Clemson University TigerPrints All Dissertations Dissertations 12-2016 Mitigating Risks of Oil Sands Process Affected Water Using Hybrid Constructed Wetland Treatment Systems Andrew David McQueen Clemson University, [email protected] Follow this and additional works at: https://tigerprints.clemson.edu/all_dissertations Recommended Citation McQueen, Andrew David, "Mitigating Risks of Oil Sands Process Affected Water Using Hybrid Constructed Wetland Treatment Systems" (2016). All Dissertations. 1827. https://tigerprints.clemson.edu/all_dissertations/1827 This Dissertation is brought to you for free and open access by the Dissertations at TigerPrints. It has been accepted for inclusion in All Dissertations by an authorized administrator of TigerPrints. For more information, please contact [email protected]. MITIGATING RISKS OF OIL SANDS PROCESS AFFECTED WATER USING HYBRID CONSTRUCTED WETLAND TREATMENT SYSTEMS A Dissertation Presented to the Graduate School of Forestry and Environmental Conservation Clemson University In Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy Wildlife and Fisheries Biology by Andrew David McQueen December, 2016 Accepted by: Dr. John H. Rodgers Jr., Committee Chair Dr. James W. Castle Dr. Burton C. Suedel Dr. George M. Huddleston Dr. William C. Bridges i ABSTRACT Mining leases in the Athabasca Oil Sands (AOS) region produce extensive volumes of oil sands process-affected water (OSPW) containing constituents that limit beneficial uses, including discharge into receiving aquatic systems. The aim of this research is to provide a scalable approach using hybrid constructed wetland treatment systems for the mitigation of problematic constituents in OSPW. In the first experiment in this dissertation, OSPW was characterized to identify constituents of concern (COCs) using chemical, physical, and toxicological analyses. Following identification of COCs, bench-scale manipulations (termed process-based manipulations [PBMs]) were used to remove or alter “classes” of COCs in an effort to eliminate toxicity to a sentinel aquatic invertebrate and discern treatment processes. COCs identified in OSPW included organics (naphthenic acids [NAs], oil and grease [O/G]), metals/metalloids, and suspended solids. Results from PBMs indicated that the organic fraction of OSPW was the primary source of toxicity, with oxidation (i.e. H2O2+UV254) and granular activated charcoal treatments eliminating toxicity to Ceriodaphnia dubia (7-8 d), in terms of mortality and reproduction. In the second experiment, photocatalytic degradation of commercial (Fluka) NAs was evaluated using fixed-film titanium dioxide (TiO2) irradiated with sunlight for 8 hours. Changes in NA concentrations by photocatalytic degradation were confirmed analytically and with toxicity tests using sentinel fish and aquatic invertebrate species. The half-life for Fluka NAs achieved by photocatalytic degradation was approximately 2 hours, with toxicity eliminated for vertebrate and invertebrate sentinel organisms (Pimephales promelas and Daphnia magna) by the 5th ii hour of the sunlight exposure. In the third experiment, toxicity of the NA fraction to microbial populations was evaluated to discern adverse impacts to microbially driven processes within wetlands. Following exposures to a commercial NA, potential effects on sulfate-reducing bacteria (SRB), production of sulfides (as acid-volatile sulfides [AVS]), and precipitation of divalent metals (i.e. Cu, Ni, Zn [as aqueous and simultaneously extracted metals; SEM]) were evaluated. Extent of AVS production was sufficient in all NA exposure concentrations tested to achieve ∑SEM:AVS <1, indicating conditions were conducive for treatment of divalent metals. In addition, no adverse effects to SRB (in terms of density, relative abundance, and diversity) were observed. The lines of evidence indicated that dissimilatory sulfate reduction and subsequent metal precipitation in wetlands will not be vulnerable to NA exposures. In the final experiment, a hybrid pilot- scale CWTS was designed to promote treatment processes to alter (transfer and transform) COCs using sequential reducing and oxidizing wetland reactors and a solar photocatalytic reactor using fixed film titanium dioxide (TiO2). Performance criteria were achieved as the CWTS decreased concentrations of NAs, O/G, suspended solids, and metals to an extent that eliminated toxicity to the aquatic invertebrate C. dubia. Results from this study provide proof-of-concept data to inform hybrid passive or semi-passive treatment approaches (i.e. constructed wetlands) that could mitigate COCs contained in OSPWs. Data presented in this dissertation provide approaches to identify problematic constituents contained in complex energy derived waters (e.g. OSPW) and strategies for mitigating risks by altering exposures using passive (low-energy) treatment systems. iii DEDICATION I dedicate this dissertation to my wife Cindy, who continuously encourages me and to my sons Ethan and Samuel for helping me keep life in perspective. iv ACKNOWLEDGMENTS I would like to thank my major advisor Dr. John H. Rodgers Jr. for his devotion to students and for providing me the tools needed to achieve my goals. I would also like to thank my all my committee members, Dr. James W. Castle, Dr. Burton C. Suedel, Dr. George M. Huddleston, and Dr. William C. Bridges for their support, wisdom, technical reviews, and research guidance. I would also like to thank my fellow graduate students who have provided an exceptional research team; Alyssa Calomeni, Ciera Kinley, Kyla Iwinski, Maas Hendrikse, Tyler Geer, Daniel Gaspari, and Kayla Wardlaw. I also am grateful to the sponsors of this research for providing funding support. Finally, I thank Dr. Wayne Chao for providing analytical support and always a smiling face. I offer my extreme gratitude to all who were apart of this process. v TABLE OF CONTENTS Page TITLE PAGE .................................................................................................................... i ABSTRACT ..................................................................................................................... ii DEDICATION ................................................................................................................ iv ACKNOWLEDGMENTS ............................................................................................... v LIST OF TABLES ........................................................................................................ viii LIST OF FIGURES ......................................................................................................... x CHAPTER I. INTRODUCTION ........................................................................................ 1 Background and Approach ............................................................................ 1 Organization of Dissertation ....................................................................... 11 References .................................................................................................... 16 II. A RISK-BASED APPROACH FOR IDENTIFYING CONSTITUENTS OF CONCERN IN OILS SANDS PROCESS AFFECTED WATER FROM THE ATHABASCA OIL SANDS MINING AREA ............................. 22 Abstract ........................................................................................................ 23 Introduction .................................................................................................. 24 Materials and Methods ................................................................................. 28 Results and Discussion ................................................................................ 34 Conclusion ................................................................................................... 44 References .................................................................................................... 46 III. PHOTOCATALYSIS OF A COMMERCIAL NAPHTHENIC ACID IN ..... WATER USING FIXED-FILM TIO2 ................................................... 64 Abstract ........................................................................................................ 65 Introduction .................................................................................................. 66 Materials and Methods ................................................................................. 69 Results and Discussion ................................................................................ 73 Conclusion ................................................................................................... 77 vi Table of Contents (Continued) Page References .................................................................................................... 79 IV. INFLUENCE OF COMMERCIAL (FLUKA) NAPHTHENIC ACIDS ON . ACID VOLATILE SULFIDE PRODUCTION AND DIVALENT ......... METAL PRECIPITATION .................................................................. 93 Abstract ........................................................................................................ 94 Introduction .................................................................................................. 95 Materials and Methods ................................................................................. 98 Results and Discussion .............................................................................. 104 Conclusion ................................................................................................