University of Alberta Dissolved Oxygen Model and Passive Samplers for the Athabasca River by Nancy Martin A thesis submitted to the Faculty of Graduate Studies and Research in partial fulfillment of the requirements for the degree of Doctor of Philosophy in Environmental Engineering Department of Civil and Environmental Engineering ©Nancy Martin Spring 2014 Edmonton, Alberta Permission is hereby granted to the University of Alberta Libraries to reproduce single copies of this thesis and to lend or sell such copies for private, scholarly or scientific research purposes only. Where the thesis is converted to, or otherwise made available in digital form, the University of Alberta will advise potential users of the thesis of these terms. The author reserves all other publication and other rights in association with the copyright in the thesis and, except as herein before provided, neither the thesis nor any substantial portion thereof may be printed or otherwise reproduced in any material form whatsoever without the author's prior written permission. Dedication I want to dedicate this thesis to my family. Their words of support keep me going when I needed more encouragement. I want to especially thank my husband. This adventure was in part possible due to the vision and leadership of my life companion. Thank you for being there in my nights of desperation and through my successes. Thank you for your love and patience. I want to thank my parents who always gave me their trust and the freedom to dream. Thank you for showing me the importance of hardwork and dedication, and for being close even though the distance. I also want to thank my grandparents and parents-in-law who are a great inspiration for me. I am so blessed to have you in my life. I also want to show my appreciation to the people who made this experience unforgettable with their friendship: Hamed, Azadeh, Mario, Deisy, Ruzma, Waqar, Helen, Alan, Po Yee and Gavin. I want to especially thank Evelyn for her kindness and invaluable help to gain confidence in my English pronunciation and writing. Above all, thank you to Him who gives us the denarius and place angels in our way. . Quiero dedicar esta tesis a mi familia. Sus palabras de apoyo me motivaron cuando más lo necesitaba. En especial quiero dar gracias a mi esposo. Gracias por escucharme en mis noches de desesperación y por celebrar mis éxitos. Esta aventura fue en parte resultado de tu visión y liderazgo… siempre hemos hecho un gran equipo. Gracias por tu amor y paciencia. También estoy profundamente agradecida a mis papás, Judith y Agustín. Ustedes me dieron las herramientas, confianza y libertad para perseguir mis sueños. Gracias por enseñarme la importancia de poner dedicación en lo que haces y por siempre estar a mi lado a pesar de la distancia. Asimismo quiero agradecer a mis abuelitos y a mis suegros quienes son una gran fuente de inspiración y un ejemplo a seguir. Estoy muy bendecida por tenerlos en mi vida… ustedes siempre me echaron porras y quiero que sepan que los quiero mucho. Esta experiencia fue inolvidable gracias a Hamed, Azadeh, Mario, Deisy, Ruzma, Waqar, Helen, Alan, Po Yee y Gavin. Quiero agradecer especialmente a Evelyn por su bondad e invaluable ayuda para ganar confianza con mi pronunciación y escritura de Ingles. Gracias ante todo a Él que nos da los denarios y que nos pone ángeles en el camino. Abstract This thesis documents the research undertaken to develop and assess modeling and monitoring tools to improve the water quality management in the Athabasca River, Alberta. The Upper Athabasca River (UAR) has experienced dissolved oxygen (DO) sags, which may affect the aquatic ecosystem. A water quality model for an 800 km reach of this river was customized, calibrated, and validated for DO and the factors that determine its concentration. The model showed that the sediment oxygen demand (SOD) represents about 50% of the DO sink in winter. The DO calibration was improved by implementing an annual SOD based on the biochemical oxygen demand (BOD) load. The model was used to estimate the assimilative capacity of the river based on a trigger DO concentration of 7 mg/L. The results revealed a maximum assimilative BOD load of 8.9 ton/d at average flow conditions, which is lower than the maximum permitted load. In addition, the model predicted a minimum assimilative flow at average BOD load of 52 m3/s. A three-level warning-system is proposed to manage the BOD load proactively at different river discharges. Other mitigation options were explored such as upgrading the wastewater treatment from the major BOD point source, and oxygen injection into the effluents. The model can be used as a management tool to forecast the DO in low flow years and evaluate mitigation measures. After improving the modeling tools for the UAR, monitoring tools for the Lower Athabasca River (LAR) were assessed. Naphthenic acids (NAs) have been identified as a main toxic component in the oil sands process affected water. However, it is desired to improve the current monitoring methods for NAs. Having a state-of-the-art monitoring system to quantify NAs in the LAR and its tributaries will allow calibrating robust models for this reach of the Athabasca River in the future. Passive samplers and the application of fluorescence spectroscopy using organic solvents were explored as a cost-effective alternative to quantify mass loading of NAs. Nine organic solvents, polar protic (methanol, ethanol, and propanol), polar aprotic (dichloromethane, acetone, and acetonitrile) and non-polar (hexane, toluene, and diethyl ether) were evaluated for quantification of NAs using fluorescence. The calibration curves of the polar protic solvents performed the best with lower light scattering and higher method sensitivity. Methanol was selected for further experiments having a strong linearity for concentrations lower than 250 mg/L (R2 > 0.99), and a low relative standard deviation (< 10%). The synchronous fluorescence mode with a reduced offset value of = 10 nm demonstrated potential for fingerprinting. Two passive samplers, the polar organic chemical integrative sampler (POCIS) and the Chemcatcher, were assessed for naphthenic acid monitoring. POCIS presented high partitioning of NAs to the polyether-sulphone (PES) membrane in combination with low diffusion to the resin. The Chemcatcher sampler with PTFE (Teflon ®) membrane and C18 disk presented a high mass transfer, and it was further evaluated using commercial NAs. The sampler was integrative for a 30-day experiment having a reduced lag time, allowing the sampler to satisfactorily account for changes of NAs concentration in water. The temperature and turbulence had a high effect on the uptake rate with a 4-fold increase from 4 to 20 oC, and a 2-fold increase from 60 to 300 rpm. Furthermore, the uptake rate of commercial NAs was lower using river water, likely due to partitioning to colloids. The uptake rate of NAs from the oil sands process water was one order of magnitude lower than that obtained for commercial NAs, which may be due to the selective adsorption of acyclic (Z = 0) compounds with high number of carbons (n). These compounds were more abundant in the commercial NAs. Uptake rates may be required for each compound or group of compounds in the NA mixture depending on the n and Z distribution. Due to the complexity of the NAs mixture (> 3000 different compounds at isomer level), it is recommended to target the compounds with greater toxicity and abundance for further uptake rate evaluation and sampler optimization. Acknowledgement I would like to thank Dr. Yuefeng Xie, Dr. Selma Guigard, Dr. Scott Chang, Dr. Tong Yu, Dr. Preston McEachern and Dr. David Zhu for being part of my PhD Thesis defense committee. I thank my supervisor Dr. Yu for giving me very interesting projects and providing me with the resources to perform my work. Thank you for the opportunities that you gave me to upgrade my degree, and to start an early career in my field. Thank you to Dr. McEachern for always finding a time to meet with me, and for pointing out new vertices to my work. I highly appreciate that you introduced me to great people in Alberta Environment who were very helpful to my research. I especially want to thank Zvonko Burkus who constantly challenged me in my experimental work. Thank you for your thorough review of my papers and for the advice that you always provided. I would like to thank Jela Burkus and Maria Demeter for providing technical support in the laboratory experiments. I also want to acknowledge the financial support from the Mexican National Council of Science and Technology (CONACYT), Natural Sciences and Engineering Research Council of Canada (NSERC). Many people in Alberta Environment and Sustainable Resource Development helped me with advice and data for this project. Table of Contents Chapter 1. General introduction .......................................................................................... 1 1.1. Background ......................................................................................................... 1 1.2. Thesis objectives ................................................................................................. 2 1.3. Thesis outline ...................................................................................................... 3 1.4. References .......................................................................................................... 3 Chapter 2. Literature review: dissolved oxygen model for the Upper Athabasca