Jil T. Geller

Mass transfer from nonaqueous phase organic liquids in water‐saturated porous media

Results of dissolution experiments with trapped nonaqueous phase liquids (NAPLs) are modeled by a mass transfer analysis. The model represents the NAPL as isolated spheres that shrink with dissolution and uses a mass transfer coefficient correlation reported in the literature for dissolving spherical solids. The model accounts for the reduced permeability of a region of residual NAPL relative to the permeability of the surrounding clean media that causes the flowing water to partially bypass the residual NAPL. The dissolution experiments with toluene alone and a benzene-toluene mixture were conducted in a water-saturated column of homogeneous glass beads over a range of Darcy velocities from 0.5 to 10 m d(-1). The model could represent the observed effluent concentrations as the NAPL underwent complete dissolution. The changing pressure drop across the column was predicted following an initial period of NAPL reconfiguration. The fitted NAPL sphere diameters of 0.15 to 0.40 cm are consistent with the size of NAPL ganglia observed by others and are the smallest at the largest flow velocity.

Experimental studies of water seepage and intermittent flow in unsaturated, rough-walled fractures

Flow visualization experiments were conducted on a transparent replica of a natural, rough-walled rock fracture from the Stripa Mine, Sweden, for inlet conditions of constant pressure and flow rate over a range of angles of inclination. The experiments demonstrated that infiltrating water proceeds through unsaturated rock fractures along nonuniform, localized preferential flow paths. Even though constant inlet conditions were maintained, pervasive unsteady or intermittent flow was also observed in these experiments, where portions of the flow channel underwent cycles of snapping and reforming. Experiments conducted on parallel plates with a sequence of apertures progressing from small to large to small reproduced intermittent flow. Measurements of the frequency of intermittent flow events and the volume of water metered between events were obtained from the fracture replica and parallel plate experiments and related to the Bond and capillary numbers to generalize the results. The frequency data from the fracture replica experiments did not follow the same trend as the data from the parallel plate experiments for similar Bond and capillary numbers, but the volume of water metered data was consistent in these experiments.

Cell-Wide Responses to Low-Oxygen Exposure in Desulfovibrio vulgaris Hildenborough

The responses of the anaerobic, sulfate-reducing organism Desulfovibrio vulgaris Hildenborough to low-oxygen exposure (0.1% O(2)) were monitored via transcriptomics and proteomics. Exposure to 0.1% O(2) caused a decrease in the growth rate without affecting viability. Concerted upregulation of the predicted peroxide stress response regulon (PerR) genes was observed in response to the 0.1% O(2) exposure. Several of the candidates also showed increases in protein abundance. Among the remaining small number of transcript changes was the upregulation of the predicted transmembrane tetraheme cytochrome c(3) complex. Other known oxidative stress response candidates remained unchanged during the low-O(2) exposure. To fully understand the results of the 0.1% O(2) exposure, transcriptomics and proteomics data were collected for exposure to air using a similar experimental protocol. In contrast to the 0.1% O(2) exposure, air exposure was detrimental to both the growth rate and viability and caused dramatic changes at both the transcriptome and proteome levels. Interestingly, the transcripts of the predicted PerR regulon genes were downregulated during air exposure. Our results highlight the differences in the cell-wide responses to low and high O(2) levels in D. vulgaris and suggest that while exposure to air is highly detrimental to D. vulgaris, this bacterium can successfully cope with periodic exposure to low O(2) levels in its environment.

Physiological and transcriptional studies of Cr(VI) reduction under aerobic and denitrifying conditions by an aquifer-derived pseudomonad.

Cr(VI) is a widespread groundwater contaminant that is a potent toxin, mutagen, and carcinogen. In situ reductive immobilization is a favored approach for Cr(VI) bioremediation, and Cr(VI) reduction has been reported in a variety of aerobic, facultative, and anaerobic bacteria, including a number of pseudomonads. However, studies comparing Cr(VI) reduction under aerobic and denitrifying conditions in the same organism are not available. We have conducted studies with strain RCH2, a bacterium similar to Pseudomonas stutzeri that we isolated from a Cr-contaminated aquifer. Cell suspension studies with lactate demonstrated that Cr(VI) reduction could occur under either denitrifying or aerobic conditions (at comparable specific rates) and that reduction was at least 20-fold more rapid when the terminal electron acceptor (i.e., nitrate or O(2)) was present. Our results suggest that Cr(VI) reduction by strain RCH2 under either aerobic or denitrifying conditions is primarily cometabolic in the sense that the physiological electron acceptor (oxygen or nitrate) appears to be required. Under both aerobic and denitrifying conditions, the gene(s) associated with chromate reduction are not inducible by Cr. Continuous culture (chemostat) studies showed strong correlations (r(2) values >0.93) between nitrate reduction rate and the transcript copy number of either nirS (cytochrome cd(1) nitrite reductase) or narG (nitrate reductase α subunit). As our studies indicate that anaerobic Cr(VI) reduction by this pseudomonad requires active denitrification and that denitrification and chromate reduction rates are highly correlated (r(2) > 0.99), monitoring expression of such denitrification genes in biostimulated aquifers could provide valuable proxy information for in situ chromate reduction by similar bacteria even if the specific genes involved in chromate reduction have not been identified. We also report incomplete removal of reduced Cr from solution and on artifacts in the widely used diphenylcarbazide assay for Cr(VI), most notably, its complete inactivation in the presence of millimolar nitrite.

Solute transport along preferential flow paths in unsaturated fractures

Laboratory experiments were conducted to study solute transport along preferential flow paths in unsaturated, inclined fractures. Qualitative aspects of solute transport were identified in a miscible dye tracer experiment conducted in a transparent replica of a natural granite fracture. Additional experiments were conducted to measure the breakthrough curves of a conservative tracer introduced into an established preferential flow path in two different fracture replicas and a rock-replica combination. The influence of gravity was investigated by varying fracture inclination. The relationship between the travel times of the solute and the relative influence of gravity was substantially affected by two modes of intermittent flow that occurred: the snapping rivulet and the pulsating blob modes. The measured travel times of the solute were evaluated with three transfer function models: the axial dispersion, the reactors-in-series, and the lognormal models. The three models described the solute travel times nearly equally well. A mechanistic model was also formulated to describe transport when the pulsating blob mode occurred which assumed blobs of water containing solute mixed with residual pools of water along the flow path.

Ultrasonic imaging of organic liquid contaminants in unconsolidated porous media

Laboratory experiments were conducted to measure the change in the ultrasonic wave signature as a function of the fraction of nonaqueous-phase liquid (NAPL) contaminants in initially water-saturated sand samples. This represents a fundamental step in the application of high-frequency seismic measurements to detect and delineate NAPL contamination in groundwater. The NAPLs used are n-dodecane, iso-octane and Freon 113®. P-wave velocity changes almost linearly as a function of the fraction of pore space occupied by NAPL. At a given NAPL fraction, the velocities rank with the bulk moduli of the NAPLs. The percent change in velocity at residual water saturation relative to the water-saturated medium ranges from 15% for n-dodecane to 31% for Freon 113®. Velocity changes are significant relative to the ability of seismic methods to detect changes on the order of 5%. These data are described by a model previously derived by G.T. Kuster and M.N. Toksoz of P-wave transmission through a fluid matrix with spherical inclusions that is modified to account for a two-fluid-phase matrix. Amplitude data as a function of NAPL fraction are described by assuming the distribution of NAPL in the column and using attenuation coefficients for the water-saturated and residual-water medium. Amplitudes are shown to be sensitive to both the fraction of NAPL and its distribution, whereas velocity is only a function of NAPL fraction.

Geophysics at the interface: Response of geophysical properties to solid‐fluid, fluid‐fluid, and solid‐solid interfaces

Laboratory studies reveal the sensitivity of measured geophysical properties to solid-fluid, fluid-fluid, and solid-solid interfaces in granular and fractured materials. In granular materials, electrical properties and nuclear magnetic resonance relaxation times exhibit a strong dependence on the size and properties of the solid-fluid interface. The electrical and seismic properties of granular materials and the seismic properties of fractured materials reveal a dependence on the size or geometry of fluid-fluid interfaces. Seismic properties of granular and fractured materials are affected by the effective stress and cementing material at solid-solid interfaces. There have been some recent studies demonstrating the use of field-scale measurements to obtain information about pore-scale interfaces. In addition, a new approach to geophysical field measurements focuses on the geophysical response of the field-scale interface itself, with successful applications in imaging the water table and a redox front. The observed sensitivity of geophysical data to interfaces highlights new ways in which geophysical measurements could be used to obtain information about subsurface properties and processes.

Survey of large protein complexes in D. vulgaris reveals great structural diversity

An unbiased survey has been made of the stable, most abundant multi-protein complexes in Desulfovibrio vulgaris Hildenborough (DvH) that are larger than Mr ≈ 400 k. The quaternary structures for 8 of the 16 complexes purified during this work were determined by single-particle reconstruction of negatively stained specimens, a success rate ≈10 times greater than that of previous “proteomic” screens. In addition, the subunit compositions and stoichiometries of the remaining complexes were determined by biochemical methods. Our data show that the structures of only two of these large complexes, out of the 13 in this set that have recognizable functions, can be modeled with confidence based on the structures of known homologs. These results indicate that there is significantly greater variability in the way that homologous prokaryotic macromolecular complexes are assembled than has generally been appreciated. As a consequence, we suggest that relying solely on previously determined quaternary structures for homologous proteins may not be sufficient to properly understand their role in another cell of interest.

Acoustic detection of Immiscible Liquids in Sand

Laboratory cross-well P-wave transmission at 90 kHz was measured in a 61 cm diameter by 76 cm tall water-saturated sand pack, before and after introducing a non-aqueous phase organic liquid (NAPL) (n-dodecane). In one experiment NAPL was introduced to form a lens trapped by a low permeability layer; a second experiment considered NAPL residual trapped behind the front of flowing NAPL. The NAPL caused significant changes in the travel time and amplitude of first arrivals, as well as the generation of diffracted waves arriving after the direct wave. The spatial variations in NAPL saturation obtained from excavation at the end of the experiment correlated well with the observed variations in the P-wave amplitudes and travel times. NAPL residual saturation changes from NAPL flow channels of 3 to 4% were detectable and the 40 to 80% NAPL saturation in the NAPL lens was clearly visible at acoustic frequencies. The results of these experiments demonstrate that small NAPL saturations may be more easily detected with amplitude rather than travel time data, but that the relationships between the amplitude changes and NAPL saturation maybe more complex than those for velocity.

Effect of P-wave scattering on velocity and attenuation in unconsolidated sand saturated with immiscible liquids

Seismic wave tomography is a potentially powerful tool for detecting and delineating nonaqueous phase liquid (NAPL) contaminants in the shallow subsurface. To develop this application, we are conducting laboratory and numerical studies to understand the mechanisms of P-wave transmission through NAPL-water‐sand systems. P-wave measurements of traveltime and amplitude were taken in the 100–900 kHz frequency range through saturated sand with variable NAPL content. To simulate the stress conditions of the shallow surface, a low confining and axial pressure of 60 and 140 kPa, respectively, was applied. The measurements show a significant change in the traveltime and amplitude of the primary arrival as a function of NAPL saturation. To simulate the laboratory measurements, we performed numerical calculations of P-wave propagation through a 1-D medium. The results show that the main behavior of traveltime and amplitude variation can be explained by P-wave scattering. This represents an alternative explanation to...