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M H Schroth

Publications and source records attributed to M H Schroth.

4 recordsLinked to original sources

Nitrate-consuming processes in a petroleum-contaminated aquifer quantified using push-pull tests combined with 15N isotope and acetylene-inhibition methods.

Nitrate consumption in aquifers may result from several biogenic and abiotic processes such as denitrification, assimilatory NO3- reduction, dissimilatory NO3- reduction to ammonium (DNRA), or abiotic NO3- (or NO2-) reduction. The objectives of this study were to investigate the fate of NO3- in a petroleum-contaminated aquifer, and to assess the feasibility of using single-well push-pull tests (PPTs) in combination with 15N isotope and C2H2 inhibition methods for the quantification of processes contributing to NO3- consumption. Three consecutive PPTs were performed in a monitoring well of a heating oil-contaminated aquifer in Erlen, Switzerland. For each test, we injected 500 l of test solution containing 0.5 mM Br- as conservative tracer and either 0.5 mM unlabeled NO3- or approximately 0.3 mM 15N-labeled NO3- as reactant. Test solutions were sparged during preparation and injection with either N2, Ar or 10% C2H2 in Ar. After an initial incubation period of 1.5-3.2 h, we extracted the test solution/groundwater mixtures from the same location and measured concentrations of relevant species including Br-, NO3-, NO2-, N2O, N2, and NH4+. In addition, we determined the 15N contents of N2, N2O, NH4+, and suspended biomass from 15N/14N isotope-ratio measurements. Average total test duration was 50.5 h. First-order rate coefficients (k) were computed from measured NO3- consumption, N2-15N production and N2O-15N production. From measured NO3- consumption we obtained nearly identical estimates of k for all PPTs with small 95% confidence intervals, indicating good reproducibility and accuracy for the tests. Estimates of k from N2-15N production and N2O-15N production indicated that denitrification accounted for only 46-49% of observed NO3- consumption. Production of N2-15N in the presence of C2H2 was observed during one of the tests, which may be an indicator for abiotic NO3- reduction. Moreover, 15N isotope analyses confirmed occurrence of assimilatory NO3- reduction (0.58 at.% 15N in suspended biomass) and to a smaller extent DNRA (up to 4 at.% 15N in NH4+). Our results indicated that the combination of PPTs, 15N-isotope and C2H2 inhibition methods provided improved information on denitrification as well as alternative fates of NO3- in this aquifer.

Acetylene↗

In-situ oxidation of trichloroethene by permanganate: effects on porous medium hydraulic properties.

In-situ oxidation of dense nonaqueous-phase liquids (DNAPLs) by strong oxidants such as potassium permanganate (KMnO4) has been proposed as a possible DNAPL remediation strategy. In this study, we investigated the effects of in-situ trichloroethene (TCE) oxidation by KMnO4 on porous medium hydraulic properties. In particular, we wanted to determine the overall effects of concurrent solid phase (MnO2) precipitation, gas (CO2) evolution and TCE dissolution resulting from the oxidation reaction on the porous medium's aqueous-phase relative permeability, krw. Three TCE removal experiments were conducted in a 95-cm long, 5.1-cm i.d. glass column, which was homogeneously packed with well-characterized 30/40-mesh silica sand. TCE was emplaced in the sand-pack in residual, entrapped form through a sequence of water/TCE imbibition and drainage steps. The column was then flushed under constant aqueous flux conditions for up to 104 h with either deionized water (reference experiment), deionized water containing 5 mM KMnO4 or deionized water containing 5 mM KMnO4 and 300 mM Na2HPO4. Aqueous-phase relative permeabilities were computed from measured flow rates and measurements of aqueous-phase pressure head, h obtained using pressure transducers connected to tensiometers distributed along the column length. A dual-energy gamma radiation system was used to monitor changes in fluid saturation that occurred during each experiment. In addition, column effluent samples were collected for chemical analyses. Dissolution of TCE during deionized water flushing led to an increase in krw by approximately 22% and a local reduction in h. On the other hand, vigorous CO2 gas production and precipitation of MnO2 was visually observed during flushing with deionized water that contained 5 mM KMnO4. As a consequence, krw declined by approximately 96% and h increased locally by more than 1000 cm H2O during the first 24 h of the experiment, causing sand-pack ruptures and pump failure. Conversely, less CO2 gas production and MnO2 precipitation was visually observed during flushing with deionized water that contained 5 mM KMnO4 and 300 mM Na2HPO4. Consequently, only small increases in h (< 15 cm H2O) were observed in this experiment due to a reduction in krw of approximately 53%. While we must attribute changes in h due to variations in krw to our specific experimental design (constant aqueous flux, one-dimensional flow experiments), these experiments nevertheless confirm that successful application of in situ chemical oxidation of TCE requires consideration of detrimental processes such as MnO2 precipitation and CO2 gas formation. In addition, our results indicate that utilization of a buffered oxidant solution may improve the effectiveness of in-situ oxidation of TCE by KMnO4 in otherwise weakly buffered porous media.

Chemical Precipitation↗

In situ assessment of microbial sulfate reduction in a petroleum-contaminated aquifer using push-pull tests and stable sulfur isotope analyses.

Anaerobic microbial activities such as sulfate reduction are important for the degradation of petroleum hydrocarbons (PHC) in contaminated aquifers. The objective of this study was to evaluate the feasibility of single-well push-pull tests in combination with stable sulfur isotope analyses for the in situ quantification of microbial sulfate reduction. A series of push-pull tests was performed in an existing monitoring well of a PHC-contaminated aquifer in Studen (Switzerland). Sulfate transport behavior was evaluated in a first test. In three subsequent tests, we injected anoxic test solutions (up to 1000 l), which contained 0.5 mM bromide (Br-) as conservative tracer and 1 mM sulfate (SO4(2-)) as reactant. After an initial incubation period of 42.5 to 67.9 h, up to 1100 l of test solution/groundwater mixture was extracted in each test from the same location. During the extraction phases, we measured concentrations of relevant species including Br-, SO4(2-) and sulfide (S(-II)), as well as stable sulfur isotope ratios (delta 34S) of extracted, unconsumed SO4(2-) and extracted S(-II). Results indicated sulfate reduction activity in the vicinity of the test well. Computed first-order rate coefficients for sulfate reduction ranged from 0.043 +/- 0.013 to 0.130 +/- 0.015 day-1. Isotope enrichment factors (epsilon) computed from sulfur isotope fractionation of extracted, unconsumed SO4(2-) ranged from 20.2 +/- 5.5@1000 to 22.8 +/- 3.4@1000. Together with observed fractionation in extracted S(-II), isotope enrichment factors provided strong evidence for microbially mediated sulfate reduction. Thus, push-pull tests combined with stable sulfur isotope analyses proved useful for the in situ quantification of microbial sulfate reduction in a PHC-contaminated aquifer.

Biodegradation, Environmental↗

In situ determination of subsurface microbial enzyme kinetics.

The single-well, push-pull test has been used in previous field studies to measure in situ zero- and first-order rates for aerobic and anaerobic microbial respiration in the saturated zone. In this paper we demonstrate that the test can also be used to obtain more generalized descriptions of the kinetics of microbially mediated enzymatic reactions. Laboratory and field tests were performed with the model enzyme substrate p-nitrophenyl-beta-D-glucopyranoside (PNG). During a push-pull test, injected PNG is hydrolyzed in situ to p-nitrophenol (PNP); the rate of PNP production is taken as a measure of the beta-glucosidase activity expressed by indigenous microorganisms. Laboratory tests were performed in physical aquifer models packed with natural aquifer sediment; field tests were performed in a shallow unconfined alluvial aquifer at a petroleum contaminated site. The laboratory and field tests demonstrate that it is possible to compute the in situ rate of PNP production as a function of PNG concentration using only data from a single push-pull test. These data can then be used to estimate the Michaelis-Menton kinetic parameters Vmax and Km for the hydrolysis reaction. This approach potentially extends the range of applicability of the push-pull test approach for use in determining kinetic parameters for a wide range of microbial processes in situ. These could include the broad class of substituted nitrophenyl substrates used to assay other enzyme systems, as well as microbially mediated redox reactions that occur during contaminant transformations.

Enzymes↗