The Role of Microorganisms in Uranium Behavior in the Water–Rock System

Geochemical processes involving redox reactions and leading to either formation or transformation of geochemical barriers may be largely induced or enhanced by microbial activity. The microbial reduction of uranium is studied as a strategy for rehabilitation of uranium-containing groundwater. The bioremediation mechanism converts dissolved uranium(VI) into low-solubility U(IV). The processes involving dissimilatory reducing bacteria, which facilitate the reduction and retention of U(VI) in soils and rocks, are considered. The diversity of microorganisms involved in anaerobic reduction of uranium is shown. The geochemical conditions that may affect the rate of microbial reduction of U(VI) are specified, i.e., the presence of nitrate ions, phosphate ions, calcium ions, and iron oxides. The mechanisms of their action are examined. Geochemical barriers with the participation of microorganisms are proposed for the rehabilitation of groundwater with uranium removed from groundwater and deposited locally as a result of microbial reduction of U(VI).     

Comparison of Electrostatic and Non‐Electrostatic Models for U(VI) Sorption on Aquifer Sediments

A non‐electrostatic generalized composite surface complexation model (SCM) was developed for U(VI) sorption on contaminated F‐Area sediments from the U.S. Department of Energy Savannah River Site, South Carolina. The objective of this study was to test if a simpler, semi‐empirical, non‐electrostatic U(VI) sorption model (NEM) could achieve the same predictive performance as a SCM with electrostatic correction terms in describing U(VI) plume evolution and long‐term mobility. One‐dimensional reactive transport simulations considering key hydrodynamic processes, Al and Fe minerals, as well as H⁺ and U surface complexation, with and without electrostatic correction terms, were conducted. The NEM was first calibrated with laboratory batch H⁺ and U(VI) sorption data on F‐Area sediments, and then the surface area of the NEM was adjusted to match field observations of dissolved U(VI). Modeling results indicate that the calibrated NEM was able to perform as well as the previously developed electrostatic model in predicting the long‐term evolution of H⁺ and U(VI) at the site, given the variability of field‐site data. The electrostatic and NEM models yield somewhat different results for the time period when basin discharge was active; however, it is not clear which modeling approach may be better to model this early time period because groundwater quality data during this period were not available. A key finding of this study is that the applicability of NEM (and thus robustness of its predictions) to the field system evolves with time and is strongly dependent on the pH range that was used to develop the model.     

Reduced Sediments: A Factor in the Design of Subsurface Oxidant Delivery Systems

A preliminary field performance evaluation of in situ bioremediation of a contaminated aquifer at the Libby, Montana, Superfund site, a former wood preserving site, was conducted for the Bioremediation Field Initiative sponsored by the U.S. Environmental Protection Agency (U.S. EPA). The current approach for site remediation involves injecting oxygen and nutrients into the aquifer to stimulate microbial degradation of target compounds that include polycyclic aromatic hydrocarbons and pentachlorophenol. The preliminary field evaluation determined that, in addition to the oxygen demand associated with the microbial oxidation of the organic contamination, uncontaminated aquifer sediments at the site are naturally reduced and also exert a significant oxygen demand. This conclusion is supported by three types of information: (1) analyses of ground water samples; (2) results from a field-scale tracer test; and (3) results of laboratory evaluations of oxygen use by reduced aquifer sediment samples. An estimate of the cost of supplying hydrogen peroxide to satisfy the oxygen demand of the uncontaminated reduced sediments is provided to demonstrate that the additional cost of oxidizing the reduced sediments could be significant. The presence of naturally occurring reduced sediments at a contamination site should be considered in the design of subsurface oxidant delivery systems.     

Experimental study on reduction of U (VI) by an anaerobic bacterium, <Emphasis Type="Italic">Shewanella putrefaciens</Emphasis>: Application to sandstone-hosted interlayer oxidation-zone type uranium deposits,China

An experimental study on reduction of U (VI) by anaerobic bacteria, Shewanella putrefaciens, is first reported here in China. The experimental conditions were: 35°C and pH= 7.0-7.4, corresponding to a physicochemical environments in which the sandstone-hosted interlayer oxidation-zone type uranium deposit formed in Northwest China’s Xinjiang. Bacteria adopted in the present experiment, Shewanella putrefaciens, occur extensively in natural environment. Our study shows that nano-crystal precipitates of uraninite quickly occurred on the surface of the cells within one week. It was found that the pitchblende was characterized by a random arrangement of uraninite nanocrystals (2-4 nm) in it, significantly different from natural pitchblende in which uraninite nanocrystals are arranged in order. Finally, a possible mechanism of uranium biomineralization by microorganisms in the deposits is discussed. Our investigation may supply a technical train of thoughts for bioremediation of nuclear-contaminated water environments and for underground dissolving extraction of the sandstone-hosted uranium ores.     

Arrays of Unpumped Wells for Plume Migration Control by Semi-Passive In Situ Remediation

Arrays of unpumped wells can be used as discontinuous permeable walls in which each well serves both as a means to focus ground water flow into the well for treatment and as a container either for permeable reactive media which directly destroy dissolved ground water contaminants or for devices or materials which release amendments that support in situ degradation of contaminants within the aquifer downgradient of the wells. This paper addresses the use of wells for amendment delivery, recognizing the potential utility of amendments such as electron acceptors (e.g., oxygen nitrate), electron donors (primary substrates), and microbial nutrients for stimulating bioremediation, and the potential utility of oxidizers, reducers, etc., for controlled abiotic degradation. Depending on its rate and constraints, the remedial reaction may occur within the well and/or downgradient. For complete remediation of ground water passing through the well array, the total flux of amendment released must meet or exceed the total flux demand imposed by the plume. When there are constraints on the released concentration of amendment (relative to the demand), close spacing of the wells may be required. If the flux balance allows wider spacing, it is likely that limited downgradient spreading of the released amendment will then be the primary constraint on interwell spacing. Divergent flow from the wells, roughly two times the well diameter, provides the bulk of downgradient spreading and constrains maximum well spacing in the absence of significant lateral dispersion. Stronger lateral dispersion enhances the spreading of amendment, thereby increasing the lateral impact of each well, which allows for wider well spacing.     

Release of Chromium from Soils with Persulfate Chemical Oxidation

An important part of the evaluation of the effectiveness of persulfate in situ chemical oxidation (ISCO) for treating organic contaminants is to identify and understand its potential impact on metal co‐contaminants in the subsurface. Chromium is a redox‐sensitive and toxic metal the release of which poses considerable risk to human health. The objective of this study was to investigate the impact of persulfate chemical oxidation on the release of chromium from three soils varying in physical‐chemical properties. Soils were treated with unactivated and activated persulfate [activated with Fe(II), Fe(II)‐EDTA, and alkaline pH] at two different concentrations (i.e., 41 mM and 2.1 mM persulfate) for 48 h and 6 months and were analyzed for release of chromium. Results show that release of chromium with persulfate chemical oxidation depends on the soil type and the activation method. Sandy soil with low oxidant demand released more chromium compared to soils with high oxidant demand. More chromium was released with alkaline pH activation. Alkaline pH and high Eh conditions favor oxidation of Cr(III) to Cr(VI), which is the main mechanism of release of chromium with persulfate chemical oxidation. Unactivated and Fe(II)‐activated persulfate decreased pH and at low pH in absence of EDTA chromium release is not a concern. These results indicate that chromium release can be anticipated based on the given site and treatment conditions, and ISCO system can be designed to minimize potential chromium release when treating soils and groundwater contaminated with both organic and metal contaminants.     

Gladstone, Australia Field Studies: Weathering and Degradation of Hydrocarbons in Oiled Mangrove and Salt Marsh Sediments With and Without the Application of an Experimental Bioremediation Protocol

This field study was a combined chemical and biological investigation of the relative rates of weathering and biodegradation of oil spilled in sediments and testing the influence of a bioremediation protocol. The aim of the chemistry work presented here was to determine whether the bioremediation protocol affected the rate of penetration, dissipation or long-term retention of a medium range crude oil (Gippsland) and a Bunker C oil stranded in tropical Rhizophora sp. mangrove and Halosarcia sp. salt marsh environments. Permission for the planned oil spills was granted in the Port Authority area of Gladstone, Queensland (Australia). Sediment cores from three replicate plots of each treatment for mangroves and four replicate plots for the salt marsh (oil only and oil plus bioremediation) were analysed for total hydrocarbons (THC) and for individual alkane markers using gas chromatography with flame ionization detection (GC–FID). Sediments were collected at day 2, then 1, 2, 5 or 6 and 12 or 13 months post-spill for mangroves and day 2, 1, 3 and 9 months post-spill for salt marshes. Over this time, hydrocarbons in all of the oil treated plots decreased exponentially. There was no statistical difference in initial oil concentrations, penetration of oil to depth, or in the rates of oil dissipation between untreated oil and bioremediated oil in the mangrove plots. The salt marsh plots treated with the waxy Gippsland oil showed a faster rate of biodegradation of the oil in the bioremediated plots. In this case only, the degradation rate significantly impacted the mass balance of remaining oil. The Bunker C oil contained only minor amounts of highly degradable n-alkanes and bioremediation did not significantly impact its rate of loss in the salt marsh sediments. At the end of each experiment, there were still n-alkanes visible in the gas chromatograms of residual oils. Thus it was concluded that there was unlikely to be any change in the stable internal biomarkers of the oils over this time period. The predominant removal processes in both habitats were evaporation and dissolution, with a lag-phase of 1–2 months before the start of microbial degradation.     

The estuarine chemistry and isotope systematics of U in the Amazon and Fly Rivers

Natural concentrations of ²³⁸U and δ²³⁴U values were determined in estuarine surface waters and pore waters of the Amazon and Fly (Papua New Guinea) Rivers to investigate U transport phenomena across river-dominated land–sea margins. Discharge from large, tropical rivers is a major source of dissolved and solid materials transported to the oceans, and are important in defining not only oceanic mass budgets, but also terrestrial weathering rates.On the Amazon shelf, salinity-property plots of dissolved organic carbon, pH and total suspended matter revealed two vastly contrasting water masses that were energetically mixed. In this mixing zone, the distribution of uranium was highly non-conservative and exhibited extensive removal from the water column. Uranium removal was most pronounced within a salinity range of 0–16.6, and likely the result of scavenging and flocculation reactions with inorganic (i.e., Fe/Mn oxides) and organic colloids/particles. Removal of uranium may also be closely coupled to exchange and resuspension processes at the sediment/water interface. An inner-shelf pore water profile indicated the following diagenetic processes: extensive (1 m) zones of Fe(III)—and, to a lesser degree, Mn(IV)—reduction in the absence of significant S(II) concentrations appeared to facilitate the formation of various authigenic minerals (e.g., siderite, rhodocrosite and uraninite). The pore water dissolved ²³⁸U profile co-varied closely with Mn(II). Isotopic variations as evidenced in δ²³⁴U pore waters values from this site revealed information on the origin and history of particulate uranium. Only after a depth of about 1 m did the δ²³⁴U value approach unity (secular equilibrium), denoting a residual lattice bound uranium complex that is likely an upper-drainage basin weathering product. This suggests that the enriched δ²³⁴U values represent a riverine surface complexation product that is actively involved in Mn–Fe diagenetic cycles and surface complexation reactions.In the Fly River estuary, ²³⁸U appears to exhibit a reasonably conservative distribution as a function of salinity. The absence of observed U removal does not necessarily imply non-reactivity, but instead may record an integration of concurrent U removal and release processes. There is not a linear correlation between δ²³⁴U vs. 1/²³⁸U that would imply simple two component mixing. It is likely that resuspension of bottom sediments, prolonged residence times in the lower reaches of the Fly River, and energetic particle–colloid interactions contribute to the observed estuarine U distribution. The supply of uranium discharged from humid, tropical river systems to the sea appears to be foremost influenced by particle/water interactions that are ultimately governed by the particular physiographic and hydrologic characteristics of an estuary.     

Plume and lithologic profiling with surface resistivity and seismic tomography

Improved surface-based geophysical technologies that are commercially available provide a new level of detail that can be used to guide ground water remediation. Surface-based multielectrode resistivity methods and tomographic seismic refraction techniques were used to image to a depth of approximately 30 m below the surface at the Natural and Accelerated Bioremediation Research Field Research Center. The U.S. Department of Energy (DOE) established the research center on the DOE Oak Ridge Reservation in Oak Ridge, Tennessee, to conduct in situ field-scale studies on bioremediation of metals and radionuclides. Bioremediation studies are being conducted on the saprolite, shale bedrock, and ground water at the site that have been contaminated with nitrate, uranium, technetium, tetrachloroethylene, and other contaminants (U.S. DOE 1997). Geophysical methods were effective in imaging the high-ionic strength plume and in defining the transition zone between saprolite and bedrock zones that appears to have a significant influence on contaminant transport. The geophysical data were used to help select the location and depth of investigation for field research plots. Drilling, borehole geophysics, and ground water sampling were used to verify the surface geophysical studies.     

Removal of Cr(VI) by Zero‐valent,Iron‐encapsulated Alginate Beads

Zero‐valent, iron‐encapsulated alginate beads were synthesized and were applied for the removal of Cr(VI) from aqueous solutions. The effects of several important parameters including solution pH, contact time, initial concentration and reaction temperature on Cr(VI) removal levels were investigated in batch studies. An initial solution pH of 1.0 was seen to be most favorable for Cr(VI) removal. The removal process was quick and almost 80% of the removal was attained within 60 min. The kinetic data followed the second‐order equation well. The Cr(VI) removal was almost reaction temperature‐independent and decreased with an increase in Cr(VI) initial concentration. The removal of Cr(VI) by iron‐encapsulated alginate beads was found to be significantly higher than that of non‐encapsulated alginate beads.     

Electrokinetic Migration of Nitrate Through Heterogeneous Granular Porous Media

This study investigates and quantifies the influence of physical heterogeneity in granular porous media, represented by materials with different hydraulic conductivity, on the migration of nitrate, used as an amendment to enhance bioremediation, under an electric field. Laboratory experiments were conducted in a bench‐scale test cell under a low applied direct current using glass bead and clay mixes and synthetic groundwater to represent ideal conditions. The experiments included bromide tracer tests in homogeneous settings to deduce controls on electrokinetic transport of inorganic solutes in the different materials, and comparison of nitrate migration under homogeneous and heterogeneous scenarios. The results indicate that physical heterogeneity of subsurface materials, represented by a contrast between a higher‐hydraulic conductivity and lower‐hydraulic conductivity material normal to the direction of the applied electric field exerts the following controls on nitrate migration: (1) a spatial change in nitrate migration rate due to changes in effective ionic mobility and subsequent accumulation of nitrate at the interface between these materials; and (2) a spatial change in the voltage gradient distribution across the hydraulic conductivity contrast, due to the inverse relationship with effective ionic mobility. These factors will contribute to higher mass transport of nitrate through low hydraulic conductivity zones in heterogeneous porous media, relative to homogeneous host materials. Overall electrokinetic migration of amendments such as nitrate can be increased in heterogeneous granular porous media to enhance the in situ bioremediation of organic contaminants present in low hydraulic conductivity zones.     

Evidence of methylmercury production and modification of the microbial community structure in estuary sediments contaminated with wastewater treatment plant effluents

The Seine’s estuary (France) waters are the receptacle of effluents originating from wastewater treatment plants (WWTP). In this estuary, mudflats are deposition zones for sediments and their associated contaminants, and play an essential role in the mercury (Hg) biogeochemical cycle mainly due to indigenous microorganisms. Microcosms were used to assess the impact of WWTP-effluents on mercury methylation by monitoring Hg species (total dissolved Hg in porewater, methylmercury and total mercury) and on microbial communities in sediments. After effluent amendment, methylmercury (MeHg) concentrations increased in relation with the total Hg and organic matter content of the WWTP-effluents. A correlation was observed between MeHg and acid-volatile-sulfides concentrations. Quantification of sulfate-reducing microorganisms involved in Hg methylation showed no increase of their abundance but their activity was probably enhanced by the organic matter supplied with the effluents. WWTP-effluent spiking modified the bacterial community fingerprint, mainly influenced by Hg contamination and the organic matter amendment.     

Response of estuarine meio- and macrofauna to in situ bioremediation of oil-contaminated sediment

Numerous studies have demonstrated the efficacy of bioremediation for enhancing oil removal but the ecological effect on shoreline biota is unclear. Therefore, a field experiment was designed at an intertidal sandflat in SW England to assess the effects of nutrient addition to oiled sediments on meio- and macrofauna for a period of up to 45 weeks. Natural assemblages were exposed to different types of experimental treatments (no oil, oil alone, oil treated with slow-release fertiliser or liquid fertiliser). Bioremediation stimulated the microbial population and increased oil biodegradation. This, however, did not result in faster recolonisation rates of fertilised versus non-fertilised oiled sediments. Mild effects of oil and bioremediation treatments on benthic fauna were observed, including short-term shifts in dominance patterns. Decreased abundance of dominant species in the oiled compared to unoiled sediments resulted in significantly higher evenness of benthic assemblages within the first 11 weeks of the experiment.     

Effect of Co‐culture and Nutrients Supplementation on Bioremediation of Crude Petroleum Sludge

Ex‐situ bioremediation of real‐field crude petroleum sludge was evaluated to elucidate the role of co‐culture (bioaugmentation) and external nutrients supplementation (biostimulation) under anaerobic microenvironment. Maximum removal of total petroleum hydrocarbons (TPH) was observed by integrating biostimulation with bioaugmentation (R5, 44.01%) followed by bioaugmentation alone (R4, 34.47%), co‐substrate supplemented operations [R6, 23.36%; R3, 16.5%; R2, 9.88%] and control (R1, 4.36%). Aromatics fraction showed higher degradation in all the conditions studied. Fate of six selected polycyclic aromatic hydrocarbons (PAHs) was evaluated during bioremediation. Among these, four ring PAHs compounds showed good degradation by integration of biostimulation with bioaugmentation (R5) while bioaugmentation alone (R4) documented good degradation of three ring PAHs. Lower ring PAHs compounds showed good degradation with the application of biostimulation (R6). Fluorescent in situ hybridization (FISH) detected the presence of known PAHs degrading microorganisms viz., Bacillus, Pseudomonas, Acido bacteria, Sulphur reducing bacteria Firmicutes, etc. Application of biostimulation and bioaugmentation strategies alone or in combinations documented noticeable influence on the degradation of petroleum sludge.     

Geochemical Assessment of a Subtropical Reservoir: A Case Study in Curitiba,Southern Brazil

Suspended particles and dissolved substances in water provide reactive surfaces, influence metabolic activity and contribute to the net sediment deposition. It therefore plays an important part in the ecology and quality of the water mass. The water quality in reservoirs is crucial and it is naturally maintained by flushing and sedimentation, which continuously remove phosphorus from the water. In some reservoirs, however, these removal processes are countered by recycling of ions which could play a key role to start and/or maintain the eutrophic state. The combination of macro‐, trace‐ and microanalysis techniques can be useful to trace pollution sources through a chemical fingerprint, whether be during an acute environmental disaster or a long‐term release of pollutants. The water quality and total metal content of reservoir sediments were assessed in a reservoir, situated in the capital of the Paraná State, in the South‐Eastern part of Brazil. The goal of this paper was to determine the metal presence in the sediment and metal and ionic speciation in the Green River reservoir water. Water and bed sediment samples, collected from various sites during 2008 and 2009, were investigated using XRF, ICP‐OES, ICP‐MS, XRD and zeta potential measurements. Based on the results, the heavy metal concentration and chemical composition of the suspended matter in the water samples, as well as the sediment's chemical composition will be discussed.     

Engineering and hydrogeological problems associated with in situ treatment

Abstract

Most organic materials that contaminate soil and the subsurface environment are readily degraded by natural biological processes. To this degree, in situ bioremediation can be thought of as a highly successful purification process. However, some organic molecules are naturally refractory to biodegradation, or other environmental factors induce molecular recalcitrance such as the absence of a proper microbial population or the presence of unsuitable environmental conditions. Examples of recalcitrant groundwater contaminants are soluble components of petroleum hydrocarbons (BTEX) and chlorinated aliphatic hydrocarbons (CAHs). Organic recalcitrance may be changed through introduction of degrading populations of microorganisms or by changing the environmental conditions through introduction of nutrients or other chemicals. The most significant engineering deficiency in in situ bioremediation is the absence of proven methods to introduce such materials into the subsurface environment for efficient mixing with microorganisms and the contaminants of concern.     

Uranium and thorium isotopes in the rivers of the Amazonian basin: hydrology and weathering processes

Two expeditions (October 1989 and May 1992) were carried out to two points of the main Amazon River channel and four tributaries. The Solimões and Madeira rivers, taking their origin in the Andes, are whitewater rivers. The Negro River is a typical acid, blackwater river. The Trombetas River flows through bauxite‐rich areas, and is characterized by low concentrations of dissolved humic substances. The ²³⁸U, ²³⁴U, ²³²Th and ²³⁰Th activities were recorded from dissolved, suspended particulate phases and river bank sediments. The latter were analysed for their ²²⁶Ra, ²²⁸Ra and ²¹⁰Pb contents, and also subjected to leaching with 0·2 M hydroxylamine–hydrochloride solution to determine the concentrations of radionuclides bound to amorphous Fe hydroxides and Mn oxides and hydroxides. The dissolved U average concentration in the Amazon system is ten times lower than the mean world river concentration. The uranium concentration observed at Óbidos in the lower Amazon (0·095 µg L^?1), where the U content in the river bank sediments and suspended matter is lowest, suggests U release from the solid phase during river transport. About 485 t of U are transported annually to the Amazon delta area in dissolved form, and 1943 t bound to suspended particulate matter. Total U and Th concentrations in the river bank sediments ranged from 1·59 to 7·14 µg g^?1 and from 6·74 to 32 µg g^?1, respectively. The highest concentrations were observed in the Trombetas River. The proportion extracted by means of the hydroxylamine solution (HL) was relatively high for U in the Trombetas river bank sediment (31%) and for Th in the Solimões sediment (30%). According to the alpha recoil effects, the ²³⁴U/²³⁸U activity ratios of the Andean river waters and downstream Amazon water (Óbidos) were >1, but were <1 in the Negro River (at Manaus). The activity ratios of dissolved U correlate with pH and also with the U activity ratios in the river bank sediment hydroxylamine extracts. As expected, the ²³⁴U/²³⁸U activity ratios in river bank sediments were <1 in the Andean rivers and in the downstream Amazon, but they were >1 in the Trombetas and Negro rivers. Such ratios probably result from the binding of dissolved uranium to solid sediment. The ²²⁸Th/²³²Th ratios of river bank sediments were close to unity (except for the Negro River, where it is lower), suggesting no significant Th exchanges between the river water and the sediment. The ²²⁶Ra/²³²Th activity ratios were <1, and the ²²⁶Ra/²²⁸Ra activity ratios generally were significantly higher than the activity ratios of their respective parents. This perhaps is the result of easier leaching of the ²²⁶Ra parent, ²³⁰Th, from solid material (owing to the alpha recoil effect) than of the ²²⁸Ra parent. Uranium and thorium isotopes were used as tools to evaluate the chemical weathering rate of rocks in the Amazon system, which was estimated to be 2·7 cm 1000 year^?1 s^?1. Copyright © 2002 John Wiley & Sons, Ltd.     

Downdrift coarsening of beach foreshore sediments at tidal inlets: An example from the coast of New Jersey

Analysis of grain size statistics of upper foreshore sediments on sand beaches at two tidal inlets in New Jersey, U.S.A. reveals that sediments are coarser at beaches flanking the inlets than updrift, although sediments become finer downdrift at the broad, regional scale. The local reversal of the regional trend in size grading is attributed to: (1) the offshore diversion of the finer sands along the surf zone on the ebb tidal delta, and (2) the removal of the finer sands from the inlet flank beach caused by low wave energy conditions at low stages of the tide and by deflation. Sediments thus become coarser at inlet beaches as a result of alterations in the interaction of waves with the beach and as a result of aeolian processes, not solely as a result of increased tidal current velocities as previously reported. The distance along the New Jersey barrier islands over which inlet processes are likely to affect changes in sediment size updrift averages less than 1100 m, but the impacts of inlets on the sedimentary record can be extended greater distances as a result of inlet migration.     

Analytical approximation to characterize the performance of in situ aquifer bioremediation

The performance of in situ bioremediation to remove organic contaminants from contaminated aquifers depends on the physical and biochemical parameters. We characterize the performance by the contaminant removal rate and the region where biodegradation occurs, the biologically active zone (BAZ). The numerical fronts obtained by one-dimensional in situ bioremediation modeling reveal a traveling wave behavior: fronts of microbial mass, organic contaminant and electron acceptor move with a constant velocity and constant front shape through the domain. Hence, only one front shape and a linear relation between the front position and time is found for each of the three compounds. We derive analytical approximations for the traveling wave front shape and front position that agree perfectly with the traveling wave behavior resulting from the bioremediation model. Using these analytical approximations, we determine the contaminant removal rate and the BAZ. Furthermore, we assess the influence of the physical and biochemical parameters on the performance of the in situ bioremediation technique.     

Time‐Lapse Electrical Geophysical Monitoring of Amendment‐Based Biostimulation

Biostimulation is increasingly used to accelerate microbial remediation of recalcitrant groundwater contaminants. Effective application of biostimulation requires successful emplacement of amendment in the contaminant target zone. Verification of remediation performance requires postemplacement assessment and contaminant monitoring. Sampling‐based approaches are expensive and provide low‐density spatial and temporal information. Time‐lapse electrical resistivity tomography (ERT) is an effective geophysical method for determining temporal changes in subsurface electrical conductivity. Because remedial amendments and biostimulation‐related biogeochemical processes often change subsurface electrical conductivity, ERT can complement and enhance sampling‐based approaches for assessing emplacement and monitoring biostimulation‐based remediation. Field studies demonstrating the ability of time‐lapse ERT to monitor amendment emplacement and behavior were performed during a biostimulation remediation effort conducted at the Department of Defense Reutilization and Marketing Office (DRMO) Yard, in Brandywine, Maryland, United States. Geochemical fluid sampling was used to calibrate a petrophysical relation in order to predict groundwater indicators of amendment distribution. The petrophysical relations were field validated by comparing predictions to sequestered fluid sample results, thus demonstrating the potential of electrical geophysics for quantitative assessment of amendment‐related geochemical properties. Crosshole radar zero‐offset profile and borehole geophysical logging were also performed to augment the data set and validate interpretation. In addition to delineating amendment transport in the first 10 months after emplacement, the time‐lapse ERT results show later changes in bulk electrical properties interpreted as mineral precipitation. Results support the use of more cost‐effective surface‐based ERT in conjunction with limited field sampling to improve spatial and temporal monitoring of amendment emplacement and remediation performance.