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Arsenic Geochemistry in Warm Spring Ponds: New Field and Experimental Results Heather Boese Montana Tech of the University of Montana

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Arsenic Geochemistry in Warm Spring Ponds: New Field and Experimental Results Heather Boese Montana Tech of the University of Montana Montana Tech Library Digital Commons @ Montana Tech Graduate Theses & Non-Theses Student Scholarship Spring 2015 Arsenic Geochemistry in Warm Spring Ponds: New Field and Experimental Results Heather Boese Montana Tech of the University of Montana Follow this and additional works at: http://digitalcommons.mtech.edu/grad_rsch Part of the Other Environmental Sciences Commons Recommended Citation Boese, Heather, "Arsenic Geochemistry in Warm Spring Ponds: New Field and Experimental Results" (2015). Graduate Theses & Non- Theses. 13. http://digitalcommons.mtech.edu/grad_rsch/13 This Thesis is brought to you for free and open access by the Student Scholarship at Digital Commons @ Montana Tech. It has been accepted for inclusion in Graduate Theses & Non-Theses by an authorized administrator of Digital Commons @ Montana Tech. For more information, please contact [email protected]. ARSENIC GEOCHMISTRY IN WARM SPRING PONDS: NEW FIELD AND EXPERIMENTAL RESULTS by Heather E. Boese A thesis submitted in partial fulfillment of the requirements for the degree of Master of Science in Environmental Engineering Montana Tech 2015 ii Abstract Silver Bow Creek (SBC) flows into the Warm Springs Ponds Operable Unit (WSPOU), where various containment cells are used to precipitate copper and other metals (e.g., Cd, Cu, Mn, Pb, Zn). Lime is added seasonally to increase the pH and assist in removal of metals from the water column. Although the WSPOU is effective at removing copper and other cationic trace metals, concentrations of dissolved arsenic exiting the facility are often above the site specific standard, 20 g/L, during low-flow periods each summer and fall. This thesis is a continuation of arsenic geochemistry studies by Montana Tech in the WSPOU. Field work focused on Pond 3, the largest and first in the series of treatment ponds. Shallow groundwater was sampled from 8 PVC piezometers located near the south end of Pond 3. Three sediment pore-water diffusion samplers (“peepers”) were also deployed at the south end of Pond 3 to examine vertical gradients in chemistry in the top 25 cm of the pond sediment. In general, the pH and Eh values of the shallow groundwater and sediment pore-water were less than in the pond water. Concentrations of arsenic were generally higher in subsurface water, and tended to pass through a maximum (up to 530 g/L) about 10 cm below the sediment-water interface. In the peeper cells, there was a strong positive correlation between dissolved As and dissolved Fe, and an inverse correlation with sulfate. Therefore, the zone of arsenic release corresponds to a zone of bacterial Fe and sulfate reduction in the shallow, organic-rich sediment. Redox speciation of arsenic shows that arsenate (As(V)) is dominant in the pond, and arsenite (As(III)) is dominant in the subsurface water. A series of laboratory experiments with pH adjustment were completed using SBC water collected near the inlet to the WSPOU as well as water and shallow sediment collected from Pond 3. Water ± sediment mesocosms were set up in 1-L Nalgene bottles (closed system) or a 20-L aquarium (open system), both with continuous stirring. The pH of the mesocosm was adjusted by addition of NaOH or HNO3 acid. The closed system provided better pH control since the water was not in contact with the atmosphere, which prevented exchange of carbon dioxide. In both the closed and open systems, dissolved arsenic concentrations either decreased or stayed roughly the same with increase in pH to values > 11. Therefore, the release of dissolved As into the treatment ponds in low-flow periods is not due to changes in pH alone. All of these results support the hypothesis that the arsenic release in WSPOU is linked to microbial reduction of ferric oxide minerals in the organic-rich sediment. Upwards diffusion of dissolved As from the sediment pore-water into the pond water is the most likely explanation for the increase in As concentration of the WSPOU in low-flow periods. Keywords: Arsenic Speciation, Lime Treatment, Iron Reducing Bacteria, Sulfate Reducing Bacteria, Peepers, Geochemical Modeling iii Dedication I dedicate this master’s thesis to my family. They have been my cheerleaders all along this road believing that I could achieve this significant accomplishment. I want to extend my sincere gratitude to my parents, Dick and Debbie Crockford, for their unconditional love and words of encouragement and raising me with the attitude that anything is possible with perseverance and motivation. I want to acknowledge my husband, Chauncey, for his love and support and his patience when there were unexpected changes in my schedule on this project and he needed to step up and fulfill duties as mom and dad to our two sons. I want to thank my two amazing sons, Liam and Quincey Boese, who have taught me much along this road and love me for who I am. They always brighten my day with their humor and remind me that tomorrow is a whole new day; I love that they are so inquisitive and love to learn. And last, but definitely not least, I want to thank my sisters, Rebecca Combs and Theresa Unbehend, and my aunt, Mary Ellen Crockford, whom provided me with inspiration and support whenever I needed it. iv Acknowledgements I want to thank Dr. Chris Gammons for providing me this amazing opportunity to work with him on this stimulating project. He shared an enormous amount of knowledge with me and patiently guided me throughout the process - his dedication to his students is unsurpassed. Also, I would like to thank Dr. Kumar Ganesan, Jeanne Larson, and Gary Wyss whom served on my committee and provided me with words of wisdom as well as edited my thesis. I’d like to give additional appreciation to the Environmental Engineering Department who funded my graduate schooling and opened more doors for my professional career by providing me this opportunity. My project would not have been successful without the help of Gary Wyss who gladly helped me operate the ICP-OES and assisted me with preparation of my lab samples. I’d like to thank Seth Reedy, Corey Swisher, and Angela Bolton, fellow graduate students, for assisting me in the field and in the lab during this project. I’m appreciative of the help provided by the operators at the Warm Springs Ponds during field work. Finally, I want to thank Jim Chatham with ARCO/BP for funding this thesis project; the support provided by companies such as ARCO/BP is tremendously appreciated by the students and Montana Tech and hopefully the symbiotic relationship continues far into the future. The learning opportunities on projects like these provide an unmeasurable amount of education and practical experience as well as a valuable springboard for our careers. v Table of Contents ABSTRACT ................................................................................................................................................ II DEDICATION ........................................................................................................................................... III ACKNOWLEDGEMENTS ........................................................................................................................... IV TABLE OF CONTENTS ................................................................................................................................ V LIST OF TABLES ...................................................................................................................................... VII LIST OF FIGURES .................................................................................................................................... VIII GLOSSARY OF TERMS ............................................................................................................................... X 1. INTRODUCTION ................................................................................................................................. 1 1.1. Background ........................................................................................................................ 1 1.2. WSPOU Layout ................................................................................................................... 2 1.3. Possible causes of arsenic releases from the WSPOU ........................................................ 4 1.4. Previous Work by Montana Tech ....................................................................................... 5 1.5. Thesis Objectives ................................................................................................................ 6 2. METHODS ........................................................................................................................................ 8 2.1. Laboratory experiment and sampling methods ................................................................. 8 2.2. Field Methods ................................................................................................................... 11 2.3. Analytical Methods .......................................................................................................... 17 2.4. pH and Eh ......................................................................................................................... 18 2.5. Alkalinity .......................................................................................................................... 19 2.6. Ammonia .......................................................................................................................... 19 2.7. Soluble
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