Mario Schirmer

Biodegradation modelling of a dissolved gasoline plume applying independent laboratory and field parameters

Abstract Biodegradation of organic contaminants in groundwater is a microscale process which is often observed on scales of 100s of metres or larger. Unfortunately, there are no known equivalent parameters for characterizing the biodegradation process at the macroscale as there are, for example, in the case of hydrodynamic dispersion. Zero- and first-order degradation rates estimated at the laboratory scale by model fitting generally overpredict the rate of biodegradation when applied to the field scale because limited electron acceptor availability and microbial growth are not considered. On the other hand, field-estimated zero- and first-order rates are often not suitable for predicting plume development because they may oversimplify or neglect several key field scale processes, phenomena and characteristics. This study uses the numerical model BIO3D to link the laboratory and field scales by applying laboratory-derived Monod kinetic degradation parameters to simulate a dissolved gasoline field experiment at the Canadian Forces Base (CFB) Borden. All input parameters were derived from independent laboratory and field measurements or taken from the literature a priori to the simulations. The simulated results match the experimental results reasonably well without model calibration. A sensitivity analysis on the most uncertain input parameters showed only a minor influence on the simulation results. Furthermore, it is shown that the flow field, the amount of electron acceptor (oxygen) available, and the Monod kinetic parameters have a significant influence on the simulated results. It is concluded that laboratory-derived Monod kinetic parameters can adequately describe field scale degradation, provided all controlling factors are incorporated in the field scale model. These factors include advective–dispersive transport of multiple contaminants and electron acceptors and large-scale spatial heterogeneities.

Laboratory evidence of MTBE biodegradation in Borden aquifer material.

Mainly due to intrinsic biodegradation, monitored natural attenuation can be an effective and inexpensive remediation strategy at petroleum release sites. However, gasoline additives such as methyl tert-butyl ether (MTBE) can jeopardize this strategy because these compounds often degrade, if at all, at a slower rate than the collectively benzene, toluene, ethylbenzene and the xylene (BTEX) compounds. Investigation of whether a compound degrades under certain conditions, and at what rate, is therefore important to the assessment of the intrinsic remediation potential of aquifers. A natural gradient experiment with dissolved MTBE-containing gasoline in the shallow, aerobic sand aquifer at Canadian Forces Base (CFB) Borden (Ontario, Canada) from 1988 to 1996 suggested that biodegradation was the main cause of attenuation for MTBE within the aquifer. This laboratory study demonstrates biologically catalyzed MTBE degradation in Borden aquifer-like environments, and so supports the idea that attenuation due to biodegradation may have occurred in the natural gradient experiment. In an experiment with batch microcosms of aquifer material, three of the microcosms ultimately degraded MTBE to below detection, although this required more than 189 days (or >300 days in one case). Failure to detect the daughter product tert-butyl alcohol (TBA) in the field and the batch experiments could be because TBA was more readily degradable than MTBE under Borden conditions.

Modeling the impact of ethanol on the persistence of benzene in gasoline‐contaminated groundwater

[1]xa0The effect of ethanol on the persistence of benzene in gasoline-contaminated aquifers is simulated using a multicomponent reactive transport model. The conceptual model includes a residual gasoline source which is dissolving at the water table into an aquifer containing a limited amount of dissolved oxygen. The coupled processes include nonaqueous phase liquid (NAPL) source dissolution, transport of the dissolved components, and competitive aerobic biodegradation. Comparisons are made between dissolved benzene plumes from a gasoline spill and those from an otherwise equivalent spill containing 10% ethanol (gasohol). Simulations have shown that under some conditions a 10% ethanol component in gasoline can extend the travel distance of a benzene plume by up to 150% relative to that from an equivalent ethanol-free gasoline spill. The increase occurs because ethanol preferentially consumes oxygen, which reduces the biodegradation rate of benzene. The impact is limited, however, because sufficient oxygen disperses behind the ethanol plume into the slightly retarded benzene plume. A sensitivity analysis for two common spill scenarios showed that background oxygen concentrations and benzene retardation have the most significant influence on ethanol-induced benzene persistence. The results are highly relevant in light of the increasing use of ethanol-enhanced fuels throughout the world and the forthcoming ban of methyl tertiary-butyl-ether (MTBE) in California and its probable replacement by ethanol by the end of 2002.

Benzene oxidation under sulfate-reducing conditions in columns simulating in situ conditions

The oxidation of benzene under sulfate-reducing conditions was examined in column and batch experiments under close to in situ conditions. Mass balances and degradation rates for benzene oxidation were determined in four sand and four lava granules filled columns percolated with groundwater from an anoxic benzene-contaminated aquifer. The stoichiometry of oxidized benzene, produced hydrogen carbonate and reduced sulfate correlated well with the theoretical equation for mineralization of benzene with sulfate as electron acceptor. Mean retention times of water in four columns were determined using radon (222Rn) as tracer. The retention times were used to calculate average benzene oxidation rates of 8–36xa0μMxa0benzenexa0day−1. Benzene-degrading, sulfide-producing microcosms were successfully established from sand material of all sand filled columns, strongly indicating that the columns were colonized by anoxic benzene-degrading microorganisms. In general, these data indicate a high potential for Natural Attenuation of benzene under sulfate-reducing conditions at the field site Zeitz. In spite of this existing potential to degrade benzene with sulfate as electron acceptor, the benzene plume at the field site is much longer than expected if benzene would be degraded at the rates observed in the column experiment, indicating that benzene oxidation under sulfate-reducing conditions is limited in situ.

A relative-least-squares technique to determine unique Monod kinetic parameters of BTEX compounds using batch experiments

An analysis of aerobic m-xylene biodegradation kinetics was performed on the results of laboratory batch microcosms. A modified version of the computer model BIO3D was used to determine the Monod kinetic parameters, kmax (maximum utilization rate) and KS (half-utilization constant), as well as the Haldane inhibition concentration, KI, for pristine Borden aquifer material. The proposed method allows for substrate degradation under microbial growth conditions. The problem of non-uniqueness of the calculated parameters was overcome by using several different initial substrate concentrations. With a relative-least-squares technique, unique kinetic degradation parameters were obtained. Calculation of the microbial yield, Y, based on microbial counts from the beginning and the end of the experiments was crucial for reducing the number of unknowns in the system and therefore for the accurate determination of the kinetic degradation parameters. The kinetic parameters obtained in the present study were found to agree well with values reported in the literature.

Evaluation of biodegradation and dispersion as natural attenuation processes of MTBE and benzene at the Borden field site

Abstract A natural gradient tracer test was performed in the shallow, aerobic sand aquifer at Canadian Forces Bases (CFB) Borden in 1988. A mixture of groundwater, spiked with dissolved oxygenate-containing gasoline, was injected below the water table along with chloride (Cl − ) as a conservative tracer. The mass of BTEX compounds in the plume diminished significantly over 16 months of monitoring due to intrinsic aerobic biodegradation; MTBE showed only a small decrease in mass over the same period. In 1995/1996, a comprehensive groundwater sampling program was undertaken to define the mass of MTBE still present in the aquifer. Only 3% of the original MTBE mass remained. Sorption, volatilization and abiotic degradation were ruled out as significant attenuation processes for the field conditions. As well, a study on the phytoremediation potential of the site showed that the plants in the study area were unlikely to contribute to the disappearance of the aqueous MTBE mass. These results indicate that biodegradation may have played a major role in the attenuation of MTBE within the Borden aquifer. In support of this hypothesis, significant MTBE mass losses were observed in aerobic batch experiments that used authentic Borden aquifer material and groundwater. Therefore, it appears that MTBE, like BTEX, can be remediated intrinsically due to biodegradation. Unlike BTEX, however, MTBE is biodegraded very slowly making biodegradation less likely to be sufficient in protecting aquifers and downgradient receptors once MTBE is spilled at a site.

Who is chasing whom? A call for a more integrated approach to reduce the load of micro-pollutants in the environment

One of the key questions arising from the presence of micro-pollutants in surface-, ground-, and drinking water is whether they pose a risk to human and ecosystem health. In our laboratories we have identified a number of biological effects by several pharmaceuticals and personal care products (PPCPs) on human, animal and/or plant cells at different levels of biological organisation. In part, these effects occur at concentrations even below those reported in drinking water. Even though it is often still difficult to fully deduce the role of some of these effects on the whole organism or population level as well as after chronic exposure, the effects observed illustrate that the input of micro-pollutants into the environment must be avoided or as far as possible reduced. Much effort has already been devoted to improved treatment of sewage and raw drinking water. A comprehensive protection from aquatic micro-pollutants, however, cannot reside in water treatment technology alone. Instead, all components of the life cycle of these chemicals must be put to the table to turn around the current trend of increasing environmental loads. The goal of this report is to illustrate why a more comprehensive way of risk assessment is needed and what this should include.

Pulsed gas injection: A minimum effort approach for enhanced natural attenuation of chlorobenzene in contaminated groundwater

Chlorobenzene-contaminated groundwater was used to assess pulsed gas sparging as a minimum effort aeration strategy to enhance intrinsic natural attenuation. In contrast to existing biosparging operations, oxygen was supplied at minimum rate by reducing the gas injection frequency to 0.33 day(-1). Field tests in a model aquifer were conducted in a 12 m long reactor, filled with indigenous aquifer material and continuously recharged with polluted groundwater over 3 years. The closed arrangement allowed yield balances, cost accounting as well as the investigation of spatial distributions of parameters which are sensitive to the biodegradation process. Depending on the injection frequency and on the gas chosen for injection (pure oxygen or air) oxygen-deficient conditions prevailed in the aquifer. Despite the limiting availability of dissolved oxygen in the groundwater, chlorobenzene degradation under oxygen-deficient conditions proved to be more effective than under conditions with dissolved oxygen being available in high concentrations.

Interplay between oxygen demand reactions and kinetic gas-water transfer in porous media

Gas-water phase transfer associated with the dissolution of trapped gas in porous media is a key process that occurs during pulsed gas sparging operations in contaminated aquifers. Recently, we applied a numerical model that was experimentally validated for abiotic situations, where multi-species kinetic inter-phase mass transfer and dissolved gas transport occurred during pulsed gas penetration-dissolution events [Balcke, G.U., Meenken, S., Hoefer, C. and Oswald, S.E., 2007. Kinetic gas-water transfer and gas accumulation in porous media during pulsed oxygen sparging. Environmental Science & Technology 41(12), 4428-4434]. Here we extend the model by using a reactive term to describe dissolved oxygen demand reactions via the formation of a reaction product, and to study the effects of such an aerobic degradation process on gas-water mass transfer and dissolution of trapped gas in porous media. As a surrogate for microbial oxygen reduction, first-order oxygen demand reactions were based on the measured oxidation of alkaline pyrogallol in column experiments. This reaction allows for adjusting the rate to values close to expected biodegradation rates and detection of the reaction product. The experiments and model consistently demonstrated accelerated oxygen gas-water mass transfer with increasing oxygen demand rates associated with an influence on the partitioning of other gases. Thus, as the oxygen demand accelerates, less gas phase residues, consisting mainly of nitrogen, are observed, which is in general beneficial to the performance of field biosparging operations. Model results additionally predict how oxygen demand influences oxygen mass transfer for a range of biodegradation rates. A typical field case scenario was simulated to illustrate the observed coupling of oxygen consumption and gas bubble dissolution. The model provides a tool to improve understanding of trapped gas behavior in porous media and contributes to a model-assisted biosparging.

New methods to estimate 2D water level distributions of dynamic rivers.

River restoration measures are becoming increasingly popular and are leading to dynamic river bed morphologies that in turn result in complex water level distributions in a river. Disconnected river branches, nonlinear longitudinal water level profiles and morphologically induced lateral water level gradients can evolve rapidly. The modeling of such river-groundwater systems is of high practical relevance in order to assess the impact of restoration measures on the exchange flux between a river and groundwater or on the residence times between a river and a pumping well. However, the model input includes a proper definition of the river boundary condition, which requires a detailed spatial and temporal river water level distribution. In this study, we present two new methods to estimate river water level distributions that are based directly on measured data. Comparing generated time series of water levels with those obtained by a hydraulic model as a reference, the new methods proved to offer an accurate and faster alternative with a simpler implementation.