Georgia Southern University Digital Commons@Georgia Southern Electronic Theses and Dissertations Graduate Studies, Jack N. Averitt College of Summer 2017 Silver Nanoparticle Fate and Accumulation in the Aquatic Food Web of Stream Microcosms Stefan J. Petersen Follow this and additional works at: https://digitalcommons.georgiasouthern.edu/etd Part of the Terrestrial and Aquatic Ecology Commons Recommended Citation Petersen, S.J., SILVER NANOPARTICLE FATE AND ACCUMULATION IN THE AQUATIC FOOD WEB OF STREAM MICROCOSMS, GSU, 2017 This thesis (open access) is brought to you for free and open access by the Graduate Studies, Jack N. Averitt College of at Digital Commons@Georgia Southern. It has been accepted for inclusion in Electronic Theses and Dissertations by an authorized administrator of Digital Commons@Georgia Southern. For more information, please contact [email protected]. SILVER NANOPARTICLE FATE AND ACCUMULATION IN THE AQUATIC FOOD WEB OF STREAM MICROCOSMS by STEFAN PETERSEN (Under the Direction of Risa A. Cohen) ABSTRACT Silver nanoparticles (AgNPs) are used in 25% of all nano-enabled products and applied for anti-microbial properties. Silver nanoparticles are discharged into aquatic environments through wastewater discharge, runoff, and chemical spills. Once in aquatic environments silver nanoparticles have the potential to harm aquatic organisms. While the fate of silver nanoparticles in lentic systems has been investigated, limited information is available for the fate of silver nanoparticles in flowing environments. The purpose of this study was to compare the fate of AgNPs following a one-time pulsed application simulating a chemical spill, or small repetitive applications simulating effluent discharge, in artificial stream communities containing river water, sediment, periphyton, snails, and fish under realistic environmental conditions. In addition to comparing the fate of AgNPs between application types, the fate of AgNPs were also compared between 35 and 70 µg L-1 concentrations of AgNPs. Water samples were collected on days 0, 7, and 14 to quantify total Ag (TAg) in the water column. Periphyton samples were taken on days 0 and 14, and sediment, snail, and fish samples were taken on day 14 for silver content. Results from this study show that AgNP concentrations applied to streams only affects the fate of AgNPs in sediment where the majority of AgNPs settled and in fish which had limited exposure to AgNPs in the water column. Additionally, application type only affected the fate of AgNPs in periphyton samples of pulsed treated streams where snails and flowing conditions had a longer period of time to reduce Ag adsorption to periphyton compared to repetitively treated streams. In this study, silver nanoparticles rapidly settled in lotic environments placing benthic organisms at risk for Ag accumulation. Furthermore, exposure to 70 µg L-1 and 35 µg L-1 AgNPs concentrations in artificial streams was not toxic to aquatic organisms regardless of application type. This study emphasizes the importance of testing AgNP exposure under environmentally relevant conditions to assess their fate and toxicity in the environment. INDEX WORDS: Mesocosms, Ionic strength, Sedimentation, Suspension, Dissolved organic carbon, Toxicity, Periphyton, Snails, Fish, Settling SILVER NANOPARTICLE FATE AND ACCUMULATION IN THE AQUATIC FOOD WEB OF STREAM MICROCOSMS by STEFAN PETERSEN B.S., Buena Vista University, 2012 A Thesis Submitted to the Graduate Faculty of Georgia Southern University in Partial Fulfillment of the Requirements for the Degree MASTER OF SCIENCE STATESBORO, GEORGIA © 2017 STEFAN PETERSEN All Rights Reserved 1 SILVER NANOPARTICLE FATE AND ACCUMULATION IN THE AQUATIC FOOD WEB OF STREAM MICROCOSMS by STEFAN PETERSEN Major Professor: Risa A. Cohen Committee: John Stone Vinoth Sittaramane Johanne Lewis Electronic Version Approved: July 2017 2 ACKNOWLEDGEMENTS I would like to thank my family for supporting my career goals and encouraging me to pursue a master’s degree. I would like to thank Jessica Devitt for supporting me during graduate school and helping me throughout my experiment, as well as Jason Duff, Jack Eschenshroeder, Lauren Neel, Byron Collins, Garret Strickland, Becky Scott, Preston Pound, Jackson Tomlinson, Elizabeth Craddock, Allison Lutz, and Anna Wagner for collecting and processing streams samples. I would like to thank my funding sources the Georgia Southern College of Science and Mathematics, Georgia Southern Graduate Student Organization, Ogeechee River Project in addition to the Richmond Hill Fish Hatchery for providing me with the fish used in this experiment. I would also like to thank John Stone, Stephanie Canonico-May, and the Georgia Southern Chemistry department for providing the silver nanoparticles and instrumentation needed to complete my studies. I would like to thank my committee members Vinoth Sittaramane and Johanne Lewis for providing their insight and help with questions arising during this project. Lastly, I would like to thank my advisor, Risa Cohen for helping me become a better scientist and writer. 3 TABLE OF CONTENTS ACKNOWLEDGEMENTS……………………………………………………………………….2 LIST OF TABLES………………………………………………………………………………...4 LIST OF FIGURES…………………………………………………………………………….....5 CHAPTER 1 SILVER NANOPARTICLE FATE AND ACCUMULATION IN THE AQUATIC FOOD WEB OF STREAM MICROCOSMS…………………………………………...6 Chapter 1 Introduction……………………………………………………….........6 Chapter 1 Methods……………………………………………………………….12 Chapter 1 Results………………………………………………………………...20 Chapter 1 Discussion…………………………………………………………….22 REFERENCES……………………………………………………………………………..……46 APPENDIX SILVER NANOPARTICLE AND SILVER ION TOXICITY TO NAVICULA SP. IN ARTIFICIAL STREAMS Appendix Introduction………………………………………….………………..54 Appendix Methods…………………………………………………….……........55 Appendix Results………………………………………………………………...58 Appendix Discussion…………………………………………………………….60 REFERENCES……………………………………………………………………………...…...70 4 LIST OF TABLES CHAPTER 1 Page Table 1: Total water column Ag concentration after initial AgNP exposure and one and two weeks after the start of the experiment............................................................30 Table 2: Average stream pH, DO, specific conductivity, and temperature in all streams over two weeks..............................……………………………………................................31 Table 3: Comparisons showing the overall differences between treatments in Ag accumulation Day 0 periphyton, Day 14 periphyton, snails, fish, and sediment, in addition to the corresponding Tukey-Kramer, Wilcoxon Each Pair, and Steel-Dwass All Pairs Post-Hoc tests……………………………………………………………………........32 Table 4: Results of Ag accumulation in Day 14 periphyton, snails, fish, sediment, and water samples..........................................................................................................................33 Table 5: Comparisons of initial periphyton biomass, water chlorophyll a, periphyton chlorophyll a, and DOC concentration………………………………………………...……...…...35 Table 6: Analyses of the effects of AgNP concentration and application type on final periphyton biomass, water chlorophyll a, periphyton chlorophyll a, and DOC concentrations................................................................................................................36 APPENDIX Page Table 1: Average stream pH, DO, specific conductivity, and temperature in artificial streams...67 Table 2: Mean total Ag concentrations in the water column……………………………..….…..63 Table 3: Comparisons of initial DOC concentrations on Day 7 and relationships between DOC concentrations and Ag concentration in the water column…..………………….……63 Table 4: Comparisons of initial and final water chlorophyll a concentrations on Days 0 and 14……………………………………………………………………….…….…..64 Table 5: Comparisons of Navicula sp. populations over the seven-day experiment and comparisons of initial and final stream cell counts…………………………………...65 5 LIST OF FIGURES CHAPTER 1 Page Figure 1: Artificial stream microcosm showing dimensions, individual microcosm setup, and experimental set up in the greenhouse....................................................................37 Figure 2: Citrate capped AgNPs (~50nm) used in the experiment................................................38 Figure 3: Concentration of total Ag in the water column measured on Days 0, 7, and 14 by AgNP treatment.............................................................................................................39 Figure 4: Initial Ag values determined in periphyton samples comparing µg. of Ag. per g. of periphyton vs AgNP treatments....................................................................................40 Figure 5: Final periphyton Ag values after two weeks comparing µg. of Ag. per g. of periphyton vs AgNP treatments....................................................................................41 Figure 6: Accumulation of AgNPs by snails after two weeks comparing µg. of Ag. per g. of snail vs AgNP treatments..............................................................................................42 Figure 7: Accumulation of AgNPs by fish after two weeks comparing µg. of Ag. per g. of fish vs AgNP treatments................................................................................................43 Figure 8: Ag accumulation in sediment after two weeks shown comparing µg. of Ag. per g. of sediment vs AgNP treatments...................................................................................44 Figure 9: Diagram showing the recovery of AgNP fate and possible trophic interactions...........45 APPENDIX Page Figure 1: Stream and pond mesocosm design…………………………………………………....68 Figure 2: Mean Navicula sp. cell counts in ponds and streams taken on day 0, 1, 3, 5, and 7…..69
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