Dissolution of an emplaced source of DNAPL in a natural aquifer setting

Field-scale dissolution of a multicomponent DNAPL (dense nonaqueous-phase liquid) source intentionally emplaced below the water table is evaluated in a well-characterized natural aquifer setting. The block-shaped source contained 23 kg of a trichloromethane, trichloroethene, and perchloroethene mixture homogeneously distributed at 5% saturation of pore space. Dissolution was monitored for 3 yr via down-gradient samplers (1-m fence) and occasional intra-source sampling. Although intra-source equilibrium dissolution was shown and endorsed by supporting modeling and literature lab data, less than equilibrium concentrations were predominantly monitored in the 1-m fence. This was ascribed to significant by-passing of the source by groundwater flow due to its low permeability relative to the aquifer and associated dilution of concentrations emitted from the source. Heterogeneous source dissolution occurred despite the relative homogeneity of the source and aquifer and was ascribed to dissolution fingering, which has not been previously field-demonstrated. Bulk bypass of groundwater flow around the source zone caused slow dissolution rates, with 77% of the source remaining after 3 yr and a projected longevity of approximately 25 yr. Observed dissolution fingering would have significantly increased longevity as it increasingly caused intra-source bypass of remaining DNAPL. Our dissolution interpretations were endorsed by additional data collected after 6 yr during source remediation via permanganate oxidation.     

Field, experimental, and modeling study of arsenic partitioning across a redox transition in a Bangladesh aquifer

To understand redox-dependent arsenic partitioning, we performed batch sorption and desorption experiments using aquifer sands subjected to chemical and mineralogical characterization. Sands collected from the redox transition zone between reducing groundwater and oxic river water at the Meghna riverbank with HCl extractable Fe(III)/Fe ratio ranging from 0.32 to 0.74 are representative of the redox conditions of aquifers common in nature. One brown suboxic sediment displayed a partitioning coefficient (K(d)) of 7-8 L kg(-1) at equilibrium with 100 μg L(-1) As(III), while two gray reducing sediments showed K(d) of 1-2 L kg(-1). Lactate amendment to aquifer sands containing 91 mg kg(-1) P-extractable As resulted in the reduction of As and Fe with sediment Fe(III)/Fe decreasing from 0.54 to 0.44, and mobilized an equivalent of 64 mg kg(-1) As over a month. Desorption of As from nonlactate-amended sediment was negligible with little change in sediment Fe(III)/Fe. This release of As is consistent with microbial reduction of Fe(III) oxyhydroxides and the resulting decrease in the number of surface sites on Fe(III) oxyhydroxides. Arsenic partitioning (K(d)) in iron-rich, sulfur-poor aquifers with circumneutral pH is redox-dependent and can be estimated by HCl leachable sediment Fe(III)/Fe ratio with typical Fe concentrations.     

Mass-transfer limitations for nitrate removal in a uranium-contaminated aquifer

A field test on in situ subsurface bioremediation of uranium(VI) is underway at the Y-12 National Security Complex in the Oak Ridge Reservation, Oak Ridge, TN. Nitrate has a high concentration at the site, which prevents U(VI) reduction, and thus must be removed. An acidic-flush strategy for nitrate removal was proposed to create a treatment zone with low levels of accessible nitrate. The subsurface at the site contains highly interconnected fractures surrounded by matrix blocks of low permeability and high porosity and is therefore subject to preferential flow and matrix diffusion. To identify the heterogeneous mass transfer properties, we performed a novel forced-gradient tracer test, which involved the addition of bromide, the displacement of nitrate, and the rebound of nitrate after completion of pumping. The simplest conceptualization consistent with the data is that the pore-space consists of a single mobile domain, as well as a fast and a slowly reacting immobile domain. The slowly reacting immobile domain (shale matrix) constitutes over 80% of the pore volume and acts as a long-term reservoir of nitrate. According to simulations, the nitrate stored in the slowly interacting immobile domain in the fast flow layer, at depths of about 12.2-13.7 m, will be reduced by an order of magnitude over a period of about a year. By contrast, the mobile domain rapidly responds to flushing, and a low average nitrate concentration can be maintained if the nitrate is removed as soon as it enters the mobile domain. A field-scale experiment in which the aquifer was flushed with acidic solution confirmed our understanding of the system. For the ongoing experiments on microbial U(VI) reduction, nitrate concentrations must be low in the mobile domain to ensure U(VI) reducing conditions. We therefore conclude that the nitrate leaching out of the immobile pore space must continuously be removed by in situ denitrification to maintain favorable conditions.     

Numerical simulation of a steam-injection pilot study for a PCP-contaminated aquifer

The following study was focused on the simulation of a steam-injection field pilottest conducted in our past research. The scope of research contained two main subjects: heat transfer and contaminant transport when steam was injected into a pentachlorophenol (PCP)-contaminated aquifer. Numerical simulation of the heat transfer during the field test showed that vertical permeability is more influential to the distribution of water temperature than the horizontal permeability. If the vertical permeability is relatively high, the steam in the aquifer has a higher tendency to migrate upward and cause the aquifer temperature to rise faster. The simulation results also showed that heat convection is very sensitive to the soil permeability. Therefore, high permeability media makes the effect of heat convection more important on applying the steam-injection method. Heat conduction dominates the heat transfer within the hot aqueous zone. However, the hot aqueous zone is relatively smaller than the steam zone when steam is injected into the aquifer. Therefore, heat conduction is not as important as heat convection within the steam zone, which is the same result observed in the field test. Specific heat of soil media is also a sensitive factor. A numerical simulator, T2VOC, was utilized to simulate the PCP transport in the aquifer when steam was injected into the aquifer. The results showed that the shape of PCP distribution was identical to that of steam. It illustrated thatthe steam carried PCP upward and laterally. The high vertical soil permeability causes the steam to migrate upward with PCP easily. A low partitioning coefficient allows PCP to be desorbed easier, also an important factor. A majority of the PCP in the soil was transferred to the aqueous phase as the water temperature increased, showing similar results to those observed in the field test. According to the sensitivity analysis, PCP transport is more sensitive to the vertical permeability than the partitioning coefficient. The steam-injection rate is also an important operation parameter and may determine the success of the remediation work.     

Geochemical cycling of arsenic in a coastal aquifer

Biogeochemically modified pore waters from subterranean estuaries, defined as the mixing zone between freshwater and saltwater in a coastal aquifer, are transported to coastal waters through submarine groundwater discharge (SGD). SGD has been shown to impact coastal and perhaps global trace metal budgets. The focus of this study was to investigate the biogeochemical processes that control arsenic cycling in subterranean estuaries. Total dissolved As, as well as a suite of other trace metals and nutrients, were measured in a series of wells and sediment cores at the head of Waquoit Bay, MA. Dissolved As ranged from below detection to 9.5 microg/kg, and was associated with plumes of dissolved Fe, Mn, and P in the groundwater. Sedimentary As, ranging from 360 to 7500 microg/kg, was highly correlated with sedimentary Fe, Mn, and P. In addition, amorphous Fe (hydr)oxides were more efficient scavengers of dissolved As than the more crystalline forms of solid-phase Fe. Given that dissolved As in the surface bay water was lower than within the subterranean estuary, our results indicate that the distribution and type of Fe and Mn (hydr)oxides in coastal aquifers exert a major influence on the biogeochemical cycling of As in subterranean estuaries and, ultimately, the fate of groundwater-derived As in marine systems influenced by SGD.     

Fate and origin of 1,2-dichloropropane in an unconfined shallow aquifer

A shallow aquifer with different redox zones overlain by intensive agricultural activity was monitored for the occurrence of 1,2-dichloropropane (DCP) to assess the fate and origin of this pollutant. DCP was detected more frequently in groundwater samples collected in aerobic and nitrate-reducing zones than those collected from iron-reducing zones. Simulated DCP concentrations for groundwater entering an iron-reducing zone were calculated from a fate and transport model that included dispersion, sorption, and hydrolysis but not degradation. Simulated concentrations were well in excess of measured values, suggesting that microbial degradation occurred in the iron-reducing zone. Microcosm experiments were conducted using aquifer samples collected from iron-reducing and aerobic zones to evaluate the potential for microbial degradation of DCP and to explain field observations. Hydrogenolysis of DCP and production of monochlorinated propanes in microcosm experiments occurred only with aquifer materials collected from the iron-reducing zone, and no dechlorination was observed in microcosms established with aquifer materials collected from the aerobic zones. Careful analyses of the DCP/1,2,2-trichloropropane ratios in groundwater indicated that older fumigant formulations were responsible for the high levels of DCP present in this aquifer.     

Cr stable isotopes in Snake River Plain aquifer groundwater: evidence for natural reduction of dissolved Cr(VI)

At Idaho National Laboratory, Cr(VI) concentrations in a groundwater plume once exceeded regulatory limits in some monitoring wells but have generally decreased over time. This study used Cr stable isotope measurements to determine if part of this decrease resulted from removal of Cr(VI) via reduction to insoluble Cr(III). Although waters in the study area contain dissolved oxygen, the basalt host rock contains abundant Fe(II) and may contain reducing microenvironments or aerobic microbes that reduce Cr(VI). In some contaminated locations, (53)Cr/(52)Cr ratios are close to that of the contaminant source, indicating a lack of Cr(VI) reduction. In other locations, ratios are elevated. Part of this shift may be caused by mixing with natural background Cr(VI), which is present at low concentrations but in some locations has elevated (53)Cr/(52)Cr. Some contaminated wells have (53)Cr/(52)Cr ratios greater than the maximum attainable by mixing between the inferred contaminant and the range of natural background observed in several uncontaminated wells, suggesting that Cr(VI) reduction has occurred. Definitive proof of reduction would require additional evidence. Depth profiles of (53)Cr/(52)Cr suggest that reduction occurs immediately below the water table, where basalts are likely least weathered and most reactive, and is weak or nonexistent at greater depth.     

Genetic evidence for a role of Saccharomyces cerevisiae Mph1 in recombinational DNA repair under replicative stress

In yeast as in human, DNA helicases play critical roles in assisting replication fork progression. The Saccharomyces cerevisiae MPH1 gene, homologue of human FANCM, has been involved in homologous recombination and DNA repair. We describe a synthetic growth defect of an mph1 deletion if combined with an srs2 deletion that can result—depending on the genetic background—in synthetic lethality. The lethality is suppressed by mutations in homologous recombination (rad51, rad52, rad55, rad57) and in the DNA damage checkpoint (rad9, rad24, rad17). Importantly, rad54 and mph1, epistatic for damage sensitivity, are subadditive for spontaneous mutator phenotype. Therefore, Mph1 could be placed at the Rad51‐mediated strand invasion process, with a function distinct from Rad54. Moreover, siz1 mutation is viable with mph1 and additive for DNA damage sensitivity. mph1 srs2 double mutants, isolated in a background where they are viable, are synergistically sensitive to DNA damage. Moderate overexpression of SGS1 partially suppresses this sensitivity. Finally, we observe an epistatic relationship in terms of sensitivity to camptothecin of mms4 or mus81 to mph1. Overall, our results support a role of Mph1 in assisting replication progression. We propose two models for the resumption of DNA synthesis under replicative stress where Mph1 is placed at the sister chromatid interaction step. Copyright © 2009 John Wiley & Sons, Ltd.     

Use of pretreatment zones and zero-valent iron for the remediation of chloroalkenes in an oxic aquifer

Pretreatment zones (PTZs) composed of sand, 10% zero-valent iron [Fe(0)]/sand, and 10% pyrite (FeS2)/sand were examined for their ability to prolong Fe(0) reactivity in above ground column reactors and a subsurface permeable reactive barrier (PRB). The test site had an acidic, oxic aquifer contaminated with tetrachloroethylene (PCE) and trichloroethylene (TCE). The 10% FeS2 and 10% Fe(0) PTZs removed dissolved oxygen and affected the pH and E(h) in the PTZ. None of the PTZs had any effect on pH or E(h) in the 100% Fe(0) zone. Nitrate and sulfate were removed more quickly in the Fe(0) zones preceded by either the 10% Fe(0) PTZ or 10% FeS2. PCE first-order degradation rate constants (k(obs)) decreased significantly (> 80%) with increasing column pore volumes regardless of the PTZ material used. k(obs) finally leveled off after approximately 1 yr of operation. The column results predict that the PRB will experience a breakthrough of PCE in 3-5 yr and illustrate the importance of incorporating temporal variations in degradation rate constants when designing PRBs.     

Effect of exposure history on microbial herbicide degradation in an aerobic aquifer affected by a point source

The effects of in situ exposure to low concentrations (micrograms per liter) of herbicides on aerobic degradation of herbicides in aquifers were studied by laboratory batch experiments. Aquifer material and groundwater were collected from a point source with known exposure histories to the herbicides mecoprop (MCPP), dichlorprop, BAM, bentazone, isoproturon, and DNOC. Degradation of the phenoxy acids, mecoprop and dichlorprop, was observed in five of six sampling points from within the plume. Mecoprop was mineralized, and up to 70% was recovered as 14CO2. DNOC was degraded in only two of six sampling points from within the plume, and neither BAM, bentazone, nor isoproturon was degraded in any sampling point. A linear correlation (R2 > or = 0.83) between pre-exposure and amount of herbicide degraded within 50 days was observed for the phenoxy acids, mecoprop and dichlorprop. An improved model fit was obtained from using Monod degradation kinetics compared to zero- and first-order degradation kinetics. An exponential correlation (R2 > or = 0.85) was also found between numbers of specific phenoxy acid degrading bacteria and pre-exposure. Combination of these results strongly indicates that the low concentration exposure to phenoxy acids in the aquifer resulted in the presence of acclimated microbial communities, illustrated bythe elevated numbers of specific degraders as well as the enhanced degradation capability. The findings support application of natural attenuation to remediate aerobic aquifers contaminated by phenoxy acids from point sources.     

Genetic/genomic evidence for a key role of polarized endocytosis in filamentous differentiation of S. cerevisiae

Unicellular S. cerevisiae cells switch from the yeast form to pseudohyphal or filamentous form in response to environmental cues. We report that wild-type BY diploids (in which yeast ORFs have been systematically deleted) undergo normal HU-induced filamentous growth and discernable nitrogen starvation-induced filamentous growth, despite their perceived filamentation-deficient S288C genetic background. This finding allowed us to perform a genome-wide survey for non-essential genes that are required for filamentous growth with the homozygous deletion strains. We report that genes involved in endocytosis are required for both HU-induced and nitrogen starvation-induced filamentous growth. Surprisingly, no known genes involved in exocytosis are required. Despite the fact that polarized growth involves transport of vesicles to the site of growth, we failed to obtain genetic/genomic evidence that exocytosis plays an essential role in filamentous growth. A possible key role of polarized endocytosis (from the growth tip) is consistent with the proposed biological function of filamentous growth as a foraging behaviour. In addition, BUD8 that encodes the distal landmark in yeast-form bipolar budding is required for nitrogen starvation-induced but not HU-induced filamentous growth. Moreover, BUD5, SPA2, PEA2 and BUD6 that regulate bipolar bud site selection do not regulate the unipolar distal budding pattern in HU-induced filamentous growth.     

Pilot-scale demonstration of cyclodextrin as a solubility-enhancement agent for remediation of a tetrachloroethene-contaminated aquifer

The limitations associated with conventional pump and treat technology have generated interest in using enhanced in-situ flushing as an alternative for remediating source zones contaminated with immiscible liquid. This research investigates the effectiveness of cyclodextrin as a solubility-enhancement agent to enhance the removal of tetrachloroethene (PCE) from a physically isolated section of an aquifer. An important component of this project was the implementation of reagent recovery and reuse. This field experiment presented the rare opportunity, under strict regulatory guidance, to inject PCE into the surficial aquifer cell created with two sets of sheet piles driven into an underlying clay unit. The well-controlled conditions specific to this experiment allowed quantification of mass balances, which is problematic for many contaminated field sites. The fact that mass balances can be obtained provides the ability to determine remediation effectiveness with unusual accuracy for a field project. The saturated zone within the test cell was flushed with a 15 wt % cyclodextrin solution. The cyclodextrin solution increased the aqueous concentration of PCE in the extraction-well effluent to as much as 22 times the concentrations obtained during the water flush conducted prior to the complexing sugar flush (CSF). The seven pore-volume CSF removed the equivalent of approximately 33 L of PCE from the subsurface. This equates to 48% of the total initial mass, based on the volume of PCE present prior to the CSF (68.6 L). Conversely, the seven pore-volume water flush conducted prior to the CSF removed the equivalent of 2.7 L of PCE. The use of cyclodextrin as a flushing agent, especially in a recycling configuration, appears to hold promise for successful remediation of chlorinated-solvent-contaminated source zones.     

Visualization of mixing processes in a heterogeneous sand box aquifer

Mixing is increasingly recognized as a critical process for understanding and modeling reactive transport. Yet, mixing is hard to characterize because it depends nonlinearly on concentrations. Visualization of optical tracers in the laboratory at high spatial and temporal resolution can help advance the study of mixing processes. The solute distribution is obtained by analyzing the relationship between pixel intensity and tracer concentration. The problem with such techniques is that grain borders, light fluctuations, and nonuniform brightness contribute to produce noisy images of concentrations that cannot be directly used to estimate mixing at the local scale. We present a nonparametric regression methodology to visualize local values of mixing from noisy images of optical tracers that minimizes smoothing in the direction of concentration gradients. This is achieved by weighting pixel data along concentration isolines. The methodology is used to provide a full visualization of mixing dynamics in a tracer experiment performed in a reconstructed aquifer consisting of two materials with contrasting hydraulic properties. The experiment reveals that mixing is largest at the contact area of regions with different permeability. Also, the temporal evolutions of mixing and dilution rates are significantly different. The mixing rate is more persistent than the dilution rate during tracer invasion, and the opposite is true during flushing, which helps in understanding the complementary nature of these two measures.     

Sources of sulfate supporting anaerobic metabolism in a contaminated aquifer

Field and laboratory techniques were used to identify the biogeochemical factors affecting sulfate reduction in a shallow, unconsolidated alluvial aquifer contaminated with landfill leachate. Depth profiles of 35S-sulfate reduction rates in aquifer sediments were positively correlated with the concentration of dissolved sulfate. Manipulation of the sulfate concentration in samples revealed a Michaelis-Menten-like relationship with an apparent Km and Vmax of approximately 80 and 0.83 microM SO4(-2) x day(-1), respectively. The concentration of sulfate in the core of the leachate plume was well below 20 microM and coincided with very low reduction rates. Thus, the concentration and availability of this anion could limit in situ sulfate-reducing activity. Three sulfate sources were identified, including iron sulfide oxidation, barite dissolution, and advective flux of sulfate. The relative importance of these sources varied with depth in the alluvium. The relatively high concentration of dissolved sulfate at the water table is attributed to the microbial oxidation of iron sulfides in response to fluctuations of the water table. At intermediate depths, barite dissolves in undersaturated pore water containing relatively high concentrations of dissolved barium (approximately 100 microM) and low concentrations of sulfate. Dissolution is consistent with the surface texture of detrital barite grains in contact with leachate. Laboratory incubations of unamended and barite-amended aquifer slurries supported the field observation of increasing concentrations of barium in solution when sulfate reached low levels. At a deeper highly permeable interval just above the confining bottom layer of the aquifer, sulfate reduction rates were markedly higher than rates at intermediate depths. Sulfate is supplied to this deeper zone by advection of uncontaminated groundwater beneath the landfill. The measured rates of sulfate reduction in the aquifer also correlated with the abundance of accumulated iron sulfide in this zone. This suggests that the current and past distributions of sulfate-reducing activity are similar and that the supply of sulfate has been sustained at these sites.     

Importance of adsorption (hole-filling) mechanism for hydrophobic organic contaminants on an aquifer kerogen isolate

Sorption and desorption behaviors of four hydrophobic organic compounds (HOCs) were investigated for an isolated kerogen material from Borden aquifer material with total organic carbon of 0.021%. The solubility-normalized modified Freundlich equation and the combined linear and Polanyi-Dubinin (PD) equation can quite well describe the sorption or desorption isotherms. The partition component is estimated and compared using desorption data, dual-mode modeling, and the reported partition coefficients. The result suggests that the dual-mode modeling and the combined linear and PD modeling may overestimate the partitioning component. The partition component is not so important as assumed before in sorption of HOCs for the studied sorbent. As the fitted PD equation has an exponent parameter b' approaching 1, it is equivalent to the modified Freundlich equation. The small molecules 1,2-dichlorobenzene (DCB) and naphthalene (Naph) have higher adsorption volumes. The lower adsorption volumes for 1,3,5-trichlorobenzene (TCB) and phenanthrene (Phen) suggest that accessibility to the holes of kerogen by large HOC molecules is reduced. The desorption hysteresis is approximately constant for DCB when the relative aqueous concentration ranges from 0.0007 to 0.6, but for Phen is only obvious at higher relative aqueous concentrations. The varied sorption and desorption behaviors for DCB and Phen are satisfactorily explained by an adsorption/ hole filling mechanism and entrapment of some adsorbates in the kerogen matrix and by possible pore deformation mechanism at high concentrations.     

Optimization of surfactant-enhanced aquifer remediation for a laboratory BTEX system under parameter uncertainty

This study develops a nonlinear chance-constrained programming (NCCP) model for optimizing surfactant-enhanced aquifer remediation (SEAR) processes. The model can not only address the parameter uncertainty, but provide a reliability level for the identified optimal remediation strategy. To solve the NCCP model, stepwise cluster analysis (SCA) is used to create a set of proxy simulators for quantifying the relationships between operating conditions (i.e., pumping rate) and probabilities of benzene levels in violation of standard. Compared to conventional parametric inference techniques, SCA is independent of prior assumptions for model forms (e.g., linear or exponential ones) and capable of reflecting complex nonlinear relationships between operating conditions and probabilities. To alleviate the computational efforts in the optimization process, the generated proxy simulators are repeatedly called by simulated annealing (SA) to test the feasibility of each potential solution. The implicit of the optimal NCCP solutions is discussed through a laboratory-scale SEAR system where porosity and intrinsic permeability are treated as stochastic parameters. It is observed that well locations, environmental standards, reliability levels and remediation durations would have significant effects on optimal SEAR strategies. By comparing the predicted benzene concentration without and with remediation actions, it is indicated that the optimal SEAR process can guarantee the benzene concentration to meet the environmental standard with a high reliability level.