Linear alkylbenzenesulfonate (LAS) is the most widely used anionic surfactant in commercial detergent formulations. The environmental fate of LAS is of interest because of its disposal to wastewater treatment facilities and subsequent occurrence as a micropollutant in surface waters and groundwater. While LAS fate in wastewater treatment systems and surface waters is well-documented, few studies describe LAS fate in groundwater. This work investigates the transport and biodegradation of LAS in sewage-contaminated groundwater using natural-gradient pulsed and continuous field tracer tests and laboratory column experiments. An "in-vial" disk elution technique that couples solid phase extraction disk elution of LAS as tetrabutylammonium ion pairs with injection-port derivatization was developed for the determination of LAS in groundwater. Pulsed tracer tests then were conducted in an aerobic (~9 mg/L dissolved oxygen) uncontaminated zone, and a moderately aerobic (~1 mg/L dissolved oxygen), sewage-contaminated zone. A continuous injection test also was conducted in the sewage-contaminated zone. Chromatographic separation of the surfactant mixture was observed and attributed to the greater retardation of the longer alkyl chain homologs during transport. In the sewage-contaminated groundwater, biodegradation preferentially removed the longer alkyl chain homologs and external isomers resulting in LAS mixtures that were enriched in the more mobile and biologically-resistant components. LAS mass removal coincided with a decrease in dissolved oxygen concentrations, the appearance of LAS metabolites, and an increase in the number of free-living bacteria. The composition of the LAS mixture changed in the continuous field and column experiments and biodegradation rates increased as dissolved oxygen concentration increased. Mass removal rates were generally 2-3 times greater in the column experiments than in the field for similar dissolved oxygen concentrations. Rate constants for the continuous and pulsed tests conducted in the field were comparable indicating that increased exposure time of the aquifer sediments to the LAS did not increase biodegradation rates. / Graduation date: 1998

Graduation date: 1996

In situ bioremediation of pentachlorophenol-contaminated ground water in a sequential anaerobic-aerobic down borehole permeable barrier reactor requires a non-toxic primary substrate for dichlorophenol cometabolism. Serum bottle tests comparing the effectiveness of eight primary substrates for aerobic dichlorophenol degradation showed phenol to be the most effective followed by imitation vanilla flavoring, guaiacol, sodium benzoate, molasses, acetic acid, propylene glycol and ethyl vanillin in propylene glycol. As phenol is a pollutant, imitation vanilla flavoring is the recommended primary substrate for field use. In a second bottle test, 3,4,5-trichlorophenol was not sufficiently biotransformed, emphasizing the need for biotransformation to occur in the anaerobic zone of the reactor. / Graduation date: 1996

This project was a part of a study to evaluate natural attenuation (NA) as a viable remedial option for petroleum hydrocarbon (PHC) contamination at upstream oil- and gas-contaminated sites in Alberta, Canada. Laboratory mesocosms were set up using groundwater and sediment materials collected from two PHC contaminated sites (Site 1 and Site 3) in Alberta to investigate the enhancement of anaerobic PHC biodegradation by amendment of terminal electraon acceptors (TEAs, nitrate or sulfate) and/or nutrients (ammonium and phosphate). Multiple lines of evidence, including the removal of benzene, toluene, ethylbenzene and xylenes (BTEX) and CCME F1 fraction hydrocarbons (C6 to C10), rapid depletion of TEAs, the production of biogenic gases, and detection of the metabolites verified that anaerobic PHC biodegradation was occurring in both laboratory mesocosm studies. Selective biodegradation of PHCs under different reducing conditions was observed. However, there was no conclusive evidence that one reducing condition will universally favor the biodegradation of specific PHCs. In both studies, nutrient amendment showed no enhancement effects. The calculated first-order biodegradation rates in Site 1 mesocosm study ranged from 0.0032 to 0.033 d-1 for benzene, 0 to 0.028 d-1 for ethylbenzene, 0.0021 to 0.036 d-1 for m-, p-xylenes, and 0.0006 to 0.0045 d-1 for F1-BEX (F1 hydrocarbons exclduding BEX) under the tested conditions. The laboratory first-order biodegradation rates of BEX were higher than the estimated field rates, indicating the potential of enhanced anaerobic biodegradation in situ. However, when comparing the TEA amended mesocosms with the unamended controls (in which iron reduction might be the predominant process), the enhancement effects were less apparent and inconsistent. The calculated first-order biodegradation rates in Site 3 mesocosm study ranged from 0 to 0.0009 d-1 for benzene, 0 to 0.011 d-1 for ethylbenzene, 0 to 0.0016 d-1 for m- and p-xylenes, and 0 to 0.15 d-1 for o-xylene. Sulfate amendment significantly stimulated biodegradation of all xylenes and CCME F1 hydrocarbons. However, there was no definitive evidence that nitrate or sulfate amendment could enhance benzene or ethylbenzene biodegradation. / Environmental Engineering

A low, but significant, fraction of the carbohydrate portion of herbaceous biomass may be composed of fructose/fructosyl-containing components (“fructose equivalents”); such carbohydrates include sucrose, fructo-oligosaccharides, and fructans. Standard methods used for the quantification of structural-carbohydrate-derived neutral monosaccharide-equivalents in biomass are not particularly well suited for the quantification of fructose equivalents due to the inherent instability of fructose in conditions commonly used for hemicellulose/cellulose hydrolysis (> 80% degradation of fructose standards treated at 4% sulfuric acid, 121oC, 1 hr). Alternative time, temperature and acid concentration combinations for fructan hydrolysis were considered using model fructans (inulin, β-2,1 and levan, β-2,6) and a grass seed straw (Tall Fescue, Festuca arundinacea) as representative feedstocks. The instability of fructose, relative to glucose and xylose, at higher acid/temperature combinations is demonstrated, all rates of fructose degradation being acid and temperature dependent. Fructans are shown to be completely hydrolyzed at acid concentrations well below that used for the structural carbohydrates, as low as 0.2%, at 121oC for 1 hr. Lower temperatures are also shown to be effective, with corresponding adjustments in acid concentration and time. Thus, fructans can be effectively hydrolyzed under conditions where fructose degradation is maintained below 10%. Hydrolysis of the β-2,1 fructans at temperatures ≥ 50oC, at all conditions consistent with complete hydrolysis, appear to generate difructose dianhydrides. These same compounds were not detected upon hydrolysis of levan, sucrose, or straw components. It is suggested that fructan hydrolysis conditions be chosen such that hydrolysis goes to completion, fructose degradation is minimized, and difructose dianhydride production is accounted for. / Graduation date: 2009

Polyacid modified composite resins (PMCR) are designed to combine the aesthetics of composites-resins with the fluoride release of glass-ionomers. Objectives: to compare the relative biostability and fluoride release of PMCR (F2000 [3M]; Dyract eXtra [DENTSPLY]) and a composite-resin (Z250 [3M]). Standardized samples were incubated in either buffer or human saliva derived esterases (HSDE) for up to 14 days. High- performance-liquid-chromatography revealed higher amounts of degradation products for all HSDE incubated groups, as compared with the buffer. Z250 samples released higher amounts of bishydroxypropoxyphenylpropane (Bis-HPPP) and triethylene-glycol-dimethacrylate (TEGDMA) than both PMCR. Dyract eXtra and F2000 samples released unique degradation products, respectively di-ester of 2-hydroxyethyl di-methacrylate with butane tetracarboxylic acid (TCB) and glyceryl dimethacrylate (GDMA). F2000 samples released more fluoride for both incubation periods in the presence of HSDE as compared with Dyract eXtra samples. Scanning electron microscopy analysis confirmed the greater degradation of both PMCR, as compared with Z250.

Background: Human salivary esterases have been shown to degrade dental resin composite restorations in vivo. Objective: To optimize in vivo protocols to recover biodegradation products and to compare the biostability of urethane-modified-bisGMA- (ubis) and bisGMA-based (bis) commercial resin composites. Methods: Class V and III composite restorations were placed in patients using adhesive and composite resin. Gingival crevicular fluid (GCF), plaque and a 2-minute oral rinse with 20% ethanol in saline (n=10) were collected immediately and 7-days after restoration placement. Samples were analyzed for biodegradation products using high performance liquid chromatography. The oral rinse protocol was then used to compare the bis and ubis composite resins (Z250, 3M; TPH, Dentsply) (n=58). Results and conclusions: The bisGMA composite matrix derived product, bishydroxypropoxyphenylpropane (BisHPPP) was only detected from oral rinse collected immediately after restoration placement. There was no statistical difference in the amount of bisHPPP collected from bis and ubis composite resins. This research was supported by CIHR (MOP 68947).

Background: Human salivary esterases have been shown to degrade dental resin composite restorations in vivo. Objective: To optimize in vivo protocols to recover biodegradation products and to compare the biostability of urethane-modified-bisGMA- (ubis) and bisGMA-based (bis) commercial resin composites. Methods: Class V and III composite restorations were placed in patients using adhesive and composite resin. Gingival crevicular fluid (GCF), plaque and a 2-minute oral rinse with 20% ethanol in saline (n=10) were collected immediately and 7-days after restoration placement. Samples were analyzed for biodegradation products using high performance liquid chromatography. The oral rinse protocol was then used to compare the bis and ubis composite resins (Z250, 3M; TPH, Dentsply) (n=58). Results and conclusions: The bisGMA composite matrix derived product, bishydroxypropoxyphenylpropane (BisHPPP) was only detected from oral rinse collected immediately after restoration placement. There was no statistical difference in the amount of bisHPPP collected from bis and ubis composite resins. This research was supported by CIHR (MOP 68947).

A gas-fluidized bed bioreactor was developed in this research as a new method for treating polluted air. The fluidization characteristics of selected packing materials were investigated. Then, bioremediation was tested using two types of packing in a fluidized bioreactor, as well as in a comparable packed bed. Microorganisms on the particles biodegrade contaminants in the polluted air, which flows up through the bed. At high flowrates, the polluted air fluidizes the particles, while at low velocities the operation is in packed bed mode.<p>Initially, sawdust was selected for use as a packing material. Due to the poor fluidization properties of sawdust, glass spheres were added. A mixture of sawdust and glass spheres remained well mixed during fluidization. In the mixture, interparticle forces increased with increasing moisture in the sawdust, eventually causing defluidization of the bed. In the absence of bioremediation, mass transfer was studied between ethanol-contaminated air and sawdust/glass sphere packing, and found to be higher in the fluidized versus packed mode. In bioremediation experiments, ethanol removal efficiencies were as high as 95% in both operating modes. The maximum elimination capacities (EC) of ethanol were 75 and 225 g m^-3 sawdust h^-1 in the fluidized and packed beds respectively.<p>The packing of the fluidized bed bioreactor was optimized in order to boost bioremediation rates. Experiments showed that peat granules fluidized well in a bubbling regime, likely due to their relatively high density and sphericity. In peat bioremediation trials, the fluidized mode outperformed the packed bed; the maximum ECs were 1520 and 530 g m^-3 peat h^-1, respectively. Removal efficiency in the fluidized mode decreased with velocity, because the size and amount of large bubbles increased.<p>A steady-state model of the fluidized bioreactor was developed. By taking account of bubble properties during fluidization, the model helps to explain how bubble size, microbial properties and bioreactor residence time affect removal efficiency and elimination capacity of the bioreactor.<p>A peat gas-fluidized bioreactor shows promise as an efficient, low-cost technology for air treatment. Particle mixing in the fluidized bed may prevent operating problems associated with the packed bed bioreactor. Fluidized bioreactors are ideal for the treatment of high volume, low concentration air emissions.

The herbicide, Dacthal (dimethyl 2,3,5,6,-tetrachloroterephthalate) is hydrolyzed to give the corresponding diacid and this derivative is a common contaminant in ground water. In the Ontario region of eastern Oregon the use of this herbicide on onions has resulted in the contamination of an aquifer with this derivative. Since movement to groundwater is determined by the hydrolysis of the parent compound to a more soluble derivative. The rate at which this hydrolysis reaction occurs and the stability of the metabolite must be defined. These parameters have been determined using soils from Ontario in which onions had been raised. At room temperature and 50% field capacity, the parent was hydrolyzed rapidly (half-life 16 days) to the diacid derivative. An increase of the incubation temperature to 38°C reduced the hydrolysis rate significantly (half-life 86.8 days). It is assumed that this response reflects reduced microbial activity at the higher temperature. At both temperatures only small amounts of the monoacid intermediate were detected suggesting that the Dacthal monoacid was being hydrolyzed at a faster rate than the parent. It was established that at room temperature, the half-life of the monoacid was only 2.8 days. Over the 300 days the experiments were carried out, little if any degradation of the diacid metabolite could be detected. There was virtually no degradation of the parent over a 60 day period in sterilized soil, suggesting that microbial activity is primarily responsible for this step. By contract, the monoacid was hydrolyzed at comparable rates in sterilized and nonsterilized soil. This study explains why the Dacthal metabolite is a common contaminant in groundwater. The parent is rapidly hydrolyzed to the diacid which is much more water soluble. More important, however, is the persistence of the diacid metabolite in the environment. / Graduation date: 1992