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Geochemistry of Trace Elements in the Bolivian Altiplano

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Geochemistry of Trace Elements in the Bolivian Altiplano GEOCHEMISTRY OF TRACE ELEMENTS IN THE BOLIVIAN ALTIPLANO Effects of natural processes and anthropogenic activities Oswaldo Eduardo Ramos Ramos June 2014 TRITA-LWR PHD-2014:04 ISSN 1650-8602 ISBN 978-91-7595-177-5 Oswaldo Eduardo Ramos Ramos TRITA LWR PHD-2014:04 Cover illustration: Top left: Lake Poopó landscape; Top right: Machacamarquita mine; Botton left: sediment of thermal water; Botton center: waste material in the Tiwanaku tailing (Photograph: Prosun Bhattacharya ©, 2009); Botton right: model concept of trace elements in Poopó Basin (Figure: Oswaldo Eduardo Ramos Ramos©, 2014). © Oswaldo Eduardo Ramos Ramos 2014 PhD Thesis KTH-International Groundwater Arsenic Research Group Division of Land and Water Resources Engineering Department of Sustainable Development, Environmental Science and Engineering (SEED) KTH Royal Institute of Technology SE-100 44 STOCKHOLM, Sweden Reference to this publication should be written as: Ramos Ramos, O. E. (2014) “Geochemistry of trace elements in the Bolivian Altiplano - Effects of natural processes and anthropogenic activities”. PhD Thesis, TRITA LWR PHD-2014:04 ii Geochemistry of trace elements in the Bolivian Altiplano Dedicated to Zaret Astrid, Leonardo Fabian and Brenda Alison iii Oswaldo Eduardo Ramos Ramos TRITA LWR PHD-2014:04 iv Geochemistry of trace elements in the Bolivian Altiplano FOREWORD The thesis deals with the levels of trace metals and their mobility in the Bolivian Al- tiplano and aims at an evaluation of the risk for human exposure via different path- ways, such as drinking water and food items. The area is affected by long term min- ing activities, covering hundreds of years from precolonial time until present day. The production of metals like tin, silver, lead and zinc is still a major share of the Bo- livian economy and is likely to remain so. The thesis deals with a multitude of ma- trixes, like surface water, groundwater, agricultural soils, crops, and lake sediments in order to evaluate the risk of mobilizing metals which might threaten the human health. An extensive literature survey has been done to set the conditions in relation to notably the South American conditions. The geology of the Titicaca region, part of the Bolivian Altiplano is complex and constitutes an important background for the study. Not only the mining activities are governing the behaviour of trace metals as the mineral deposits are present in different host rocks determining the pH and redox conditions of the terrestrial and aquatic environments. Regarding trace metals in surface water sampling and analysis has been done from headwater areas, above the mining areas down to the Poopó basin. Arsenic, cadmium, manganese and zinc concentrations in surface water exceed the WHO guidelines in some of the streams. The presence of iron hydroxyoxides provides a control of the arsenic content in groundwater as they are excellent adsorbents for arsenic under oxidizing conditions which is revealed by sequential extraction. DTPA extraction has been used to assess the plant availability of trace metals in soils. The investigation of crops has revealed that arsenic and cadmium do not exceed guideline but that lead does so in beans and potatoes. The computer code PHREEQC has been used to study trace metal species and possible equilibria with solid phases. A particular magnesium arsenate has been detected in the mineralogical studies of soils. A number of approaches has been used to assess the environmental risk of trace metals such as RAC (Risk Assessment Code), Igeo (Geoaccumulation ratio) and EF (Metal Enrichement Factor). In conclu- sion is turn out that the behaviour of arsenic requires further studies in relation to the hydrogeological conditions. The bioavailability in crops of different trace metals species, inorganic and organic deserve further attention. Prof. Em. Gunnar Jacks Stockholm, KTH, June 2014 v Oswaldo Eduardo Ramos Ramos TRITA LWR PHD-2014:04 vi Geochemistry of trace elements in the Bolivian Altiplano ACKNOWLEDGEMENTS I would like to express my sincere gratitude to Sida/SAREC for financial support, which has made this research possible and has contributed significantly to the capaci- ty building at Universidad Mayor de San Andrés (UMSA), also to Swedish Interna- tional (SI) and International Science Programme (ISP) in Sweden and DIPGIS at Universidad Mayor de San Andrés in Bolivia for administrative assistance, coordina- tion and management of funds and scholarship. This research was funded through the Swedish International Development Coopera- tion Agency in Bolivia (Sida Contribution: 7500707606) and also acknowledge the support of the CAMINAR project (INCO-CT-2006-032539) funded by the Interna- tional Cooperation section of the European Commission under the 6th Framework Programme. I greatly appreciate the coordination, supervision and support of Prof. Prosun Bhattacharya, Prof. Roger Thunvik and Prof. Jorge Quintanilla that contributed greatly to the success of PhD studies at KTH and UMSA, respectively. I wish to extend profound gratitude to my supervisors Dr. Ondra Sracek and Dr. Jochen Bundschuh for their scientific guidance and constructive inputs to my re- search papers. My gratitude also to Jyoti Prakash Maity for his revision of my thesis and discussion, without his determined support and encouragement, I could not have accomplished this thesis. I am grateful to Prof. Gunnar Jacks at KTH for vigorous work in all the stages in lab during the sequential extractions in soil, especially in the winter vacations 2009-2010, and also for providing facilities and materials used for soils studies. I wish extend my gratitude to all of my co-authors in the papers, without their scientific discussion and input, I could not reach the publications of the scientific information. My special thanks go to my friend (Mauricio, Amalia, Israel, Efrain, Mac, Elvira, and Liliana) and colleagues (Zairis, Sandhi, Dipti, Ashis, Manoj, Tipu, Annaduzzaman, Anna and Patricia) at both UMSA and KTH for the memories times in the field and lab work, meal times and relax moments that I never ever forget. Special thanks are gratefully extended to Annaduzzaman for helping me at the formatting stage of this thesis and Mauricio for the meal times and fruitful discussion on groundwater chemistry. My gratitude to Bertil, Anna, Monica for assistance in the lab analyses at KTH; and also Aira, Britt and Jerzy for great assistance in administrative as well as health mat- ters. I value the help from Prof. Carl-Magnus Mörth at the Department of Geologi- cal Sciences, Stockholm University for providing laboratory analysis. My grateful to the administration staff at Universidad Mayor de San Andrés, Faculty and Chemistry Department and Instituto de Investigaciones Químicas (IIQ) for helping me to travel abroad without any trouble, particularly to Vice-Dean PhD Ma- ria Eugenia Garcia. My gratitude to my friends and colleagues Sulema, Rigoberto, and Luis Fernando at Especialidades Químicas who through moral, spiritual support, comments and fruit- ful discussions during at stages of preparation of conferences, papers and this thesis. My heartfelt thanks to my parents Albertina (R.I.P.), Adela (R.I.P.), Nestor, without their guide, love and moral support I could not have been as I am today. My acknowledgement to sister (Elba), brother (Ramiro), nephews and sisters and broth- ers in law are highly appreciated. My special grateful for my mother in law Teresa Vil- larroel for take care and love to my family during the travel to Sweden. My especial thanks go to my children, Leonardo Fabian (five years old) and Zaret Astrid (one year old), for understanding, patience and moral support during the trav- vii Oswaldo Eduardo Ramos Ramos TRITA LWR PHD-2014:04 els far away home. My sincere and profound gratitude is extended to my wife Brenda. Her patience, love and constant encouragement in all the stages of this challenge, particularly for understand me and moral support at times when I was written this work. Oswaldo Eduardo Ramos Ramos Stockholm, June 2014 viii Geochemistry of trace elements in the Bolivian Altiplano LIST OF APPENDED PAPERS Paper I Ramos Ramos, O.E., Cáceres Choque, L.F., Ormachea, M., Bhattacharya, P., Quino, I., Quintanilla, J., Sracek, O., Thunvik, R., Bundschuh, J., García, M.E. 2012. Source and behav- ior of arsenic and trace elements in groundwater and surface water in the Poopó Lake Basin, Bolivian Altipano. Environmental Earth. Sciences 66: 793-807. (Reprinted with permission from Springer). I participated in project designing, field work, collection of the samples and analyses, data analysis and main part of writing. Paper II Ramos Ramos, O.E., Rötting T.S., French, M., Sracek, O., Quintanilla, J., Bundschuh, J., Bhattacharya, P. 2014. Hydrochemical characteristics of groundwater and surface water in the mining region of Antequera and Poopó, Eastern Cordillera, Bolivian Altiplano. Manu- script. I performed the project designing, collection of the samples in the field work, data analysis and main part of writing. Paper III Ramos Ramos, O.E., Rötting, T.S., French, M., Sracek, O., Bundschuh, J., Quintanilla, J., Bhattacharya, P. Geochemical processes controlling mobilization of arsenic and trace ele- ments in shallow aquifers and surface waters in the Antequera and Poopó mining regions, Bolivian Altiplano. Journal of Hydrology (In review) I participated in project designing, field work, collection of the samples and analyses, data analysis and main part of writing. Paper IV Ramos Ramos, O.E., Rötting, T.S., Orsag, V., Chambi, L., Sracek, O., Quintanilla, J., Bundschuh, J., Bhattacharya, P. 2014. Total and available trace elements concentrations in soils and evaluation of uptake by crops in the mining area of the Bolivian Altiplano. Manu- script. I participated in project designing, field work, collection of the samples and analyses, data analysis and main part of writing. Paper V Cáceres Choque, L.F., Ramos Ramos, O.E., Valdez, S.N., Choque R.R., Choque R.G., Férnandez, S.G., Sracek, O., Bhattacharya, P. 2013. Fractionation of heavy metals and as- sessment of contamination of the sediments of Lake Titicaca.
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