METAL and METALLOID ACCUMULATION in SEDIMENT, WATER and FISH in LAKE TITICACA (BOLIVIA) Number of Words: 42 058
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METAL AND METALLOID ACCUMULATION IN SEDIMENT, WATER AND FISH IN LAKE TITICACA (BOLIVIA) Number of words: 42 058 Fonteyne Arthur Student number: 01509225 Promotors: Prof. dr. ir. Gijs Du Laing, Prof. dr. ir. Geert Janssens Tutors: dr. Arturo Muñoz Saravia, Bernd Mees Master’s Dissertation submitted to Ghent University in partial fulfilment of the requirements for the degree of Master of Science in Bioscience Engineering: Chemistry and Bioprocess Technology Academiejaar: 2019 – 2020 Deze pagina is niet beschikbaar omdat ze persoonsgegevens bevat. Universiteitsbibliotheek Gent, 2021. This page is not available because it contains personal information. Ghent Universit , Librar , 2021. Acknowledgements Now, after five years of hard work and perseverance, finishing this master thesis, feels like finalising my career as a student. This project was a unique and interesting experience, which wouldn’t have been the same without the help of some important people. Now, I would like to thank everyone who made it possible to have such a wonderful time during my career as a student, my field work in Bolivia, for the guidance in the laboratory, for the advice whilst writing this thesis or just helped with a warm smile and some motivating words. First of all I want to express my gratitude to Prof. dr. ir. Gijs Du Laing and Prof. dr. ir. Geert Janssens for the opportunity to work on this project and for their support. Thank you for all the tips, suggestions and critical reviews on the right moment. Furthermore I would like to thank my tutors Bernd Mees and Arturo Muñoz Saravia. Bernd, thank you for the guidance in the lab, for answering all my questions and for the critical reviews regarding this master thesis. Arturo, thank you for all the help and advice during the field work in Bolivia, the guidance throughout the year and the critical reviews. Secondly I would like to thank the Limnology department of the Universidad Mayor de San Andrés (UMSA), for their warm welcome, all their help, advise and the possibility to use their equipment. A special thanks to Erick Loayza Torrico, without you, this thesis project would not have been possible. Your knowledge and experience at the lake, were of vital importance to accomplish our goals set in this master thesis. During the fieldwork we worked extremely hard, we could work from 5 a.m. till 4 p.m. without lacking enthusiasm. I’m very grateful for all your help, information, guided tours in La Paz, Oruro, Copacabana, the bouldering and so much more. Also a special thanks to Sara Neyrot and Vivi Cruz for their support at the lab, the lake and the nice times at La Paz. Don Ricardo, thank you for all the safely driven kilometres which brought us to our sampling locations. At last, also a special thanks to Yara Fernandez, when Eric and I needed a motivational boost, you knew exactly what could help us. I’m very grateful for all the support I received from everyone in Bolivia involved in this project. Due to all of you, this project resulted in an unforgettable experience. In addition, I would like to thank all the people working in the ECOCHEM laboratory of the department of Green Chemistry and Technology. Especially Roseline Blanckaert, who guided me throughout the year, provided me information regarding digestion methods applied in the laboratory and answered all my questions with full enthusiasm. Thank you, and I wish all the best for you and your baby. Finally, I’m very grateful to my friends and family, for all the support they gave me. Thank you mom and dad, Louise and Ester for giving me the opportunity to study, the endless support, motivational speeches, warm hugs and so much more. These five years were intensive but I only succeeded because of your support. Jolien, the last three years were amazing together, I’m sorry I went for 6 long weeks to the other side of the planet for my thesis. I admire your unlimited support even when I’m in the need of undertaking such adventures. I’m looking forward to the adventures the future may bring for both of us. At last, a thank you, to all my friends who made my time as a student unforgettable! These five years were extraordinary and the time flew by at the speed of 299 792 458m/s. I II Preambule In this preambule, the impact of the corona measures in Belgium on this master thesis will be discussed. Due to the measures taken by Ghent University to ensure the safety of students and employees, the laboratory operations had to be stopped prematurely. Following analyses could not be carried out: Second measurement of the water samples to obtain better recoveries Second measurements of the muscle samples to obtain recoveries for Pb Analysis of muscle samples from O.agassizii at lake Uru Uru Analysis of liver tissue from fish samples Analysis of the amphipod samples Analysis of the Diffusive Gradient in Thin film (DGT) samplers During the summer of 2019, field work was carried out in Bolivia: prospection, sample collection and preparation. During the first semester a suitable digestion method for sediment, water, fish and amphipod samples was developed. During the second semester the digestion and analyses of the samples were carried out. Thirty sediment and water samples and 175 fish samples were digested and analysed. The analyses given above were scheduled 3 weeks before the eastern holidays (11/03-27/03/2019) and could not be carried out. Not all analyses could be conducted which affected the amount of obtained results. Due to this hindrance a more extensive literature study was done and the work needed to finish this project, including analytical methods, are described in “Future perspective”. This preambule was drawn up after consultation between the student and the supervisor and is approved by both. III IV Resume Lake Titicaca has a valuable but vulnerable ecosystem and close monitoring of its pollution is very important to avoid ecologic disasters. In South America, high arsenic geogenic background concentrations of surface and groundwater are present. Besides, As, Hg, Cd and Pb are occurring in abnormally high concentrations near to urban areas, metalliferous mines or major road works. Elevated As, Hg, Cd and Pb could pose a substantial threat to the vulnerable ecosystem of Lake Titicaca and pose a risk to the health of the local communities. It is proven that the elevated intake of these elements could have a negative effect on plant, animal and human life. The prevention of increasing metal and metalloid concentrations by mining activity, agriculture and untreated urban waste water is of great importance. This master thesis focuses on the pollution and the accompanying risk of As, Hg, Cd and Pb at Lake Titicaca. The aim is to assess the quality of water and fish as a food source for the people who are living around the Bolivian part of lake Titicaca and to assess the water and sediment quality for animal life in this ecosystem. In order to obtain the As, Hg, Cd and Pb concentrations in sediment and biota, a method was selected to digest the sample matrix and to analyse the metals and metalloids via ICP-MS. Aqua regia or nitric acid were used for microwave-assisted digestion in closed vessel. This technique was selected because it is fast, results in complete digestion of the organic matter under high pressure, and shows high repeatability and better recoveries. Recoveries were obtained within a deviation of maximum 20% from full recovery for Cd, Hg and Pb. For As, elevated recoveries were found, which could have been caused by the interference of 40Ar35Cl+ and 40Ca35Cl+, formed in the plasma of the ICP-MS. Analysing As in dynamic reaction mode (DRC) instead of collision cell mode on the ICP-MS may resolve this problem. In this study, the As, Hg, Cd and Pb concentrations were measured in sediment, water and seven fish species occurring in Lake Titicaca. It could be concluded that for As in sediment, adverse effects on the aquatic environment can be expected. The obtained results for the water samples taken at Lake Titicaca showed elevated As concentrations which are situated near to the safety threshold value (10 g/L). At lake Uru Uru, the As concentrations in water are approximately six times higher than the safety threshold level. Negative effects can be expected for aquatic and terrestrial life due to the chronic exposure to (drinking) water contaminated with As. Regarding the As, Hg, Cd and Pb bioaccumulation in the seven different fish species, As and Hg may pose a threat to the health of the local communities. The As concentrations exceeded the safety threshold level (0.1 mg/kg) in all seven fish species. For Hg, O. bonarienses had an average Hg concentration above the safety threshold level (0.5 mg/kg) and Trichomycterus spp. showed concerning elevated concentrations. Furthermore, the in captivity grown O. mykiss, had the lowest As and Hg concentrations, which could be the result of the captive breeding. If the in captivity bred up O. mykiss has the potential to accumulate lower metal and metalloid concentrations, this could possibly have a similar impact on O. bonariensis and the other fish species. Additional research is needed to investigate the impact of the captive breeding on the metal and metalloid bioaccumulation in the fish species from Lake Titicaca. Finally, consumption limits were calculated. From this evaluation it seems advisable to replace the water of Lake Titicaca by treated or non-contaminated water for consumption by children under the age of 12 years. Besides, recommended maximum daily intakes of fish from Lake Titicaca were calculated.