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A Comparative Water and Sediment Quality Assessment of the Nyl River System, Limpopo, South Africa By Simone Dahms MINOR DISSERTATION Submitted in Fulfilment of the Requirements for the Degree MAGISTER SCIENTIAE In Aquatic Health In the FACULTY OF SCIENCE At the UNIVERSITY OF JOHANNESBURG Supervisor: Dr. R Greenfield November 2015 The financial assistance of the National Research Foundation (NRF) towards this research is hereby acknowledged. Opinions expressed and conclusions arrived at are those of the author and are not necessarily to be attributed to the NRF CONTENTS LIST OF TABLES…………………………………...……………………………………...iii LIST OF FIGURES……………………………………………………………………….....v LIST OF ABBREVIATIONS……….…………………………………………………….vii ACKNOWLEDGEMENTS…………….…………………………………………………..x SUMMARY…………..……………………………………………………………………..xi CHAPTER 1: INTRODUCTION...…………..…………………………………………….1 1.1 General Introduction………………………………………………………...….2 1.2 Hypotheses, Aims and Objectives…………………………………………….4 1.2.1 Hypotheses……………………………………………………………4 1.2.2 Aims……………………………………………………………………4 1.2.3 Objectives……………………………………………………………..4 1.3 Chapter Outline…………………………………………………………………5 CHAPTER 2: LITERATURE REVIEW……………………………………………………6 2.1 Study Background………………………………………………………………7 2.2 Study Sites………………………………………………………………………8 2.3 Experimental Design....………………………...……………………...……..13 2.4 Conclusion……………………………………………………………………..16 CHAPTER 3: WATER AND ARTIFICIAL MUSSELS......……………………………..17 3.1 Introduction………………………………………………………………….....18 3.2 Materials and Methods………………………………………………………..19 3.2.1 In situ water quality parameters…………………………………...19 3.2.2 Water…………………………………………………………………19 3.2.3 Artificial Mussels…………………………………………………….23 3.2.4 Statistical Analysis……………………………………………...…..26 3.3 Results………………………………………………………………………….26 3.3.1 In situ water quality parameters…………………………………...26 3.3.2 Water…………………………………………………………………28 i 3.3.3 Artificial Mussels…………………………………………………….36 3.3.4 Water and AMs……………………………………………………...40 3.4 Discussion……………………………………………………………………...42 3.4.1 In situ water quality parameters……………………………………42 3.4.2 Water and AMs………………………………………………………42 3.5 Conclusion……………………………………………………………………...48 CHAPTER 4: SEDIMENT AND ECOLOGICAL RISK ASSESSMENT……………....50 4.1 Introduction……………………………………………………………………..51 4.2 Materials and Methods………………………………………………………..52 4.2.1 Site Selection……………………………………………………….. 52 4.2.2 Sample Collection and Preparation…………………………...…..52 4.2.3 ICP-OES Analysis…………………………………………………...53 4.2.4 Statistical Analysis…………………………………………………..54 4.2.5 Ecological Risk Assessment……………………………………….54 4.3 Results………………………………………………………………………….58 4.3.1 Metal Concentrations in Sediment………………………………...58 4.3.2 Ecological Risk Assessment……………………………………….62 4.4 Discussion……………………………………………………………………...68 4.5 Conclusion……………………………………………………………………...72 CHAPTER 5: CONCLUSIONS AND RECOMMENDATIONS………………………74 5.1 Concluding Remarks………………………………………………………….75 5.2 Recommendations…………………………………………………………….76 CHAPTER 6: REFERENCES……………………………………………………………...78 APPENDIX A………………………………………………………………………………87 APPENDIX B…………………………………...………………………………………….88 ii LIST OF TABLES: Table 2.1: Locations, abbreviations and GPS coordinates of study sites Table 2.2: A review of the history of AMs (Adapted from Claassens et al. 2016) Table 3.1: Sampling dates of water, AMs and In situ parameters for determining metal concentrations in the Nyl River system. Table 3.2: Recoveries of CRMs from ICP-MS analyses including Dogfish Liver Tissue (DOLT-4), Lake Sediment (LKSD-3) and Freshwater Sediment (FWSD) analysed for QA/QC purposes. Table 3.3: ICP-MS LODs for water sample analysis. LOD numbers are expressed in µg/l. Table 3.4: ICP-MS LODs for AM analysis analysed for QA/QC purposes. LODs are expressed in µg/l. Table 3.5: Total Hardness of water samples from the Nyl River system, Limpopo, South Africa. Measurements given in mg/L CaCO3. Water Hardness is determined according to the DWAF guidelines for aquatic ecosystems (DWAF, 1996), <60mg/L is Soft, 60-119mg/L is Medium, 120-180mg/L is Hard and >180mg/L is Very Hard. Table 4.1: The detection limits as calculated by the ICP-OES for each of the metals expressed in parts per million (ppm) as well as CRM Recovery percentages for Lake Sediment-3 and Freshwater Sediment. Table 4.2: Description of Contamination Factor (CF) values as described by Thomilson et al. (1980). Table 4.3: Descriptions of the Geo-Accumulation Index (Igeo) values and classes (0- 6) as described by Muller (1979). Table 4.4: The Enrichment Factor (EF) Index description of values as described by Li et al. (2013). iii Table 4.5: Contamination Factor (CF), Geo-accumulation Index (Igeo) and Enrichment Factor for High Flow (HF) February-April 2014 and Low Flow (LF) July-August 2014 for Al, Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn for seven sites along the upper Nyl River. Table 4.6: Results of the Pollution Load Index for High Flow (HF) (February-April 2014) and Low Flow (LF) (July-August 2014) periods for seven sites along the Nyl River. iv LIST OF FIGURES: Figure 2.1: A Map of the Nyl River, Limpopo Province, South Africa with the sampling sites indicated. Sampling sites include the Klein Nyl Oog (KNO), Donkerpoort Dam (DPD), Golf Course (GC), Sewage Treatment Works (STW), Jasper (JAS), Nylsvley Nature Reserve (NYL) and the Moorddrift Dam (MDD). Figure 2.2: Sampling sites along the Nyl River, Limpopo, South Africa. A: Klein Nyl Oog (KNO), B: Donkerpoort Dam (DPD), C: Golf Course (GC), D: Sewage Treatment Works (STW), E: Jasper (JAS), F: Nylsvley Nature Reserve (NYL), G: Moorddrift Dam (MDD) Figure 3.1: Recoveries of internal standards during ICP-MS analysis for Rh and Lu expressed in % recovery of each element. Figure 3.2: A constructed Artificial Mussel as designed by Wu et al. (2007). Figure 3.3: A flow diagram representation of the process of constructing an AM as described by Hossain et al. (2015). Figure 3.4: In situ water quality parameters including Conductivity, pH and Oxygen Saturation measured in the Nyl River system for 27/02/2014 and 02/04/2014 in the wet season and 27/07/2014 and 22/08/2014 in the dry season. The acid spill sampling took place on 06/06/2015. Figure 3.5: Metal concentrations from water sample ICP-MS analysis for Al, Cd, Cr, Co, Cu, Fe, Mn, Ni, Pb and Zn, from seven sites along the Nyl River in Limpopo, South Africa, expressed in µg/l. Sampling periods were from 27/02/2014-02/04/2014 for the wet season and 27/07/2014-22/08/2014 for the dry season. The acid spill sampling took place on 06/06/2015. Common superscripts denounce significant differences (p<0.05). Figure 3.6: A Canonical Discriminant Function Analysis (DFA) showing grouping of water samples for seven sites along the Nyl River system, Limpopo. The acid spill sampling (AS) took place on 06/06/2015. Sampling periods were from 27/02/2014- 02/04/2014 for the wet season (HFW) and 27/07/2014-22/08/2014 for the dry season (LFW). v Figure 3.7: A Canonical Discriminant Function Analysis (DFA) showing grouping of water samples for seven sites along the Nyl River system, Limpopo. Sampling periods were from 27/02/2014-02/04/2014 for the wet season (HFW) and 27/07/2014- 22/08/2014 for the dry season (LFW). Figure 3.8: Metal concentrations from AM sample ICP-MS analysis for Al, Cd, Cr, Co, Cu, Fe, Mn, Ni, Pb and Zn, from five sites along the Nyl River in Limpopo, South Africa, expressed in µg/l. Sampling periods were from 27/02/2014-02/04/2014 for the wet season and 27/07/2014-22/08/2014 for the dry season. Common superscripts denounce significant differences (p<0.05). Figure 3.9: A Canonical Discriminant Function Analysis (DFA) showing grouping of AM samples for five sites along the Nyl River system, Limpopo. Sampling periods were from 27/02/2014-02/04/2014 for the wet season (HF AM) and 27/07/2014-22/08/2014 for the dry season (LF AM). Figure 3.10: A Canonical Discriminant Function Analysis (DFA) showing grouping of water and AM samples for seven sites along the Nyl River system, Limpopo. Sampling periods were from 27/02/2014-02/04/2014 for the wet season (HF) and 27/07/2014- 22/08/2014 for the dry season (LF). Dry season AMs are labelled LFAM, wet season AMs HFAM, dry season water LFW, wet season water HFW. Figure 4.1: Metal levels from seven sites along the Nyl River collected for February (HF1), April (HF2), July (LF1) and August (LF2) for 2014. Red lines indicate SQGs (CCME, 2002) for Cd, Cu, Cr and Zn and the guidelines set out by MacDonald et al (2000) for Ni. Concentrations were determined by means of ICP-OES and are expressed in µg/g dry weight. Figure 4.2: A Canonical Discriminant Function Analysis showing variation of Al, Cd, Cr, Co, Cu, Fe, Mn, Ni, Pb and Zn in sediment samples from February, April, July and August 2014. Concentrations