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Clinton D. Church

Publications and source records attributed to Clinton D. Church.

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Application of a watershed model (HSPF) for evaluating sources and transport of pathogen indicators in the Chino Basin drainage area, San Bernardino County, California

A watershed model using Hydrologic Simulation Program-FORTRAN (HSPF) was developed for the urbanized Chino Basin in southern California to simulate the transport of pathogen indicator bacteria, evaluate the flow-component and land-use contributions to bacteria contamination and water-quality degradation throughout the basin, and develop a better understanding of the potential effects of climate and land-use change on water quality. The calibration of the model for indicator bacteria was supported by historical data collected before this study and by samples collected by the U.S. Geological Survey from targeted land-use areas during storms in water-year 2004. The model was successfully calibrated for streamflow at 5 gage locations representing the Chino Creek and Mill Creek drainages. Although representing pathogens as dissolved constituents limits the model's ability to simulate the transport of pathogen indicator bacteria, the bacteria concentrations measured over the period 1998-2004 were well represented by the simulated concentrations for most locations. Hourly concentrations were more difficult to predict because of high variability in measured bacteria concentrations. In general, model simulations indicated that the residential and commercial land uses were the dominant sources for most of the pathogen indicator bacteria during low streamflows. However, simulations indicated that land used for intensive livestock (dairies and feedlots) and mixed agriculture contributed the most bacteria during storms. The calibrated model was used to evaluate how various land use, air temperature, and precipitation scenarios would affect flow and transport of bacteria. Results indicated that snow pack formation and melt were sensitive to changes in air temperature in the northern, mountainous part of the Chino Basin, causing the timing and magnitude of streamflow to shift in the natural drainages and impact the urbanized areas of the central Chino Basin. The relation between bacteria concentrations and air temperature was more complicated, and did not substantially affect the quality of water discharging from the Chino Basin into the Santa Ana River. Changes in precipitation had a greater basin-wide affect on bacteria concentrations than changes in air temperature, and varied according to location. Drainages representing natural conditions had a decrease in bacteria concentrations in correlation with an increase in precipitation, whereas drainages in the central and southern part of the Chino Basin had an increase in bacteria concentrations. Drier climate conditions tended to result in higher sensitivity of simulated bacteria concentrations to changes in precipitation. Simulated bacteria concentrations in wetter climates were usually less sensitive to changes in precipitation because bacteria transport becomes more dependent on the land-use specified bacteria loading rates and the storage limits. Bacteria contamination from impervious-area runoff is affected to a greater degree by drier climates, whereas contamination from pervious-area runoff is affected to a greater degree by wetter climates. Model results indicated that the relation between precipitation, runoff, and bacteria contamination is complicated because after the initial bacteria washoff and transport from the land surfaces during the beginning of a storm period, subsequent runoff has fewer bacteria available for washoff, which then dilutes the concentrations of bacteria in the downstream reach. It was illustrated that pathogen indicator bacteria transport depends most significantly on the relation of imperviousness to runoff, which controls the frequency, and often the magnitude, of transport, and on the contribution of higher bacteria loading rates used for pervious land areas, especially intensive feedlots, to the infrequent, but very high, peaks of bacteria contamination. The indicator bacteria transport model for the Chino Basin was based on the assumption that no

California

Fate of MTBE relative to benzene in a gasoline-contaminated aquifer (1993-98):

Methyl tert -butyl ether (MTBE) and benzene have been measured since 1993 in a shallow, sandy aquifer contaminated by a mid-1980s release of gasoline containing fuel oxygenates. In wells downgradient of the release area, MTBK was detected before benzene, reflecting a chromatographic-like separation of these compounds in the direction of ground water flow. Higher concentrations of MTBE and benzene were measured in the deeper sampling ports of multilevel sampling wells located near the release area, and also up to 10 feet (3 m) below the water table surface in nested wells located farther from the release area. This distribution of higher concentrations at depth is caused by recharge events that deflect originally horizontal ground water flowlines. In the laboratory, microcosms containing aquifer material incubated with uniformly labeled 14 C-MTBE under aerobic and anaerobic. Fe(III)-reducing conditions indicated a low but measurable biodegradation potential (<3% 14 C-MTBW as 14 CO 2 ) after a seven-month incubation period, Tert -butyl alcohol (TBA), a proposed microbial-MTBE transformation intermediate, was detected in MTBE-contaminated wells, but TBA was also measured in unsaturated release area sediments. This suggests that TBA may have been present in the original fuel spilled and does not necessarily reflect microbial degradation of MTBE. Combined, these data suggest that milligram per liter to microgram per liter decreases in MTBE concentrations relative to benzene are caused by the natural attenuation processes of dilution and dispersion with less-contaminated ground water in the direction of flow rather than biodegradation at this point source gasoline release site.

Groundwater Monitoring & Remediation

Hydrolysis of tert-butyl formate: Kinetics, products, and implications for the environmental impact of methyl tert-butyl ether

Asessing the environmental fate of methyl tert -butyl ether (MTBE) has become a subject of renewed interest because of the large quantities of this compound that are being used as an oxygenated additive in gasoline. Various studies on the fate of MTBE have shown that it can be degraded to tert -butyl formate (TBF), particularly in the atmosphere. Although it is generally recognized that TBF is subject to hydrolysis, the kinetics and products of this reaction under environmentally relevant conditions have not been described previously. In this study, we determined the kinetics of TBF hydrolysis as a function of pH and temperature. Over the pH range of 5 to 7, the neutral hydrolysis pathway predominates, with k N = (1.0 ± 0.2) × 10 −6 /s. Outside this range, strong pH effects were observed because of acidic and basic hydrolyses, from which we determined that k A = (2.7 ± 0.5) × 10 −3 /(M·s) and k B = 1.7 ± 0.3/(M·s). Buffered and unbuffered systems gave the same hydrolysis rates for a given pH, indicating that buffer catalysis was not significant under the conditions tested. The activation energies corresponding to k N , k A , and k B were determined to be 78 ± 5, 59 ± 4, and 88 ±11 kJ/mol, respectively. In all experiments, tert -butyl alcohol was found at concentrations corresponding to stoichiometric formation from TBF. Based on our kinetics data, the expected half-life for hydrolysis of TBF at pH = 2 and 4°C (as per some standard preservation protocols for water sampling) is 6 h. At neutral pH and 22°C, the estimated half-life is 5 d, and at pH = 11 and 22°C, the value is only 8 min.

Environmental Toxicology and Chemistry