Riverbed depth-specific microplastics distribution and potential use as process marker.

Riverbed sediments have been identified as temporary and long-term accumulation sites for microplastic particles (MPs), but the relocation and retention mechanisms in riverbeds still need to be better understood. In this study, we investigated the depth-specific occurrence and distribution (abundance, type, and size) of MPs in river sediments down to a depth of 100 cm, which had not been previously investigated in riverbeds. In four sediment freeze cores taken for the Main River (Germany), MPs (≥ 100 µm) were detected using two complementary analytical approaches (spectroscopy and thermoanalytical) over the entire depth with an average of 21.7 ± 21.4 MP/kg or 31.5 ± 28.0 mg/kg. Three vertical trends for MP abundance could be derived, fairly constant in top layers (0-|30 cm), a decrease in middle layers (30-60 cm), and a strong increase in deep layers (60-100 cm). The dominant polymer types were polyethylene (PE), polypropylene (PP), and polystyrene (PS). Polyethylene terephthalate (PET) and PP were also found in deep layers, albeit with the youngest age of earliest possible occurrence (EPO age of 1973 and 1954). The fraction of smaller-sized MPs (100-500 µm) increased with depth in shallow layers, but the largest MPs (> 1 mm) were detected in deep layers. Based on these findings, we elucidate the relationship between the depth-specific MP distribution and the prevailing processes of MP retention and sediment dynamics in the riverbed. We propose some implications and offer an initial conceptual approach, suggesting the use of microplastics as a potential environmental process tracer for driving riverbed sediment dynamics.

Three-dimensional in vivo analysis of water uptake and translocation in maize roots by fast neutron tomography.

Root water uptake is an essential process for terrestrial plants that strongly affects the spatiotemporal distribution of water in vegetated soil. Fast neutron tomography is a recently established non-invasive imaging technique capable to capture the 3D architecture of root systems in situ and even allows for tracking of three-dimensional water flow in soil and roots. We present an in vivo analysis of local water uptake and transport by roots of soil-grown maize plants-for the first time measured in a three-dimensional time-resolved manner. Using deuterated water as tracer in infiltration experiments, we visualized soil imbibition, local root uptake, and tracked the transport of deuterated water throughout the fibrous root system for a day and night situation. This revealed significant differences in water transport between different root types. The primary root was the preferred water transport path in the 13-days-old plants while seminal roots of comparable size and length contributed little to plant water supply. The results underline the unique potential of fast neutron tomography to provide time-resolved 3D in vivo information on the water uptake and transport dynamics of plant root systems, thus contributing to a better understanding of the complex interactions of plant, soil and water.

Seasonal dynamics modifies fate of oxygen, nitrate, and organic micropollutants during bank filtration - temperature-dependent reactive transport modeling of field data.

Bank filtration is considered to improve water quality through microbially mediated degradation of pollutants and is suitable for waterworks to increase their production. In particular, aquifer temperatures and oxygen supply have a great impact on many microbial processes. To investigate the temporal and spatial behavior of selected organic micropollutants during bank filtration in dependence of relevant biogeochemical conditions, we have set up a 2D reactive transport model using MODFLOW and PHT3D under the user interface ORTI3D. The considered 160-m-long transect ranges from the surface water to a groundwater extraction well of the adjacent waterworks. For this purpose, water levels, temperatures, and chemical parameters were regularly measured in the surface water and groundwater observation wells over one and a half years. To simulate the effect of seasonal temperature variations on microbial mediated degradation, we applied an empirical temperature factor, which yields a strong reduction of the degradation rate at groundwater temperatures below 11 °C. Except for acesulfame, the considered organic micropollutants are substantially degraded along their subsurface flow paths with maximum degradation rates in the range of 10-6 mol L-1 s-1. Preferential biodegradation of phenazone, diclofenac, and valsartan was found under oxic conditions, whereas carbamazepine and sulfamethoxazole were degraded under anoxic conditions. This study highlights the influence of seasonal variations in oxygen supply and temperature on the fate of organic micropollutants in surface water infiltrating into an aquifer.

What comes NeXT? - High-Speed Neutron Tomography at ILL.

Here, we report on a new record in the acquisition time for fast neutron tomography. With an optimized imaging setup, it was possible to acquire single radiographic projection images with 10 ms and full tomographies with 155 projections images and a physical spatial resolution of 200 µm within 1.5 s. This is about 6.7 times faster than the current record. We used the technique to investigate the water infiltration in the soil with a living lupine root system. The fast imaging setup will be part of the future NeXT instrument at ILL in Grenoble with a great field of possible future applications.

Temperature-dependent redox zonation, nitrate removal and attenuation of organic micropollutants during bank filtration.

River bank filtration (RBF) is considered to efficiently remove nitrate and trace organic micropollutants (OMP) from polluted surface waters. This is essential for maintaining good groundwater quality and providing high quality drinking water. Predicting the fate of OMP during RBF is difficult as the biogeochemical factors controlling the removal efficiency are not fully understood. To determine in-situ removal efficiency and degradation rates of nitrate and OMP indicator substances we conducted a field study in a RBF system during a period of one and a half years incorporating temporally and spatially varying redox conditions and temperature changes typically occurring in temperate climates. RBF was analyzed by means of mixing ratios between infiltrated river water and groundwater as well as average residence times of surface water towards the individual groundwater observation wells. These results were used to calculate temperature dependent first order degradation rates of redox sensitive species and several OMP. Five out of ten investigated OMP were completely removed along RBF pathways. We demonstrate that degradation rates of several OMP during bank filtration were controlled by redox conditions and temperature whereby temperature itself also had a significant influence on the extent of the most reactive oxic zone. The seasonal variations in temperature alone could explain a considerable percentage of the variance in dissolved oxygen (34%), nitrate (81%) as well as the OMPs diclofenac (44%) and sulfamethoxazole (76%). Estimated in-situ degradation rates roughly varied within one order of magnitude for temperature changes between 5 °C and 20 °C. This study highlights that temporal variability in temperature and redox zonation is a significant factor for migration and degradation of nitrate and several OMPs.

Multi-temporal surveys for microplastic particles enabled by a novel and fast application of SWIR imaging spectroscopy - Study of an urban watercourse traversing the city of Berlin, Germany.

Following the widespread assumption that a majority of ubiquitous marine microplastic particles originate from land-based sources, recent studies identify rivers as important pathways for microplastic particles (MPP) to the oceans. Yet a detailed understanding of the underlying processes and dominant sources is difficult to obtain with the existing accurate but extremely time-consuming methods available for the identification of MPP. Thus in the presented study, a novel approach applying short-wave infrared imaging spectroscopy for the quick and semi-automated identification of MPP is applied in combination with a multitemporal survey concept. Volume-reduced surface water samples were taken from transects at ten points along a major watercourse running through the South of Berlin, Germany, on six dates. After laboratory treatment, the samples were filtered onto glass fiber filters, scanned with an imaging spectrometer and analyzed by image processing. The presented method allows to count MPP, classify the plastic types and determine particle sizes. At the present stage of development particles larger than 450 µm in diameter can be identified and a visual validation showed that the results are reliable after a subsequent visual final check of certain typical error types. Therefore, the method has the potential to accelerate microplastic identification by complementing FTIR and Raman microspectroscopy. Technical advancements (e.g. new lens) will allow lower detection limits and a higher grade of automatization in the near future. The resulting microplastic concentrations in the water samples are discussed in a spatio-temporal context with respect to the influence (i) of urban areas, (ii) of effluents of three major Berlin wastewater treatment plants discharging into the canal and (iii) of precipitation events. Microplastic concentrations were higher downstream of the urban area and after precipitation. An increase in microplastic concentrations was discernible for the wastewater treatment plant located furthest upstream though not for the other two.

Capturing 3D Water Flow in Rooted Soil by Ultra-fast Neutron Tomography.

Water infiltration in soil is not only affected by the inherent heterogeneities of soil, but even more by the interaction with plant roots and their water uptake. Neutron tomography is a unique non-invasive 3D tool to visualize plant root systems together with the soil water distribution in situ. So far, acquisition times in the range of hours have been the major limitation for imaging 3D water dynamics. Implementing an alternative acquisition procedure we boosted the speed of acquisition capturing an entire tomogram within 10 s. This allows, for the first time, tracking of a water front ascending in a rooted soil column upon infiltration of deuterated water time-resolved in 3D. Image quality and resolution could be sustained to a level allowing for capturing the root system in high detail. Good signal-to-noise ratio and contrast were the key to visualize dynamic changes in water content and to localize the root uptake. We demonstrated the ability of ultra-fast tomography to quantitatively image quick changes of water content in the rhizosphere and outlined the value of such imaging data for 3D water uptake modelling. The presented method paves the way for time-resolved studies of various 3D flow and transport phenomena in porous systems.

A multi-imaging approach to study the root-soil interface.

BACKGROUND AND AIMS: Dynamic processes occurring at the soil-root interface crucially influence soil physical, chemical and biological properties at a local scale around the roots, and are technically challenging to capture in situ. This study presents a novel multi-imaging approach combining fluorescence and neutron radiography that is able to simultaneously monitor root growth, water content distribution, root respiration and root exudation. METHODS: Germinated seeds of white lupins (Lupinus albus) were planted in boron-free glass rhizotrons. After 11 d, the rhizotrons were wetted from the bottom and time series of fluorescence and neutron images were taken during the subsequent day and night cycles for 13 d. The following day (i.e. 25 d after planting) the rhizotrons were again wetted from the bottom and the measurements were repeated. Fluorescence sensor foils were attached to the inner sides of the glass and measurements of oxygen and pH were made on the basis of fluorescence intensity. The experimental set-up allowed for simultaneous fluorescence imaging and neutron radiography. KEY RESULTS: The interrelated patterns of root growth and distribution in the soil, root respiration, exudation and water uptake could all be studied non-destructively and at high temporal and spatial resolution. The older parts of the root system with greater root-length density were associated with fast decreases of water content and rapid changes in oxygen concentration. pH values around the roots located in areas with low soil water content were significantly lower than the rest of the root system. CONCLUSIONS: The results suggest that the combined imaging set-up developed here, incorporating fluorescence intensity measurements, is able to map important biogeochemical parameters in the soil around living plants with a spatial resolution that is sufficiently high enough to relate the patterns observed to the root system.

Transport of carbon colloid supported nanoscale zero-valent iron in saturated porous media.

Injection of nanoscale zero-valent iron (nZVI) has recently gained great interest as emerging technology for in-situ remediation of chlorinated organic compounds from groundwater systems. Zero-valent iron (ZVI) is able to reduce organic compounds and to render it to less harmful substances. The use of nanoscale particles instead of granular or microscale particles can increase dechlorination rates by orders of magnitude due to its high surface area. However, classical nZVI appears to be hampered in its environmental application by its limited mobility. One approach is colloid supported transport of nZVI, where the nZVI gets transported by a mobile colloid. In this study transport properties of activated carbon colloid supported nZVI (c-nZVI; d50=2.4µm) are investigated in column tests using columns of 40cm length, which were filled with porous media. A suspension was pumped through the column under different physicochemical conditions (addition of a polyanionic stabilizer and changes in pH and ionic strength). Highest observed breakthrough was 62% of the injected concentration in glass beads with addition of stabilizer. Addition of mono- and bivalent salt, e.g. more than 0.5mM/L CaCl2, can decrease mobility and changes in pH to values below six can inhibit mobility at all. Measurements of colloid sizes and zeta potentials show changes in the mean particle size by a factor of ten and an increase of zeta potential from -62mV to -80mV during the transport experiment. However, results suggest potential applicability of c-nZVI under field conditions.

Investigations on mobility of carbon colloid supported nanoscale zero-valent iron (nZVI) in a column experiment and a laboratory 2D-aquifer test system.

Nanoscale zero-valent iron (nZVI) has recently gained great interest in the scientific community as in situ reagent for installation of permeable reactive barriers in aquifer systems, since nZVI is highly reactive with chlorinated compounds and may render them to harmless substances. However, nZVI has a high tendency to agglomerate and sediment; therefore it shows very limited transport ranges. One new approach to overcome the limited transport of nZVI in porous media is using a suited carrier colloid. In this study we tested mobility of a carbon colloid supported nZVI particle "Carbo-Iron Colloids" (CIC) with a mean size of 0.63 µm in a column experiment of 40 cm length and an experiment in a two-dimensional (2D) aquifer test system with dimensions of 110 × 40 × 5 cm. Results show a breakthrough maximum of 82 % of the input concentration in the column experiment and 58 % in the 2D-aquifer test system. Detected residuals in porous media suggest a strong particle deposition in the first centimeters and few depositions in the porous media in the further travel path. Overall, this suggests a high mobility in porous media which might be a significant enhancement compared to bare or polyanionic stabilized nZVI.

Numerical modeling analysis of VOC removal processes in different aerobic vertical flow systems for groundwater remediation.

Vertical flow systems filled with porous medium have been shown to efficiently remove volatile organic contaminants (VOCs) from contaminated groundwater. To apply this semi-natural remediation strategy it is however necessary to distinguish between removal due to biodegradation and due to volatile losses to the atmosphere. Especially for (potentially) toxic VOCs, the latter needs to be minimized to limit atmospheric emissions. In this study, numerical simulation was used to investigate quantitatively the removal of volatile organic compounds in two pilot-scale water treatment systems: an unplanted vertical flow filter and a planted one, which could also be called a vertical flow constructed wetland, both used for the treatment of contaminated groundwater. These systems were intermittently loaded with contaminated water containing benzene and MTBE as main VOCs. The highly dynamic but permanently unsaturated conditions in the porous medium facilitated aerobic biodegradation but could lead to volatile emissions of the contaminants. Experimental data from porous material analyses, flow rate measurements, solute tracer and gas tracer test, as well as contaminant concentration measurements at the boundaries of the systems were used to constrain a numerical reactive transport modeling approach. Numerical simulations considered unsaturated water flow, transport of species in the aqueous and the gas phase as well as aerobic degradation processes, which made it possible to quantify the rates of biodegradation and volatile emissions and calculating their contribution to total contaminant removal. A range of degradation rates was determined using experimental results of both systems under two operation modes and validated by field data obtained at different operation modes applied to the filters. For both filters, simulations and experimental data point to high biodegradation rates, if the flow filters have had time to build up their removal capacity. For this case volatile emissions are negligible and total removal can be attributed to biodegradation, only. The simulation study thus supports the use of both of these vertical flow systems for the treatment of groundwater contaminated with VOCs and the use of reactive transport modeling for the assessment of VOCs removal and operation modes in these high performance treatment systems.

Three-dimensional visualization and quantification of water content in the rhizosphere.

• Despite the importance of rhizosphere properties for water flow from soil to roots, there is limited quantitative information on the distribution of water in the rhizosphere of plants. • Here, we used neutron tomography to quantify and visualize the water content in the rhizosphere of the plant species chickpea (Cicer arietinum), white lupin (Lupinus albus), and maize (Zea mays) 12 d after planting. • We clearly observed increasing soil water contents (θ) towards the root surface for all three plant species, as opposed to the usual assumption of decreasing water content. This was true for tap roots and lateral roots of both upper and lower parts of the root system. Furthermore, water gradients around the lower part of the roots were smaller and extended further into bulk soil compared with the upper part, where the gradients in water content were steeper. • Incorporating the hydraulic conductivity and water retention parameters of the rhizosphere into our model, we could simulate the gradual changes of θ towards the root surface, in agreement with the observations. The modelling result suggests that roots in their rhizosphere may modify the hydraulic properties of soil in a way that improves uptake under dry conditions.

Remediation of groundwater contaminated with MTBE and benzene: the potential of vertical-flow soil filter systems.

Field investigations on the treatment of MTBE and benzene from contaminated groundwater in pilot or full-scale constructed wetlands are lacking hugely. The aim of this study was to develop a biological treatment technology that can be operated in an economic, reliable and robust mode over a long period of time. Two pilot-scale vertical-flow soil filter eco-technologies, a roughing filter (RF) and a polishing filter (PF) with plants (willows), were operated independently in a single-stage configuration and coupled together in a multi-stage (RF+PF) configuration to investigate the MTBE and benzene removal performances. Both filters were loaded with groundwater from a refinery site contaminated with MTBE and benzene as the main contaminants, with a mean concentration of 2970±816 and 13,966±1998 µg L(-1), respectively. Four different hydraulic loading rates (HLRs) with a stepwise increment of 60, 120, 240 and 480 L m(-2) d(-1) were applied over a period of 388 days in the single-stage operation. At the highest HLR of 480 L m(-2) d(-1), the mean concentrations of MTBE and benzene were found to be 550±133 and 65±123 µg L(-1) in the effluent of the RF. In the effluent of the PF system, respective mean MTBE and benzene concentrations of 49±77 and 0.5±0.2 µg L(-1) were obtained, which were well below the relevant MTBE and benzene limit values of 200 and 1 µg L(-1) for drinking water quality. But a dynamic fluctuation in the effluent MTBE concentration showed a lack of stability in regards to the increase in the measured values by nearly 10%, which were higher than the limit value. Therefore, both (RF+PF) filters were combined in a multi-stage configuration and the combined system proved to be more stable and effective with a highly efficient reduction of the MTBE and benzene concentrations in the effluent. Nearly 70% of MTBE and 98% of benzene were eliminated from the influent groundwater by the first vertical filter (RF) and the remaining amount was almost completely diminished (∼100% reduction) after passing through the second filter (PF), with a mean MTBE and benzene concentration of 5±10 and 0.6±0.2 µg L(-1) in the final effluent. The emission rate of volatile organic compounds mass into the air from the systems was less than 1% of the inflow mass loading rate. The results obtained in this study not only demonstrate the feasibility of vertical-flow soil filter systems for treating groundwater contaminated with MTBE and benzene, but can also be considered a major step forward towards their application under full-scale conditions for commercial purposes in the oil and gas industries.

Nitrogen as an indicator of mass transfer during in-situ gas sparging.

Aiming at the stimulation of intrinsic microbial activity, pulses of pure oxygen or pressurized air were recurrently injected into groundwater polluted with chlorobenzene. To achieve well-controlled conditions and intensive sampling, a large, vertical underground tank was filled with the local unconfined sandy aquifer material. In the course of two individual gas injections, one using pure oxygen and one using pressurized air, the mass transfer of individual gas species between trapped gas phase and groundwater was studied. Field data on the dissolved gas composition in the groundwater were combined with a kinetic model on gas dissolution and transport in porous media. Phase mass transfer of individual gas components caused a temporary enrichment of nitrogen, and to a lower degree of methane, in trapped gas leading to the formation of excess dissolved nitrogen levels downgradient from the dissolving gas phase. By applying a novel gas sampling method for dissolved gases in groundwater it was shown that dissolved nitrogen can be used as a partitioning tracer to indicate complete gas dissolution in porous media.

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.

Kinetic gas-water transfer and gas accumulation in porous media during pulsed oxygen sparging.

Gas-water mass transfer and the transport of dissolved gases in variably saturated porous media are key processes for in-situ remediation by pulsed gas sparging. In this context, gas dissolution tests were conducted during pulsed oxygen gas injection into sand columns. The columns were recharged with anoxic water, effluents were analyzed for dissolved O2, and tracer tests were performed to detect accumulation of trapped gas. In a second series oxygen gas was blended with sulfur hexafluoride (SF6), and O2 and SF6 breakthrough curves were recorded. To interpret experimental results, a numerical model was applied that simulates multi-species kinetic mass transfer during gas dissolution. The model predicted breakthrough curves of dissolved gas species and delivered spatially resolved values for gas phase accumulation and composition, which are not directly accessible experimentally. It was shown how dissolved nitrogen accumulates increasingly in trapped gas phase and inhibits its complete dissolution, in case the pulsed gas injections were operated based on O2 breakthrough only. Accumulation of nitrogen also retarded dissolved oxygen transport and thus oxygen breakthrough. Experiments plus modeling demonstrated that SF6 measurements are highly sensitive to the gas dissolution processes, and provide a more sensitive criterion for determining gas injection frequencies during pulsed biosparging.

Biodegradation processes in a laboratory-scale groundwater contaminant plume assessed by fluorescence imaging and microbial analysis.

Flow reactors containing quartz sand colonized with biofilm were set up as physical model aquifers to allow degrading plumes of acetate or phenol to be formed from a point source. A noninvasive fluorescent tracer technique was combined with chemical and biological sampling in order to quantify transport and biodegradation processes. Chemical analysis of samples showed a substantial decrease in carbon concentration between the injection and outflow resulting primarily from dilution but also from biodegradation. Two-dimensional imaging of the aqueous oxygen [O2(aq)] concentration field quantified the depletion of O2(aq) within the contaminant plume and provided evidence for microbial respiration associated with biodegradation of the carbon source. Combined microbiological, chemical, and O2(aq) imaging data indicated that biodegradation was greatest at the plume fringe. DNA profiles of bacterial communities were assessed by temperature gradient gel electrophoresis, which revealed that diversity was limited and that community changes observed depended on the carbon source used. Spatial variation in activity within the plume could be quantitatively accounted for by the changes observed in active cell numbers rather than differences in community structure, the total biomass present, or the increased enzyme activity of individual cells. Numerical simulations and comparisons with the experimental data were used to test conceptual models of plume processes. Results demonstrated that plume behavior was best described by growth and decay of active biomass as a single functional group of organisms represented by active cell counts.

Three-dimensional saltwater-freshwater fingering in porous media: contrast agent MRI as basis for numerical simulations.

This study investigated miscible fingering phenomena in a saturated porous medium due solely to fluid density differences. The objective was to determine dissolved salt concentrations in the porous medium and, thus, local fluid density with high temporal resolution and covering substantial volume. A magnetic resonance imaging method, which can achieve this goal by adding Cu(II)SO(4) to salt solutions, has been developed. This method was applied here to observe and quantify three-dimensional miscible fingering for the initial unstable layering of saltwater above freshwater. Additionally, characteristic properties were defined and evaluated to facilitate a more meaningful comparison with numerical simulations.

Modeling the dynamics of fermentation and respiratory processes in a groundwater plume of phenolic contaminants interpreted from laboratory- to field-scale.

A biodegradation model with consecutive fermentation and respiration processes, developed from microcosm experiments and simulated mathematically with microbial growth kinetics, has been implemented into a field-scale reactive transport model of a groundwater plume of phenolic contaminants. Simulation of the anaerobic plume core with H2 and acetate as intermediate products of biodegradation allows the rates and parameter values forfermentation processes and individual respiratory terminal electron accepting processes (TEAPS) to be estimated using detailed, spatially discrete, hydrochemical field data. The modeling of field-scale plume development includes consideration of microbial acclimatization, substrate toxicity toward degradation, bioavailability of mineral oxides, and adsorption of biogenic Fe(ll) species in the aquifer, identified from complementary laboratory process studies. The results suggest that plume core processes, particularly fermentation and Fe(lll)-reduction, are more important for degradation than previously thought, possibly with a greater impact than plume fringe processes (aerobic respiration, denitrification, and SO4-reduction). The accumulation of acetate as a fermentation product within the plume contributes significantly to the mass balance for carbon. These results demonstrate the value of quantifying fermentation products within organic contaminant plumes and strongly suggest that the conceptual model selected for reactive processes plays a dominant role in the quantitative assessment of risk reduction by naturally occurring biodegradation processes.

Modeling kinetic processes controlling hydrogen and acetate concentrations in an aquifer-derived microcosm.

Groundwater contaminants may degrade via fermentation to intermediate species, which are subsequently consumed by terminal electron-accepting processes (TEAPs). A numerical model of an aquifer-derived laboratory microcosm is developed to simulate the dynamic behavior of fermentation and respiration in groundwater by coupling microbial growth and substrate utilization kinetics with a formulation that also includes aqueous speciation and other geochemical reactions including surface complexation, mineral dissolution, and precipitation. The model is used to test approaches that currently make use of H2(aq) to diagnose prevalent TEAPs in groundwater. Competition between TEAPs is integral to the conceptual model of the simulation, and the results indicate that competitive exclusion is significant but with some overlap found in the temporal sequence of TEAPs. Steady-state H2(aq) concentrations observed during different TEAPs do not differ significantly. The results are not consistent with previous applications of the partial equilibrium approach since most TEAP redox pairs exhibit free energies that suggest a particular process is able to proceed, yet observations here show that this process does not proceed.