical Processes Influencing Groundwater Quality in the Lower Pra Basin, Ghana. A PhD Thesis By Collins Tay

2. Components of the Thesis The Thesis is made of 4 parts: 1.Sources of dissolved ions in GW using;  GW geochemistry,  Major ion relationships, and  stable isotopes of 18O and 2H 2. Using the concept of differences in (TDS), to categorize waters into different Gps and SGps of similar WQ characteristics (HCA ) 3. Using multivariate statistical methods to facilitate the unveiling of hidden structures in the datasets and assist in resolving key geo-environmental problems. 4. Heavy metal pollution in GW within the basin

3. Origin of dissolved ions in GW using major ions relationship INTRODUCTION  GW remains the most dependable source of water supply for the numerous scattered rural communities in Ghana (including the Pra Basin) due to the contamination of surface water resources.  Knowledge of the chemistry of GW in these communities therefore, need to be well documented for the development and management of the water resources.  Interest in the geochemistry of GW has increased during the past decade as evidenced by hydrogeochemical studies which are becoming a firm part of regional hydrogeological studies.  Hydrogeochemistry, seeks to determine the origin of the chemical composition of GW and the relationship between water- rock -chemistry, particularly as it relate to GW movement.  The geochemistry of GW is complex due to infiltration of water through complex geological formations and human impact on flow systems

4. Introduction cont.  Water being a good solvent, dissolves chemical constituents from dissolvable materials as it passes through the atmosphere, soil and unsaturated zone into the water-table and in doing so, becomes modified in composition  These changes reflect the signatures of factors such as;  soil/rock composition,  prevailing climatic condition,  pH,  the resident time of water,and  topography  The overall implication of these changes is that the hydrochemical facies (WATER TYPES) of GW change in response to its flow path and geochemical history

5. Introduction cont.  Investigations into the origin of dissolved ions in water resources reveals a great deal of information such as:  general geology,  degree of chemical weathering  quality of recharge water, and  inputs from sources other than water-rock interaction.

6. Problem statement  The Basin like any other rural community in Ghana, depend heavily on GW as a major source of water supply due to contamination of SW as a result of farming and/or mining activities.  Exposure of sulphide rocks (pyrite and arsenopyrites) that contain gold ore, to the atmosphere often results in acid mine drainage generation and subsequent mobilisation of trace metals, particularly, As in high proportions into the GW system  The indiscriminate use of mercury (Hg) and other chemicals during mining operations,  Despite the susceptibility of GW within the basin to pollution, information on detailed hydrochemical data ensuing to the explicit understanding of GW chemistry is either very little or non existent.  Therefore, the need to evaluate the natural geochemical and biochemical processes as well as anthropogenic activities that influence the suitability of GW for drinking cannot be over emphasised.

7. Objectives Determined the origin of dissolved ions in GW within the basin using the Mass-Balance approach (major ions- relationship and equivalent ratios of ions)

8. Methodology  Sampling and analysis Sampling was carried out once every 3 months for two years. The reconnaissance sampling was carried out in March 2011 and the last batch of samples were collected in March 2013. Sampling protocol described by Classen (1982), Barcelona et al., (1985) were observed. Samples were analyzed using appropriate certified and accepetable international procedures outlined in Standard Methods for the Examination of Water and Wastewater (APHA, 1998) Charge balances were calculated using the eqn. below CB = [(∑z Mc - ∑z Ma) / (∑z Mc + ∑z Ma)] * 100  Location of the Lower Pra Basin The Lower Pra Basin is located between longitude 05 o 0 ' 0"N and Longitude 06 o 0'0"N and Latitude 01 o 0'0"W and Latitude 02 o 0'0 " W (Fig 1)

9. The Lower Pra Basin and the sampling communities

10. Results and Discussions Von Bromssen (1989), Caritat (1995) Stumm (1992); Caritat et al., (1998)

11. Results and Discussions Maclean and Jakowski (2000) Maclean and Jakowski (2000) However, HCO 3 /SiO 2 < 5 (for 75% of GW) suggesting Silicate weathering Maclean and Jakowski (2000) Brady and Walter (1989); Appelo and Postma (1999)

12. Results and Discussions CaAl 2 Si 2 O 8 + 2CO 2 + 3H 2 O Al 2 Si 2 O 5 (OH) 4 + Ca 2+ (Anorthite) (Kaolinite) + 2HCO 3 However, Na + / (Na + + Cl - ) > 0.5 for 81 % of GW, suggesting ion - exchange reactions responsible for Na + and Cl -

13. Results and Discussions Similarly, the SiO 2 /(Na + +K + +Cl - ) < 1 for 100% of GW, suggesting cation ion exchange reactions

14. Results and Discussons 2NaAlSi 2 O 8 + 2CO 2 + 11H 2 O = Al 2 Si 2 O 5 (OH) 4 + 2Na + + 2HCO 3 - + (Albite) (Kaolinite) 4H 4 SiO 4

15. Conclusions  The major processes responsible for chemical evolution of GW within the basin include: silicate (SiO 4 ) 4- weathering and ion-exchange reactions, sea aerosol spray, oxidation of pyrite (FeS 2 ) and arsenopyrite (FeAsS).  The GW is moderately acidic to neutral (3.5 - 7.0 pH units). Approximately, 89% of GWs had pH values outside the WHO (2004) Guideline Value due principally to natural biogeochemical processes.  The relative abundance of cations and anions is in the order: Na + > Ca 2+ > Mg 2+ >K + and HCO 3 - > Cl - > SO 4 2- respectively.

16. Recommendations  In terms of management and development of GW, future GW studies could be focused on similar hydrogeochemical studies in the Upper Pra Basin to generate similar data.  Data obtained from the hydrogeochemical studies in the Lower and Upper Pra Basins could be put together and the results obtained used to model the hydrogeochemical processes influencing the quality of GW within the Pra Basin.  The model could then be used to predict GW quality for decades to come thereby, providing the basis for the monitoring of water quality parameters to ensure the efficient management and development of GW within the Pra Basin

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