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Paradis, Charles J.

Publications and source records attributed to Paradis, Charles J..

Single-Well Push–Pull Tracer Test Analyses to Determine Aquifer Reactive Transport Parameters at a Former Uranium Mill Site (Grand Junction, Colorado)

At a former uranium mill site where tailings have been removed, prior work has determined several potential ongoing secondary uranium sources. These include locations with uranium sorbed to organic carbon, uranium in the unsaturated zone, and uranium associated with the presence of gypsum. To better understand uranium mobility controls at the site, four single-well push–pull tests (with a drift phase) were completed with the goal of deriving aquifer flow and contaminant transport parameters for inclusion in a future sitewide reactive transport model. This goes beyond the traditional use of a constant sorption distribution coefficient (K d ) and allows for the evaluation of alternative remedial injection fluids, which can produce variable K d values. Dispersion was first removed from the resulting data to determine possible reactions before conducting reactive transport simulations. These initial analyses indicated the potential need to include cation exchange, uranium sorption, and gypsum dissolution. A reactive transport model using multiple layers to account for partially penetrating wells was completed using the PHT-USG reactive transport modeling code and calibrated using PEST. The model results quantify the hydraulic conductivity and dispersion parameters using the injected tracer concentrations. Uranium sorption, cation exchange, and gypsum dissolution parameters were quantified by comparing the simulated versus observed geochemistry. All simulations required some cation exchange and calcite equilibrium, and one simulation required gypsum dissolution to improve the model fit for calcium and sulfate. Uranium sorption parameters were not strongly influenced by the other parameter values but were highly influenced by uranium concentrations during the drift phase, with possible kinetic rate limitations. Thus, a future recommendation for such push–pull tests is to collect more geochemical data during the drift phase. The final uranium sorption parameters were within the range of values determined from prior column testing. The flow and transport parameters derived from these single-well push–pull tests will provide initial parameters for any future sitewide reactive transport model.

54 ENVIRONMENTAL SCIENCES↗

Sustained Ability of a Natural Microbial Community to Remove Nitrate from Groundwater

Abstract Microbial‐mediated nitrate removal from groundwater is widely recognized as the predominant mechanism for nitrate attenuation in contaminated aquifers and is largely dependent on the presence of a carbon‐bearing electron donor. The repeated exposure of a natural microbial community to an electron donor can result in the sustained ability of the community to remove nitrate; this phenomenon has been clearly demonstrated at the laboratory scale. However, in situ demonstrations of this ability are lacking. For this study, ethanol (electron donor) was repeatedly injected into a groundwater well (treatment) for six consecutive weeks to establish the sustained ability of a microbial community to remove nitrate. A second well (control) located upgradient was not injected with ethanol during this time. The treatment well demonstrated strong evidence of sustained ability as evident by ethanol, nitrate, and subsequent sulfate removal up to 21, 64, and 68%, respectively, as compared to the conservative tracer (bromide) upon consecutive exposures. Both wells were then monitored for six additional weeks under natural (no injection) conditions. During the final week, ethanol was injected into both treatment and control wells. The treatment well demonstrated sustained ability as evident by ethanol and nitrate removal up to 20 and 21%, respectively, as compared to bromide, whereas the control did not show strong evidence of nitrate removal (5% removal). Surprisingly, the treatment well did not indicate a sustained and selective enrichment of a microbial community. These results suggested that the predominant mechanism(s) of sustained ability likely exist at the enzymatic‐ and/or genetic‐levels. The results of this study demonstrated the in situ ability of a microbial community to remove nitrate can be sustained in the prolonged absence of an electron donor.

54 ENVIRONMENTAL SCIENCES↗

Iron- and aluminium-induced depletion of molybdenum in acidic environments impedes the nitrogen cycle: Mo depletion by Fe/Al precipitation at ORR

Anthropogenic nitrate contamination is a serious problem in many natural environments. Nitrate removal by microbial action is dependent on the metal molybdenum (Mo), which is required by nitrate reductase for denitrification and dissimilatory nitrate reduction to ammonium. The soluble form of Mo, molybdate (MoO 4 2- ), is incorporated into and adsorbed by iron (Fe) and aluminium (Al) (oxy) hydroxide minerals. In this paper, we used Oak Ridge Reservation (ORR) as a model nitrate-contaminated acidic environment to investigate whether the formation of Fe- and Al-precipitates could impede microbial nitrate removal by depleting Mo. We demonstrate that Fe and Al mineral formation that occurs as the pH of acidic synthetic groundwater is increased, decreases soluble Mo to low picomolar concentrations, a process proposed to mimic environmental diffusion of acidic contaminated groundwater. Analysis of ORR sediments revealed recalcitrant Mo in the contaminated core that co-occurred with Fe and Al, consistent with Mo scavenging by Fe/Al precipitates. Nitrate removal by ORR isolate Pseudomonas fluorescens N2A2 is virtually abolished by Fe/Al precipitate-induced Mo depletion. Lastly, the depletion of naturally occurring Mo in nitrate- and Fe/Al-contaminated acidic environments like ORR or acid mine drainage sites has the potential to impede microbial-based nitrate reduction thereby extending the duration of nitrate in the environment.

54 ENVIRONMENTAL SCIENCES↗

Improved Method for Estimating Reaction Rates During Push‐Pull Tests

Abstract The breakthrough curve obtained from a single‐well push‐pull test can be adjusted to account for dilution of the injection fluid in the aquifer fluid. The dilution‐adjusted breakthrough curve can be analyzed to estimate the reaction rate of a solute. The conventional dilution‐adjusted method assumes that the ratios of the concentrations of the nonreactive and reactive solutes in the injection fluid vs. the aquifer fluid are equal. If this assumption is invalid, the conventional method will generate inaccurate breakthrough curves and may lead to erroneous conclusions regarding the reactivity of a solute. In this study, a new method that generates a dilution‐adjusted breakthrough curve was theoretically developed to account for any possible combination of nonreactive and reactive solute concentrations in the injection and aquifer fluids. The newly developed method was applied to a field‐based data set and was shown to generate more accurate dilution‐adjusted breakthrough curves. The improved dilution‐adjusted method presented here is simple, makes no assumptions regarding the concentrations of the nonreactive and reactive solutes in the injection and aquifer fluids, and easily allows for estimating reaction rates during push‐pull tests.

54 ENVIRONMENTAL SCIENCES↗

Push-pull tests for estimating effective porosity: expanded analytical solution and in situ application

The analytical solution describing the one-dimensional displacement of the center of mass of a tracer during an injection, drift, and extraction test (push-pull test) was expanded to account for displacement during the injection phase. The solution was expanded to improve the in situ estimation of effective porosity. The truncated equation assumed displacement during the injection phase was negligible, which may theoretically lead to an underestimation of the true value of effective porosity. To experimentally compare the expanded and truncated equations, single-well push-pull tests were conducted across six test wells located in a shallow, unconfined aquifer comprised of unconsolidated and heterogeneous silty and clayey fill materials. The push-pull tests were conducted by injection of bromide tracer, followed by a non-pumping period, and subsequent extraction of groundwater. The values of effective porosity from the expanded equation (0.6–5.0%) were substantially greater than from the truncated equation (0.1–1.3%). The expanded and truncated equations were compared to data from previous push-pull studies in the literature and demonstrated that displacement during the injection phase may or may not be negligible, depending on the aquifer properties and the push-pull test parameters. The results presented here also demonstrated the spatial variability of effective porosity within a relatively small study site can be substantial, and the error-propagated uncertainty of effective porosity can be mitigated to a reasonable level (< ± 0.5%). The tests presented here are also the first that the authors are aware of that estimate, in situ, the effective porosity of fine-grained fill material.

58 GEOSCIENCES↗