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Dissolved Oxygen Model and Passive Samplers for the Athabasca River Open Access

Descriptions

Other title
Subject/Keyword
dissolved oxygen
model
athabasca river
passive samplers
naphthenic acids
Type of item
Thesis
Degree grantor
University of Alberta
Author or creator
Martin, Nancy
Supervisor and department
Tong Yu, Department of Civil and Environmental Engineering
Examining committee member and department
David Zhu, Department of Civil and Environmental Engineering
Selma Guigard, Department of Civil and Environmental Engineering
Scott Chang, Department of Renewable Resources
Department
Department of Civil and Environmental Engineering
Specialization
Environmental Engineering
Date accepted
2014-01-20T11:11:32Z
Graduation date
2014-06
Degree
Doctor of Philosophy
Degree level
Doctoral
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.
Language
English
DOI
doi:10.7939/R31G0J08G
Rights
This thesis is made available by the University of Alberta Libraries with permission of the copyright owner solely for the purpose of private, scholarly or scientific research. This thesis, or any portion thereof, may not otherwise be copied or reproduced without the written consent of the copyright owner, except to the extent permitted by Canadian copyright law.
Citation for previous publication
Martin, N., Burkus, Z., McEachern, P., and Yu, T. (2014). "Naphthenic acids quantification in organic solvents using fluorescence spectroscopy." Journal of Environmental Science & Health, Part A: Toxic/Hazardous Substances & Environmental Engineering, 49:3, 294-306.Martin, N., McEachern, P., Yu, T., and Zhu, D. Z. (2013). "Model development for prediction and mitigation of dissolved oxygen sags in the Athabasca River, Canada." Science of the Total Environment, 443(0), 403-412.

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