In Situ Biotreatment of TBA with Recirculation/Oxygenation

The potential for in situ biodegradation of tert‐butyl alcohol (TBA) by creation of aerobic conditions in the subsurface with recirculating well pairs was investigated in two field studies conducted at Vandenberg Air Force Base. In the first experiment, a single recirculating well pair with bromide tracer and oxygen amendment successfully delivered oxygen to the subsurface for 42 d. TBA concentrations were reduced from approximately 500 μg/L to below the detection limit within the treatment zone and the treated water was detected in a monitoring transect several meters downgradient. In the second experiment, a site‐calibrated model was used to design a double recirculating well pair with oxygen amendment, which successfully delivered oxygen to the subsurface for 291 d and also decreased TBA concentrations to below the detection limit. Methylibium petroleiphilum strain PM1, a known TBA‐degrading bacterium, was detectable at the study site but addition of oxygen had little impact on the already low baseline population densities, suggesting that there was not enough carbon within the groundwater plume to support significant new growth in the PM1 population. Given favorable hydrogeologic and geochemical conditions, the use of recirculating well pairs to introduce dissolved oxygen into the subsurface is a viable method to stimulate in situ biodegradation of TBA or other aerobically degradable aquifer contaminants.     

Optimal Field Approaches for Electrokinetic In Situ Oxidation Remediation

Numerical simulations were used to identify and evaluate optimum electrode configurations and approaches for electrokinetic in situ chemical oxidation (EK‐ISCO) remediation of low‐permeability sediments. A newly developed groundwater and EK flow and reactive transport numerical model was used to conduct two‐dimensional scenario simulations of the coverage of an injected oxidant, permanganate, and the oxidation of a typical organic contaminant (tetrachloroethene, PCE). For linear configurations of vertical electrodes, the spacing of same‐polarity electrodes is recommended to be about one‐third to one‐quarter of the anode–cathode spacing. Greater coverage could also be achieved by locating additional oxidant injection wells at the divergence of the electric field in linear electrode configurations. Horizontal electrodes allowed greater contact between the injected permanganate and PCE and resulted in faster degradation of PCE compared to vertical electrodes. Pulsed oxidant injection, closer electrode spacing, and electric field reversal also resulted in faster EK‐ISCO remediation.     

Evaluation of Extensive Secondary Maximum Contaminant Level Exceedances Following Remediation by In Situ Chemical Oxidation

In situ chemical oxidation (ISCO) with activated persulfate is commonly used for the remediation of petroleum impacted soil and groundwater because of its proven efficiency and the perception that reaction end products are completely innocuous. While the reaction products are less hazardous compared to the contaminants being treated, they may inadvertently prolong site closure in areas that have adopted the U.S. Environmental Protection Agency (EPA) Secondary Maximum Contaminant Levels (SMCLs) as enforceable standards. This study examines the occurrence and persistence of iron, manganese, sulfate, sodium, and total dissolved solids (TDS) in groundwater following persulfate ISCO. The concentrations of these chemicals were observed remaining above their respective regulatory criteria almost 3 years following the chemical application. Background concentrations and mobilization due to the petroleum contamination and ISCO application are also evaluated. Baseline sampling revealed substantially higher iron and manganese concentrations inside the plume area compared to the upgradient and downgradient wells suggesting mobilization due to redox reactions occurring inside of the plume. Iron was not a component in the applied chemical formula, yet the iron concentration spiked by 366% in the key monitoring well during the first post-remediation monitoring event. Ionic interactions between the ISCO amendment and native soils are believed to be responsible for displacing significant quantities of iron from the soil. Sulfate, sodium, and TDS exceedances are primarily associated with decomposition products of the ISCO amendments. The iron, manganese, sulfate, sodium, and TDS concentrations are trending downward over time, but still exceed regulatory criteria or pre-ISCO concentrations.     

In Situ Chemical Oxidation: Permanganate Oxidant Volume Design Considerations

Contaminant rebound and low contaminant removal are reported more frequently with in situ chemical oxidation than other in situ technologies. Although there are multiple causes for these results, a critical analysis indicates that low oxidant volume delivery is a key issue. The volume of oxidant injected is critical and porosity of the aquifer matrix can be used to estimate the pore volume. The total porosity (q_T) is the volume of voids relative to the total volume of aquifer material. The mobile porosity (q_M) is the fraction of voids that readily contributes to fluid displacement, and is less than q_T leading to smaller estimates of oxidant volume. Injecting low‐oxidant volume may result in inadequate oxidant distribution and postinjection dispersal within the radius of influence, insufficient oxidant contact and oxidant loading, and incomplete treatment; whereas, greater oxidant volume achieves a greater oxidant footprint and may involve risk that the injected oxidant may migrate into nontarget areas and displacement of contaminated groundwater. Design guidelines and recommendations are provided that could help achieve more effective technology deployment, reduce the role of heterogeneities in the subsurface, and result in greater probability the oxidant is delivered to the targeted treatment zone.     

Microbial Dynamics During and After In Situ Chemical Oxidation of Chlorinated Solvents

In situ chemical oxidation (ISCO) followed by a bioremediation step is increasingly being considered as an effective biphasic technology. Information on the impact of chemical oxidants on organohalide respiring bacteria (OHRB), however, is largely lacking. Therefore, we used quantitative PCR (qPCR) to monitor the abundance of OHRB (Dehalococcoides mccartyi, Dehalobacter, Geobacter, and Desulfitobacterium) and reductive dehalogenase genes (rdh; tceA, vcrA, and bvcA) at a field location contaminated with chlorinated solvents prior to and following treatment with sodium persulfate. Natural attenuation of the contaminants tetrachloroethene (PCE) and trichloroethene (TCE) observed prior to ISCO was confirmed by the distribution of OHRB and rdh genes. In wells impacted by persulfate treatment, a 1 to 3 order of magnitude reduction in the abundances of OHRB and complete absence of rdh genes was observed 21 days after ISCO. Groundwater acidification (pH<3) and increase in the oxidation reduction potential (>500 mV) due to persulfate treatment were significant and contributed to disruption of the microbial community. In wells only mildly impacted by persulfate, a slight stimulation of the microbial community was observed, with more than 1 order of magnitude increase in the abundance of Geobacter and Desulfitobacterium 36 days after ISCO. After six months, regeneration of the OHRB community occurred, however, neither D. mccartyi nor any rdh genes were observed, indicating extended disruption of biological natural attenuation (NA) capacity following persulfate treatment. For full restoration of biological NA activity, additional time may prove sufficient; otherwise addition electron donor amendment or bioaugmentation may be required.     

In Situ Vertical Circulation Column: Containment System for Small-Scale DNAPL Field Experiments

The in situ vertical circulation column (ISVCC) is a cylindrical containment system consisting of an instrumented steel cylinder used for experimental ground water studies in sandy aquifers. Vertical flow is imposed inside the ISVCC. Although vertical wells are an option, the ISVCC installed in the Borden Aquifer is instrumented with horizontal wells and monitoring ports to avoid creating vertical preferential flow paths. The cylinder was driven downward into the aquifer using a small backhoe equipped with a vibrating plate. The ISVCC penetrates the 2.3-m-thic sand aquifer and is keyed 20 cm into the underlying clay aquitard. The cylinder was installed inside a 2 m X 2 m steel sheet pile enclosure so that the enclosed segment of aquifer could be conveniently dewatered and then excavated to allow installation of the horizontal wells. The dispersivity of the column was comparable to literature values for long sand-packed laboratory columns.
Pure phase DNAPL (tetrachloroethene and 1,1,1-trichloroethane) was slowly pumped into two ports in the center of the column. Following this DNAPL injection, an aqueous solution of vitamin B₁₂ and reduced titanium was circulated through the column to promote degradation of the solvents. Processes observed in the ISVCC included DNAPL distribution, dissolution, and degradation, and geochemical evolution of the aquifer.
The ISVCC provides a convenient means for testing in situ technologies in the experimental stage or for selection of proven technologies to find the most effective at a specific site. It is inexpensive, easy to install, and maximizes control over flow distribution in a heterogeneous aquifer. Its application will be restricted where low hydraulic conductivity beds are present in the aquifer.     

In Situ Chemical Oxidation of RDX-Contaminated Groundwater with Permanganate at the Nebraska Ordnance Plant

Groundwater beneath the former Nebraska Ordnance Plant (NOP) is contaminated with the explosive hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX). The current pump and treat facility is preventing offsite migration but does not offer a short-term solution. Our objective was to quantify the effectiveness of permanganate to degrade RDX in situ. This was accomplished by performing laboratory treatability experiments, aquifer characterization, and a pilot-scale in situ chemical oxidation (ISCO) demonstration. Treatability experiments confirmed that permanganate could mineralize RDX in the presence of NOP aquifer solids. The pilot-scale ISCO demonstration was performed using an extraction-injection well configuration to create a curtain of permanganate between two injection wells. RDX destruction was then quantified as the RDX-permanganate plume migrated downgradient through a monitoring well field. Electrical resistivity imaging (ERI) was used to identify the subsurface distribution of permanganate after injection. Results showed that RDX concentrations temporally decreased in wells closest to the injection wells by 70% to 80%. Observed degradation rates (0.12 and 0.087/d) were lower than those observed under laboratory batch conditions at 11.5 °C (0.20/d) and resulted from lower than projected permanganate concentrations. Both ERI and spatial electrical conductivity measurements verified that permanganate distribution was not uniform throughout the 6.1-m (20 feet) well screens and that groundwater sampling captured both treated and nontreated groundwater during pumping. Although heterogeneous flow paths precluded a uniform permanganate distribution, pilot-scale results provided proof-of-concept that permanganate can degrade RDX in situ and support permanganate as a possible remedial treatment for RDX-contaminated groundwater.     

Vitamin B12 and Reduced Titanium for Remediation of Residual Chlorinated Solvents: Field Experiment

A first pilot-scale field experiment using vitamin B₁₂ and reduced titanium was conducted in an in situ vertical circulation column at CFB Borden. The objective of the experiment was to test the applicability of the technology for restoring aquifer source zones contaminated by chlorinated solvents—tetrachloroethene (PCE) and 1,1,1-trichloroethane (1,1,1-TCA)—in a mixture of dense nonaqueous phase liquids (DNAPLs). Vitamin B₁₂ promotes the reductive dechlorination of chlorinated organics. A highly reducing and slightly alkaline environment must be maintained (Eh < - 480 mV and 7 < pH < 9) to maximize the rate of degradation. In this field test, PCE and 1,1,1-TCA degraded to a limited extent under experimental conditions, with 1,1,1-TCA degrading more readily. Indigenous bacteria were found to metabolize citrate, which caused titanium to precipitate, limiting degradation. The addition of glucose at the end of a second field season effectively limited citrate degradation and helped recover the optimal redox potential by keeping reduced titanium in solution. A laboratory column was used to confirm field results. The column also produced a significant biomass, which provided an additional source of organic carbon onto which the solvents sorbed.     

High-pressure disproportionation of Co2SiO4 spinel and implications for Mg2SiO4 spinel

Co₂SiO₄ spinel has been found to disproportionate into its isochemically mixed oxides with rocksalt and rutile structures at pressures between 170 and 190 kbar and temperatures between 1400 and 1800°C in a diamond-anvil press. The exact disproportionation pressure is not certain due to transient increases in pressure during the local and rapid heating by a continuous YAG laser. The slope of the phase boundary between the spinel phase and the mixed oxides is calculated to be?33 ± 20bar/deg. This negative slope is consistent with the observed anomalously large entropy of CoO (relative to its isostructural oxides) in entropy vs.(MV)^?1/2 systematics, whereM is the formula weight andV the molar volume. The sign of the slope for a phase boundary in the disproportionation of spinel depends on the values of entropy of the rocksalt oxides as well as the inverse character exhibited in the spinel phases. The normal entropy of MgO suggests that the phase boundary for the disproportionation of Mg₂SiO₄ spinel has positive slope.     

Pyroxene-garnet solid-solution equilibria in the systems Mg4Si4O12Mg3Al2Si3O12 and Fe4Si4O12Fe3Al2Si3O12 at high pressures and temperatures

Pyroxene-garnet solid-solution equilibria have been studied in the pressure range 41–200 kbar and over the temperature range 850–1,450°C for the system Mg₄Si₄O₁₂Mg₃Al₂Si₃O₁₂, and in the pressure range 30–105 kbar and over the temperature range 1,000–1,300°C for the system Fe₄Si₄O₁₂Fe₃Al₂Si₃O₁₂. At 1,000°C, the solid solubility of enstatite (MgSiO₃) in pyrope (Mg₃Al₂Si₃O₁₂) increases gradually to 140 kbar and then increases suddenly in the pressure range 140–175 kbar, resulting in the formation of a homogeneous garnet with composition Mg₃(Al_0.8Mg_0.6Si_0.6)Si₃O₁₂. In the MgSiO₃-rich field, the three-phase assemblage of β- or γ-Mg₂SiO₄, stishovite and a garnet solid solution is stable at pressures above 175 kbar at 1,000°C. The system Fe₄Si₄O₁₂Fe₃Al₂Si₃O₁₂ shows a similar trend of high-pressure transformations: the maximum solubility of ferrosilite (FeSiO₃) in almandine (Fe₃Al₂Si₃O₁₂) forming a homogeneous garnet solid solution is 40 mol% at 93 kbar and 1,000°C.If a pyrolite mantle is assumed, from the present results, the following transformation scheme is suggested for the pyroxene-garnet assemblage in the mantle. Pyroxenes begin to react with the already present pyrope-rich garnet at depths around 150 km. Although the pyroxene-garnet transformation is spread over more than 400 km in depth, the most effective transition to a complex garnet solid solution takes place at depths between 450 and 540 km. The complex garnet solid solution is expected to be stable at depths between 540 and 590 km. At greater depths, it will decompose to a mixture of modified spinel or spinel, stishovite and garnet solid solutions with smaller amounts of a pyroxene component in solution.     

Synthesis of γ-Mg2SiO4

Magnesium orthosilicate with spinel structure (γ-Mg₂SiO₄) was synthesized at about 250 kbar and 1000°C. Unit cell dimension was established to be 8.076 ± 0.001Å. X-ray powder diffraction pattern revealed a significant difference between γ-Mg₂SiO₄ and other γ-M₂SiO₄ spinels (M = Fe, Co, and Ni) in the intensities of (111) and (331) reflections, both of which are virtually absent in the Mg₂SiO₄ spinel. This feature could be thoroughly understood by the calculation of the intensities for several silicate spinels.     

High-pressure phases of Co2GeO4, Ni2GeO4, Mn2GeO4 and MnGeO3: implications for the germanate-silicate modeling scheme and the Earth's mantle

In a diamond-anvil press coupled with YAG laser heating, the spinels of Co₂GeO₄ and Ni₂GeO₄ have been found to disproportionate into their isochemical oxide mixtures at about 250 kbar and 1400–1800°C in the same manner as their silicate analogues. At about the same P-T conditions MnGeO₃ transforms to the orthorhombic perovskite structure (space group Pbnm); the lattice parameters at room temperature and 1 bar are a₀ = 5.084 ± 0.002, b₀ = 5.214 ± 0.002, and c₀ = 7.323 ± 0.003Å with Z = 4 for the perovskite phase. The zero-pressure volume change associated with the ilmenite-perovskite phase transition in MnGeO₃ is ?6.6%. Mn₂GeO₄ disproportionates into a mixture of the perovskite phase of MnGeO₃ plus the rocksalt phase of MnO at P = 250kbar and T = 1400–1800°C. The concept of utilizing germanates as high-pressure models for silicates is valid in general. The results of this study support the previous conclusion that the lower mantle comprises predominantly the orthorhombic perovskite phase of ferromagnesian silicate.     

Field Test of the In Situ Permeable Ground Water Flow Sensor

Two in situ permeable flow sensors, recently developed at Sandia National Laboratories, were field tested at the Brazos River Hydrologic Field Site near College Station, Texas. The flow sensors use a thermal perturbation technique to quantify the magnitude and direction of ground water flow in three dimensions. Two aquifer pumping tests lasting eight and 13 days were used to field test the flow sensors. Components of ground water flow as determined from piezometer gradient measurements were compared with ground water flow components derived from the 3-D flow sensors. The changes in velocity magnitude and direction of ground water flow induced by the pump were evaluated using flow sensor data and piezometric analyses. Flow sensor performance closely matched piezometric analysis results. Ground water flow direction (azimuth), as measured by the flow sensors and derived in the piezometric analysis, predicted the position of the pumping well accurately. Ground water flow velocities measured by the flow sensors compared well to velocities derived in the piezometric analysis. A significant delay in flow sensor response to relatively rapid changes in ground water flow was observed. Preliminary tests indicate that the in situ permeable flow sensor provides accurate and timely information on the velocity magnitude and direction of ground water flow.     

Factors Controlling In Situ Biogeochemical Transformation of Trichloroethene: Field Survey

We have previously defined in situ biogeochemical transformation as the biogenic formation of reactive minerals that are capable of abiotically degrading chlorinated solvents such as trichloroethene without accumulation of degradation products such as vinyl chloride (AFCEE et al. 2008 ). This process has been implemented in biowalls used to intercept contaminated groundwater. Abiotic patterns of contaminant degradation were observed at Altus Air Force Base (AFB) and in an associated column study, but not at other sites including Dover AFB. These abiotic patterns were associated with biogenic formation of reactive iron sulfide minerals. Iron sulfides in the form of small individual grains, coatings on magnetite, and sulfur‐deficient pyrite framboids were observed in samples collected from the Altus AFB biowalls and one of the EPA columns. Larger iron sulfide grains coated with oxide layers were observed in samples collected from Dover AFB. Altus AFB and the EPA column differed from Dover AFB in that groundwater flow at Dover AFB was relatively slow and potentially reversing. High volumetric sulfate consumption rates, an abiotic pattern of trichloroethene (TCE) degradation, and the formation of small, high surface area iron sulfide particles were associated with relatively high rates of TCE removal via an abiotic pattern. Geochemical modeling demonstrated that iron monosulfides such as mackinawite were near saturation, and iron disulfides such as pyrite were supersaturated at all sites. This environmental condition can be supportive of nucleation of small particles rather than crystal growth leading to larger particles. When nucleation is dominant, small, high surface area, and reactive particles result. When crystal growth dominates the crystals are larger and have lower specific surface area and reactivity. These results taken together suggest that creation of a dynamic environment can promote biogeochemical transformation based on generation of reactive iron sulfides.