Kerry McPhedran

Drinking water treatment plants (DWTPs) produce wastewaters with elevated concentrations of heavy metals, metalloids, ammonia, and other contaminants. These wastewaters require treatment via processes including wastewater stabilization ponds (WSPs). This study assessed the arsenic (As), iron (Fe), and ammonia (NH3) concentrations in a Saskatchewan DWTP WSP system of five sequential ponds. Drone imaging combined with flow and depth data was used to estimate retention times which increased from 7-9 to 8-10 days after the DWTP upgrade. Concentration trends showed Fe decreased from Pond 1 to 3 and increased in Ponds 3 and 5, while As decreased from Pond 1 to 5. Average effluent As concentrations of 10.6 µg/L were over the 5.0 µg/L guideline, while both Fe and NH3 concentrations guidelines were easily met post-upgrade in 2020. Several actions are recommended to ensure adequate WSP operation including dredging, aeration, and installing macrophytes capable of As uptake.

We present an electrochemical advanced oxidation process (eAOP) reactor employing expanded graphite, potassium iodide (KI), and electrical current, which demonstrates an exceptionally high rate of inactivation of E. coli (6log reduction in viable cells) at low current density 0.6 mA/cm^2), with low contact time (5 minutes) and low concentration of KI (10 ppm). Operando X-ray fluorescence mapping is used to show the distribution of iodine species in the reactor, and operando X-ray absorption spectroscopy in the anodic chamber reveals iodine species with higher effective oxidation state than periodate. Operando electrochemical measurements confirm the conditions in the anodic chambers are favourable for the creation of highly oxidized iodine products. The killing efficiency of this new eAOP reactor far exceeds that expected from either traditional iodine-based electrochemical water treatment or advanced oxidation systems alone, a phenomenon that may be associated with the production o...

There is movement in engineering fields and in Indigenous communities for enhancement of local participation in the design of community infrastructure. Inclusion of community priorities and unique cultural, spiritual, and traditional values harmonize the appearance, location, and functionality of developments with the social and cultural context in which they are built and contribute to holistic wellness. However, co-design processes that align community values and the technical needs of water facilities are difficult to find. A scoping review was conducted to explore the state of knowledge on co-design of water infrastructure in Indigenous Canada to build a knowledge base from which practices and processes could emerge. The scoping results revealed that articles and reports emerged only in recent years, contained case studies and meta-reviews with primary (qualitative) data, and involved community members in various capacities. Overall, 13 articles were reviewed that contributed to...

The production of oil from oil sands in northern Alberta has led to the generation of large volumes of oil sands process-affected water (OSPW) that was reported to be toxic to aquatic and other living organisms. The toxicity of OSPW has been attributed to the complex nature of OSPW matrix including the inorganic and organic compounds primarily naphthenic acids (NAs: CHO). In the present study, granular activated carbon (GAC) adsorption was investigated for its potential use to treat raw and ozonated OSPW. The results indicated that NA species removal increased with carbon number (n) for a fixed Z number; however, the NA species removal decreased with Z number for a fixed carbon number. The maximum adsorption capacities obtained from Langmuir adsorption isotherm based on acid-extractable fraction (AEF) and NAs were 98.5 mg and 60.9 mg AEF/g GAC and 60 mg and 37 mg NA/g GAC for raw and ozonated OSPW, respectively. It was found that the Freundlich isotherm model best fits the AEF and N...

Biological phosphorous (P) and nitrogen (N) removal from municipal wastewater was studied using an innovative anoxic-aerobic-anaerobic side-stream treatment system. The impact of influent water quality including chemical oxygen demand (COD), ammonium and orthophosphate concentrations on the reactor performance was evaluated. The results showed the system was very effective at removing both COD (>88%) and NH4(+)-N (>96%) despite varying influent concentrations of COD, NH4(+)-N, and total PO4(3-)-P. In contrast, it was found that the removal of P was sensitive to influent NH4(+)-N and PO4(3-)-P concentrations. The maximum PO4(3-)-P removal of 79% was achieved with the lowest influent NH4(+)-N and PO4(3-)-P concentration. Quantitative PCR (qPCR) assays showed a high abundance and diversity of phosphate accumulating organisms (PAO), nitrifiers and denitrifiers. The MiSeq microbial community structure analysis showed that the Proteobacteria (especially β-Proteobacteria, and γ-Proteobacteria) were the dominant in all reactors. Further analysis of the bacteria indicated the presence of diverse PAO genera including Candidatus Accumulibacter phosphatis, Tetrasphaera, and Rhodocyclus, and the denitrifying PAO (DPAO) genus Dechloromonas. Interestingly, no glycogen accumulating organisms (GAOs) were detected in any of the reactors, suggesting the advantage of proposed process in term of PAO selection for enhanced P removal compared with conventional main-stream processes.

Ozonation at high doses is a costly treatment for oil sands process-affected water (OSPW) naphthenic acids (NAs) degradation. To decrease costs and limit doses, different peroxone (hydrogen peroxide/ozone; H2O2:O3) processes using mild-ozone doses of 30 and 50 mg/L were investigated. The degradation efficiency of Ox-NAs (classical (O2-NAs) + oxidized NAs) improved from 58% at 30 mg/L ozone to 59%, 63% and 76% at peroxone (1:1), 50 mg/L ozone, and peroxone (1:2), respectively. Suppressing the hydroxyl radical (•OH) pathway by adding tert-butyl alcohol did significantly reduce the degradation in all treatments, while molecular ozone contribution was around 50% and 34% for O2-NAs and Ox-NAs, respectively. Structure reactivity toward degradation was observed with degradation increase for both O2-NAs and Ox-NAs with increase of both carbon (n) and hydrogen deficiency/or |-Z| numbers in all treatments. However, the combined effect of n and Z showed specific insights and differences betwee...

The current study separates colloidal organic carbon (COC) of municipal wastewater using membrane and ultrafiltration filters followed by characterization using 1H nuclear magnetic resonance (NMR) and UV absorbance with the goal of determination of size-specific characteristics, which may be used to correlate contaminant partitioning to natural COC. Passing fractions included 49.7, 44.8, 39.3, and 33.1 mg/L COC for filter sizes 1.5 μm, 0.45 μm, 100 kDa, and 1 kDa, respectively. The methodology used for processing COC prior to 1H NMR characterization was novel and successful in concentrating COC without modification of structures, which is the general drawback of other separation techniques such as resin extractions. This concentration technique is quite simple (i.e., not dependent on specialized instrumentation) and allows much shorter NMR experimental durations saving time and cost of analysis. Further work using NMR techniques will allow for greater understanding of COC molecular ...

Naphthenic acids (NAs) from oil sand process-affected water (OSPW) were liquid-liquid extracted using six organic solvents (n-pentane, n-hexane, cyclohexane, dichloromethane, ethyl ether, and ethyl acetate) at three pHs (2.0, 8.5, and 12.0). The NAs exist in ionic (ions) and non-ionic (molecules) forms in the water phase depending on their dissociation constants and the solution pH. Results showed the extractability of NA molecules depends on the solvent polarity and the extractability of NA ions on the water solubility in solvent. The organic solvent type and solution pH were found to not only impact the extracted amounts of each NA species, but also the NAs distribution in terms of molecule carbon number and hydrogen deficiency. Overall, it is concluded that ethyl ether can be used as an alternative to dichloromethane (DCM) given their similar extraction efficiencies and extracted NA profiles. This is important since DCM is known to have metabolic toxicity and transitioning to the...

Naphthenic acids (NAs) released into oil sands process-affected water (OSPW) during bitumen processing in Northern Alberta are problematic for oil sands industries due to their toxicity in the environment and resistance to degradation during conventional wastewater treatment processes. Granular activated carbon (GAC) has shown to be an effective media in removing biopersistent organics from wastewater using a combination of adsorption and biodegradation removal mechanisms. A simultaneous GAC (0.4 g GAC/L) adsorption and biodegradation (combined treatment) study was used for the treatment of raw and ozonated OSPW. After 28 days of batch treatment, classical and oxidized NAs removals for raw OSPW were 93.3% and 73.7%, and for ozonated OSPW were 96.2% and 77.1%, respectively. Synergetic effects of the combined treatment process were observed in removals of COD, the acid extractable fraction, and oxidized NAs, which indicated enhanced biodegradation and bioregeneration in GAC biofilms. A bacteria copy number >10(8) copies/g GAC on GAC surfaces was found using quantitative real time polymerase chain reaction after treatment for both raw and ozonated OSPW. A Microtox(®) acute toxicity test (Vibrio fischeri) showed effective toxicity removal (>95.3%)…

This review covers the characterization and distribution of metals and nonmetals in the Alberta oil sands region (AOSR) of Canada. The development of the oil sands industry has resulted in the release of organic, metal and nonmetal contaminants via air and water to the AOSR. For air, studies have found that atmospheric deposition of metals in the AOSR decreased exponentially with distance from the industrial emission sources. For water, toxic metal concentrations often exceeded safe levels leading to the potential for negative impacts to the receiving aquatic environments. Interestingly, although atmospheric deposition, surface waters, fish tissues, and aquatic bird eggs exhibited increasing level of metals in the AOSR, reported results from river sediments showed no increases over time. This could be attributed to physical and/or chemical dynamics of the river system to transport metals to downstream. The monitoring of the airborne emissions of relevant nonmetals (nitrogen and sulphur species) was also considered over the AOSR. These species were found to be increasing along with the oil sands developments with the resultant depositions contributing to nitrogen and sulphur accumulations resulting in ecosystem acidification and eutrophication impacts. In addition to direct monitoring of metals/nonmetals, tracing of air emissions using isotopes was also discussed. Further investigation and characterization of metals/nonmetals emissions in the AOSR are needed to determine their impacts to the ecosystem and to assess the need for further treatment measures to limit their continued output into the receiving environments.

Low concentrations (ng/L-μg/L) of emerging micropollutant contaminants in municipal wastewater treatment plant effluents affect the possibility to reuse these waters. Many of those micropollutants elicit endocrine disrupting effects in aquatic organisms resulting in an alteration of the endocrine system. A potential candidate for tertiary municipal wastewater treatment of these micropollutants is ultraviolet (UV)/hydrogen peroxide (H2O2) as an advanced oxidation process (AOP) which was currently applied to treat the secondary effluent of the Gold Bar Wastewater Treatment Plant (GBWWTP) in Edmonton, AB, Canada. A new approach is presented to predict the fluence-based degradation rate constants (kf') of environmentally occurring micropollutants including carbamazepine [(0.87-1.39) × 10(-3) cm(2)/mJ] and 2,4-Dichlorophenoxyacetic acid (2,4-D) [(0.60-0.91) × 10(-3) cm(2)/mJ for 2,4-D] in a medium pressure (MP) UV/H2O2 system based on a previous bench-scale investigation. Rather than...

Ultraperformance liquid chromatography ion mobility time-of-flight mass spectrometry (UPLC-IM-TOFMS), integrating traveling wave ion mobility spectrometry (TWIMS) with negative electrospray ionization (ESI) mode, was used to achieve two-dimensional (2D) separation (drift vs retention times) of naphthenic acids (NAs). Unprocessed and ozonated commercial NAs were used for method development. Only O2-NAs were found in unprocessed NAs with ozonation creating O3-NAs and O4-NAs. Unprocessed and ozonated oil sands process-affected waters (OSPW) were examined to validate the method for complex matrix NAs. Ozonation increased the x number for Ox-NAs (2 ≤ x ≤ 5) and also impacted the -Z number distribution. OSPW extracted using dichloromethane removed the potential for sample matrix impacts and was used for MS/MS NAs characterization. The Ox-NAs (2 ≤ x ≤ 6) were identified with O2-NAs separated into three clusters indicating isobaric and isomeric species. MS/MS was used to verify compounds, w...

ABSTRACT Porous polyvinylidene fluoride (PVDF) polymeric membranes with inclusion of Fe2O3 nanoparticles and multi-walled carbon nanotubes (MWCNTs) were developed for the Fenton-like catalytic degradation of organic contaminants at neutral pH. The PVDF was modified by in situ polymerization with methyl methacrylate to improve its hydrophilicity, and a range of membranes with different Fe2O3 and MWCNTs loadings were casted. The effect of these compositions on membrane morphology, surface functionality and hydrophilicity was investigated by microscopic, spectroscopic and surface characterization techniques. Contact angle measurements showed that MWCNTs did not change the membrane hydrophilicity, while the Fe2O3 was effective in increasing hydrophilicity. The optimum combination of 0.2% MWCNTs and 1% Fe2O3 induced pore formation and improved membrane permeability. The removal efficiency of cyclohexanoic acid (CHA) and humic acids (HAs) were evaluated. Batch studies revealed that 48% of CHA was degraded after 24 hours of membrane exposure with H2O2. For HAs, removal with H2O2 addition was significantly higher than without at 53.1±4.4% and 28.1±4.1%, respectively. These membranes also showed a significant reduction in membrane fouling. Overall, the permeate flux achieved with H2O2 was four times higher as compared to without H2O2 addition which is ascribed to the catalytic oxidation of organic molecules which accumulated at the membrane surface.

Naphthenic acids (NAs) found in oil sands process-affected waters (OSPW) have known environmental toxicity and are resistant to conventional wastewater treatments. The granular activated carbon (GAC) biofilm treatment process has been shown to effectively treat OSPW NAs via combined adsorption/biodegradation processes despite the lack of research investigating their individual contributions. Presently, the NAs removals due to the individual processes of adsorption and biodegradation in OSPW bioreactors were determined using sodium azide to inhibit biodegradation. For raw OSPW, after 28 days biodegradation and adsorption contributed 14% and 63% of NA removal, respectively. For ozonated OSPW, biodegradation removed 18% of NAs while adsorption reduced NAs by 73%. Microbial community 454-pyrosequencing of bioreactor matrices indicated the importance of biodegradation given the diverse carbon degrading families including Acidobacteriaceae, Ectothiorhodospiraceae, and Comamonadaceae. Over...

The development of biodegradation treatment processes for oil sands process-affected water (OSPW) has been progressing in recent years with the promising potential of biofilm reactors. Previously, the granular activated carbon (GAC) biofilm process was successfully employed for treatment of a large variety of recalcitrant organic compounds in domestic and industrial wastewaters. Presently, the GAC biofilm microbial development and degradation efficiency was investigated for OSPW treatment by monitoring the biofilm growth on the GAC surface in raw and ozonated OSPW in batch bioreactors. The GAC biofilm community was characterized using a next-generation 16S rRNA gene pyrosequencing technique that revealed that the phylum Proteobacteria was dominant in both OSPW and biofilms with further in depth analysis showing higher abundances of α-and γ-Proteobacteria sequences. Interestingly, many known polyaromatic hydrocarbon degraders namely, Burkholderiales, Pseudomonadales, Bdellovibrionale...

Aromatic naphthenic acids (NAs) have been shown to be more toxic than the classical NAs found in oil sands process-affected water (OSPW). To reduce this toxicity, Pseudomonas fluorescens and Pseudomonas putida were used to determine their ability to biodegrade aromatic compounds including treatments considering the impacts of external carbon and iron addition. Results showed that with added carbon P. fluorescens and P. putida have the capability of biodegrading these aromatics. In the presence of external carbon, gene expression of a functional PAH-ring hydroxylating dioxygenase (PAH-RHDα) was determined through reverse transcription real-time PCR, suggesting active degradation of OSPW aromatic compounds. Although no significant classical NAs removal was observed during this process, toxicity was reduced by 49.3% under optimal conditions. OSPW toxicity was eliminated with the combination of ozonation at a dose of 80 mg/L followed by biodegradation, indicating that it is a promising ...

Recent thermodynamics calculations and adsorption isotherms showed adsorption of a self-assembled layer (SAL) of ionized weak acids to carbon was attributed to the negatively charged hydrogen bonding (-CAHB); yet, the direct visualization and characterization of this adsorption behaviour has not been reported. Here, an Amplitude Modulation - Frequency Modulation Atomic Force Microscopy (AF-FM-AFM) technique was applied to discriminate the adsorption of decanoic acids (DA) on highly-ordered pyrolytic graphite (HOPG). Thermodynamics calculations revealed adsorption of SAL was driven by formation of -CAHB with the negatively charged functional groups of HOPG. Multilayer adsorption could occur over the adsorbed ionized SAL leading to the development of aggregates. AM-FM-AFM imaging showed the adsorption of the DA molecules forming aggregates only occurred at the HOPG functionalized steps, while DA molecules were found to adsorb over the entire functionalized HOPG surface after water-pla...

The thermodynamics of adsorption and competitive interactions of five weak acids on a graphite surface was assessed in alkaline solutions. Adsorption of the acids in mono- and multicompound solutions followed their Freundlich isotherms which suggest a diversity of graphite adsorption sites as confirmed by the presence of carboxylic and phenolic groups observed on graphite surfaces. Thermodynamic calculations assigned the formation of the negatively charged assisted hydrogen bond (-CAHB) between ionized solutes and adsorbent surface groups as the possible adsorption mechanism. However, the similar pKa values of current acids resulted in comparable free energies for -CAHB formation (ΔG(-CAHB)) being less than solvation free energies (ΔGSolv). Thus, additional ΔG is supplemented by increased hydrophobicity due to proton exchange of ionized acids with water (ΔΔG Hydrophobicity). Adsorption capacities and competition coefficients indicated that ΔΔG Hydrophobicity values depend on the neutral and ionized acid Kow. Competitive adsorption implies that multilayer adsorption may occur via hydrophobic bonding with the CH3 ends of the self-assembled layer which affects the acid adsorption capacities in mixtures as compared to monocompound solutions. The determination of adsorption mechanisms will assist in understanding of the fate and bioavailability of emerging and classical weak acids released into natural waters.