Evaluating the impact of back diffusion on groundwater cleanup time.

Back diffusion of groundwater contaminants from low permeability (K) zones can be a major factor controlling the time to reach cleanup goals in downgradient monitor wells. We identify the aquifer and contaminant characteristics that have the greatest influence on the time (TOoM) after complete source removal for contaminant concentrations to decline by 1, 2 and 3 Orders-of-Magnitude (T1, T2 and T3). Two aquifer configurations are evaluated: (a) layered geometry (LG) with finite thickness low K layers; and (b) boundary geometry (BG) with thick semi-infinite low K boundaries. A semi-analytical modeling approach (Muskus and Falta, 2018) is used to simulate the concentration decline following source removal for a range of conditions and generate ≈21,000 independent values of T1, T2 and T3. Linear regression is applied to interpret this large dataset and develop simple relationships to estimate TOoM from three characteristic parameters - the mass residence time (TM), diffusion time (TD), and ratio of low K to high K mass storage (γ). TM is most important predictor of T1, T2 and T3 for both geometries and is equal to the combined high and low K contaminant mass divided by the mass flux, at the end of the loading period (TL). For LG, T3 is strongly influenced by TD = RLLD2/(4D*), where RL is the low K retardation factor, LD is the half-thickness of the embedded low K layers, and D* is the effective diffusion coefficient. For BG, T3 is strongly influenced by γ. Contaminant decay in low K zones can significantly reduce cleanup times when λLTD > 0.01, where λL is the effective first order decay rate in the low K zone. The 1st Damköhler (Da), equal to TM/TD, provides a useful indicator of the relative importance of back diffusion on TOoM. Back diffusion impacts are greatest on T3 when 0.01 > Da > 0.1, then decrease with increasing Da. Back diffusion has less impacts on T2, with limited influence on T1. The results are summarized in a simple conceptual model to aid in evaluating the impact of back diffusion on the time for concentrations to decline by 1-3 OoM.

A Physically Based Approach for Estimating Hydraulic Conductivity from HPT Pressure and Flowrate.

The hydraulic profiling tool (HPT) is widely used to generate profiles of relative permeability vs. depth. In this work, prior numerical modeling results are used to develop a relationship between probe advance rate V (cm/s), probe diameter D (cm), water injection rate Q (mL/min), corrected pressure Pc (psi), and hydraulic conductivity K (feet/d) [Formula: see text] where E is an empirically derived hydraulic efficiency factor. The relationship is validated by 23 HPT profiles that, after averaging K vertically, were similar to slug test results in adjoining monitoring wells. The best fit value of E for these profiles was 2.02. This equation provides a physically based approach for generating hydraulic conductivity profiles with HPT tooling.

Enhanced reductive dechlorination of trichloroethene in an acidic DNAPL impacted aquifer.

A field pilot test was conducted using an emulsified vegetable oil (EVO) and colloidal magnesium hydroxide [Mg(OH)2] formulation to enhance reductive dechlorination of dense non-aqueous phase liquid (DNAPL) trichloroethene (TCE) in an acidic (pH < 4), heterogeneous aquifer. The field test consisted of i) a single well injection test to evaluate Mg(OH)2 distribution and ii) installation of two EVO-Mg(OH)2 permeable reactive barriers (PRBs; PRB-1 & PRB-2) at varying distances downgradient of the DNAPL source area. Distribution of Mg(OH)2 was observed up to 2.3 m away from the injection point within a permeable coarse sand layer; however, Mg(OH)2 transport in the overlying clayey-silty sand was minimal. Downgradient of the PRBs, colloidal Mg(OH)2 increased the pH of the coarse sand to levels appropriate for biological reductive dechlorination (pH >∼5); however, some settling of Mg(OH)2 in the injection wells generated persistent high pH (∼9-10) within the PRBs. A redesigned suspension of colloidal Mg(OH)2 was tested and proved to be more effective at raising aquifer pH without an excessive rise in pH within the PRBs. At PRB-1 (located closest to the DNAPL source area), limited TCE biodegradation was observed due to the influx of high TCE concentrations (up to 400 mg/L) and inhibition of dechlorinating bacteria. At PRB-2 (located 25 m downgradient of the DNAPL source area), TCE concentrations were much lower (13-26 mg/L) and production of cis-1,2-dichloroethene (cDCE) and some vinyl chloride (VC) was observed. Subsequent bioaugmentation with a commercial dechlorinating culture at PRB-2 improved conversion of cDCE to VC and ethene at downgradient monitoring wells over the duration of the study. These results emphasize the importance of PRB location (relative to the DNAPL source), base selection for pH adjustment, source strength, and local heterogeneities for the design and long-term performance of ERD in acidic DNAPL-impacted aquifers.

Simulation Assessment of Direct Push Injection Logging for High-Resolution Aquifer Characterization.

Direct push injection logging (DPIL) has become one of the most widely used approaches for obtaining vertical profiles of hydraulic conductivity (K) in environmental site investigations. Despite its widespread use, however, there has been no rigorous analysis of the underlying physical processes that take place during DPIL or how the approach would perform under different hydrogeological and operating conditions. We address these issues through a series of numerical simulations. Results show that the ratio of DPIL injection rate over pressure can be used for direct determination of K when K is >10-6  m/s. When K is <10-6  m/s and specific storage (Ss) is >10-3 /m, the ratio becomes increasingly sensitive to Ss; in that case, additional information on Ss is needed for reliable K estimation. For unconsolidated formations of moderate K or higher, the ratio of injection rate over pressure should provide a reasonable K estimate when Ss is <10-3 /m. Although water injection at previous depths during continuous DPIL has only a small impact on the pressure response measured at the current injection depth, probe advancement can have a significant impact when K and Ss are small. Consequently, in fine-grained materials, the advancement-generated pore water pressure increase can comprise a large portion of the measured pressure response. To diminish the impact of probe advancement in such materials, advancement speed should be kept as low as possible (e.g., 0.5 cm/s).

Laboratory Column Evaluation of High Explosives Attenuation in Grenade Range Soils.

High explosives (HEs) deposited on military ranges can leach through the soil and contaminate groundwater. We examined the transport and fate of HEs in laboratory columns containing soils from two hand grenade bays (Bays C and T) and the impact of organic amendments on biodegradation. Soil characteristics were similar; however, Bay C had somewhat higher clay and organic C. Experimental treatments included addition of crude glycerin and lignosulfonate, and parallel control columns. Experimental results showed extensive 2,4,6-trinitrotoluene (TNT) degradation with minimal leaching, consistent with prior batch microcosm results. Amendment addition enhanced TNT degradation in both Bays C and T compared with controls. Although hexahydro-1,3,5-trinitro-1,3,5-triazine (Royal Demolition Explosive, or RDX) did not biodegrade in prior aerobic batch microcosms, 64 to 77% of RDX biodegraded in untreated soil columns with O present in the mobile soil gas. The RDX biodegradation was likely associated with short-term anoxic conditions or anoxic micro-niches. In nearly saturated Bay C columns, RDX removal increased to >92%. Amendment addition to unsaturated Bay T columns increased RDX removal to >86%. In one column, the soil remained anoxic (O < 5% by volume) for about a year after amendment addition, significantly reducing RDX leaching. Nitroso degradation products were produced equivalent to 9 to 39% of the RDX degraded, with most retained in the soil (9-37%) and 0 to 3% in the effluent. These results demonstrate that RDX biodegradation can occur in soils with measurable O, and that amendment addition can reduce RDX leaching by stimulating anaerobic biodegradation.

Natural and Enhanced Attenuation of Explosives on a Hand Grenade Range.

2,4,6-Trinitrotoluene (TNT) and hexahydro-1,3,5-trinitro-1,3,5-triazine (Royal Demolition Explosive, or RDX) deposited on hand grenade training ranges can leach through the soil and impact shallow groundwater. A 27-mo field monitoring project was conducted to evaluate the transport and attenuation of high explosives in variably saturated soils at an active grenade range located at Fort Bragg, NC. Two approaches were evaluated: (i) natural attenuation in grenade Bay C; and (ii) enhanced attenuation in Grenade Bay T. There was no evidence of TNT accumulation or leaching in surface soils or pore water in either bay, consistent with parallel laboratory studies showing aerobic and anaerobic biodegradation of TNT. In the untreated Bay C, the low saturated hydraulic conductivity () combined with high rainfall and warm summer temperatures resulted in reducing conditions (low oxidation-reduction potential), an increase in dissolved Mn, and a rapid decline in nitrate and RDX. In Bay T, the somewhat greater and lower soil organic C level resulted in more oxidizing conditions with greater RDX leaching. A single-spray application of glycerin and lignosulfonate to the soil surface in Bay T was effective in generating reducing conditions and stimulating RDX biodegradation for ∼1 yr.

Impact of glycerin and lignosulfonate on biodegradation of high explosives in soil.

Soil microcosms were constructed and monitored to evaluate the impact of substrate addition and transient aerobic and anaerobic conditions on TNT, RDX and HMX biodegradation in grenade range soils. While TNT was rapidly biodegraded under both aerobic and anaerobic conditions with and without organic substrate, substantial biodegradation of RDX, HMX, and RDX daughter products was not observed under aerobic conditions. However, RDX and HMX were significantly biodegraded under anaerobic conditions, without accumulation of TNT or RDX daughter products (2-ADNT, 4-ADNT, MNX, DNX, and TNX). In separate microcosms containing grenade range soil, glycerin and lignosulfonate addition enhanced oxygen consumption, increasing the consumption rate >200% compared to untreated soils. Mathematical model simulations indicate that oxygen consumption rates of 5 to 20g/m3/d can be achieved with reasonable amendment loading rates. These results indicate that glycerin and lignosulfonate can be potentially used to stimulate RDX and HMX biodegradation by increasing oxygen consumption rates in soil.

Perchlorate natural attenuation in a riparian zone.

Multiple lines of evidence were used to document the natural attenuation of perchlorate in a shallow alluvial aquifer. In the upgradient, aerobic portion of the aquifer, perchlorate did not biodegrade. However, natural flushing by groundwater flow is reducing perchlorate concentrations in the aquifer over time. Perchlorate concentrations in the source area are expected to meet cleanup criteria in 11 to 27 years without active remedial measures. At the distal end of the plume, perchlorate is rapidly degraded as it migrates upward through organic rich littoral zone sediments. Apparent first-order degradation rates in groundwater were about 0.20 d(-1) and are consistent with laboratory macrocosm rates (0.12 d(-1)). qPCR results show a distinct region of the littoral zone where perchlorate degraders are elevated. The Eh within this zone varies from +0.1 to +0.3 V indicating perchlorate degraders can thrive in moderately oxidizing conditions. The study has shown that (i) there was no apparent perchlorate biodegradation in aerobic aquifer; (ii) perchlorate declines over time in aerobic aquifer due to flushing; (iii) there was a rapid perchlorate attenuation in organic rich littoral zone; and, (iv) qPCR results show large increases in perchlorate degraders in the littoral zone.

Enhanced reductive dechlorination of tetrachloroethene dense nonaqueous phase liquid with EVO and Mg(OH)2.

In situ treatment of dense nonaqueous phase liquids (DNAPL) by enhanced reductive dechlorination (ERD) can be limited by contaminant toxicity, low pH, and challenges in effectively delivering electron donor. Flushing emulsified vegetable oil (EVO), colloidal Mg(OH)2 buffer, and a bioaugmentation culture (BC) through a zone containing neat tetrachloroethene (PCE) was effective in reducing contaminant toxicity, limiting pH declines, and accelerating bioenhanced dissolution of the DNAPL. In the effluent of porous media columns with little fine material, PCE concentrations reached a maximum of 40-50 times PCE aqueous solubility in water, demonstrating NAPL PCE was distributed throughout the 1.5 m column length. In a column treated with only EVO+BC, reductive dechlorination was limited. However, a single injection of EVO+Mg(OH)2+BC was effective in reducing PCE to below detection for over 400 days with a large increase in Cl(-) and dichloroethene (DCE), accelerating bioenhanced DNAPL dissolution. Dechlorination rates gradually increased over time with the rate of total ethene (TE) release from the Mg(OH)2+EVO+BC column reaching 5-6 times the TE release rate from the EVO+BC column. The accelerated dechlorination was likely due to both Mg(OH)2 addition which limited pH declines from HCl, volatile fatty acids (VFAs), and inorganic carbon (IC) production, and formation of a mixed PCE-vegetable oil NAPL which provided a readily accessible electron donor, resulting in rapid PCE degradation with reduced PCE toxicity.

Impact of injection system design on ISCO performance with permanganate--mathematical modeling results.

In situ chemical oxidation (ISCO) using permanganate (MnO(4)(-)) can be a very effective technique for remediation of soil and groundwater contaminated with chlorinated solvents. However, many ISCO projects are less effective than desired because of poor delivery of the chemical reagents to the treatment zone. In this work, the numerical model RT3D was modified and applied to evaluate the effect of aquifer characteristics and injection system design on contact and treatment efficiency. MnO(4)(-) consumption was simulated assuming the natural oxidant demand (NOD) is composed of a fraction that reacts instantaneously and a fraction that slowly reacts following a 2nd order relationship where NOD consumption rate increases with increasing MnO(4)(-) concentration. MnO(4)(-) consumption by the contaminant was simulated as an instantaneous reaction. Simulation results indicate that the mass of permanganate and volume of water injected has the greatest impact on aquifer contact efficiency and contaminant treatment efficiency. Several small injection events are not expected to increase contact efficiency compared to a single large injection event, and can increase the amount of un-reacted MnO(4)(-) released down-gradient. High groundwater flow velocities can increase the fraction of aquifer contacted. Initial contaminant concentration and contaminant retardation factor have only a minor impact on volume contact efficiency. Aquifer heterogeneity can have both positive and negative impacts on remediation system performance, depending on the injection system design.

Hyaluronic acid hydrogel sustains the delivery of dexamethasone across the round window membrane.

BACKGROUND: The use of intratympanic (IT) steroids for the treatment of inner ear disorders is promising, but the clinical challenges of prolonged middle ear drug application have proven burdensome, and a sustainable delivery system is yet to be developed. METHOD: In this study, a guinea pig model was used to determine if dexamethasone in combination with a hyaluronic-acid (HA)-based hydrogel is an efficient, stable and sustainable dexamethasone delivery system to the inner ear. For each animal, right and left middle ear bullae were randomly selected to be filled with dexamethasone alone or dexamethasone-HA (Dex-HA) gel. Perilymph samples were collected at different time points and dexamethasone levels were determined using an ELISA. RESULTS: Dexamethasone was measurable in the perilymph samples up to 72 h after treatment. At 24 h after treatment, the perilymph dexamethasone concentrations were significantly higher (p = 0.01) in the ears treated with Dex-HA gel than in those treated with dexamethasone alone. While the perilymph dexamethasone concentration had decreased at 48 h after treatment with Dex-HA gel, the levels were still higher than those observed at 24 h in ears treated with dexamethasone alone. A high variability in dexamethasone concentration was observed between the samples, and the variability between matched ears receiving different treatments was remarkably lower than the variability within each treatment group, suggesting that individual parameters might play a major role in perilymph dexamethasone concentration. There was no statistically significant correlation between dexamethasone concentration and sex, weight or laterality. CONCLUSIONS: Our results show that the Dex-HA gel used in this study provides an effective and sustained dexamethasone release mechanism that might be utilized to treat conditions such as sudden sensorineural hearing loss. This could potentially reduce the morbidity and costs associated with IT treatment.

Numerical modeling of emulsified oil distribution in heterogeneous aquifers.

In situ anaerobic bioremediation using edible oil emulsions will be most effective if the oil droplets can be brought into close contact with the contaminant to be treated. However, uniformly distributing oil in heterogeneous aquifers can be difficult. The impact of injection conditions on emulsion distribution in a three-dimensional heterogeneous aquifer is examined using MODFLOW and RT3D. Emulsion retention is simulated using a rate-limited Langmuir isotherm. Volume and flow contact efficiency are shown to be functions of mass of oil injected, injection fluid volume, well spacing, and injection sequence. Regression equations are developed relating dimensionless scaling factors to expected contact efficiency for area treatment and barriers. Cleanup time for uncontacted zones is estimated using a mobile-immobile zone modeling approach.

Effective distribution of emulsified edible oil for enhanced anaerobic bioremediation.

Recent laboratory and field studies have shown that injection of emulsified edible oils can provide an effective, low-cost alternative for stimulating anaerobic biodegradation processes. A pilot-scale permeable reactive bio-barrier (PRBB) was installed at a perchlorate and chlorinated solvent impacted site by injecting 380 L of commercially available emulsion (EOS) containing emulsified soybean oil, food-grade surfactants, lactate, and yeast extract through ten direct push injection wells over a two day period. Soil cores collected six months after emulsion injection indicate the oil was distributed up to 5 m downgradient of the injection wells. A previously developed emulsion transport model was used to simulate emulsion transport and retention using independently estimated model parameters. While there was considerable variability in the soil sampling results, the model simulations generally agreed with the observed oil distribution at the field site. Model sensitivity analyses indicate that increasing the injection flow rate or diluting the oil with more water will have little effect on final oil distribution in the aquifer. The only effective approach for enhancing the spread of emulsified oil away from the injection well appears to be injecting a greater mass of oil.

Concurrent bioremediation of perchlorate and 1,1,1-trichloroethane in an emulsified oil barrier.

A detailed field pilot test was conducted to evaluate the use of edible oil emulsions for enhanced in situ biodegradation of perchlorate and chlorinated solvents in groundwater. Edible oil substrate (EOS) was injected into a line of ten direct push injection wells over a 2-day period to form a 15-m-long biologically active permeable reactive barrier (bio-barrier). Field monitoring results over a 2.5-year period indicate the oil injection generated strongly reducing conditions in the oil-treated zone with depletion of dissolved oxygen, nitrate, and sulfate, and increases in dissolved iron, manganese and methane. Perchlorate was degraded from 3100 to 20,000 microg/L to below detection (<4 microg/L) in the injection and nearby monitor wells within 5 days following the injection. Two years after the single emulsion injection, perchlorate was less than 6 microg/L in every downgradient well compared to an average upgradient concentration of 13,100 microg/L. Immediately after emulsion injection, there were large shifts in concentrations of chlorinated solvents and degradation products due to injection of clean water, sorption to the oil and adaptation of the in situ microbial community. Approximately 4 months after emulsion injection, concentrations of 1,1,1-trichloroethane (TCA), perchloroethene (PCE), trichloroethene (TCE) and their degradation products appeared to reach a quasi steady-state condition. During the period from 4 to 18 months, TCA was reduced from 30-70 microM to 0.2-4 microM during passage through the bio-barrier. However, 1-9 microM 1,1-dichloroethane (DCA) and 8-14 microM of chloroethane (CA) remained indicating significant amounts of incompletely degraded TCA were discharging from the oil-treated zone. During this same period, PCE and TCE were reduced with concurrent production of 1,2-cis-dichloroethene (cis-DCE). However, very little VC or ethene was produced indicating reductive dechlorination slowed or stopped at cis-DCE. The incomplete removal of TCA, PCE and TCE is likely associated with the short (5-20 days) hydraulic retention time of contaminants in the oil-treated zone. The permeability of the injection wells declined by 39-91% (average=68%) presumably due to biomass growth and/or gas production. However, non-reactive tracer tests and detailed monitoring of the perchlorate plume demonstrated that the permeability loss did not result in excessive flow bypassing around the bio-barrier. Contaminant transport and degradation within the bio-barrier was simulated using an advection-dispersion-reaction model where biodegradation rate was assumed to be linearly proportional to the residual oil concentration (Soil) and the contaminant concentration. Using this approach, the calibrated model was able to closely match the observed contaminant distribution. The calibrated model was then used to design a full-scale barrier to treat both ClO4 and chlorinated solvents.

Enhanced reductive dechlorination in columns treated with edible oil emulsion.

The effect of edible oil emulsion treatment on enhanced reductive dechlorination was evaluated in a 14 month laboratory column study. Experimental treatments included: (1) emulsified soybean oil and dilute HCl to inhibit biological activity; (2) emulsified oil only; (3) emulsified oil and anaerobic digester sludge; and (4) continuously feeding soluble substrate. A single application of emulsified oil was effective in generating strongly reducing, anaerobic conditions for over 14 months. PCE was rapidly reduced to cis-DCE in all three live columns. Bioaugmentation with a halorespiring enrichment culture resulted in complete dechlorination of PCE to ethene in the soluble substrate column (yeast extract and lactate). However, an additional treatment with a pulse of yeast extract and bioaugmentation culture was required to stimulate complete dechlorination in the emulsion treated columns. Once the dechlorinating population was established, the emulsion only column degraded PCE from 90-120 microM to below detection with concurrent ethene production in a 33 day contact time. The lower biodegradation rates in the emulsion treated columns compared to the soluble substrate column suggest that emulsified oil barriers may require a somewhat longer contact time for effective treatment. In the HCl inhibited column, partitioning of PCE to the retained oil substantially delayed PCE breakthrough. However, reduction of PCE to more soluble degradation products (cis-DCE, VC and ethene) greatly reduced the impact of oil-water partitioning in live columns. There was only a small decline in the hydraulic conductivity (K) of column #1 (low pH+emulsion, K(final)/K(initial)=0.57) and column #2 (live+emulsion, K(final)/K(initial)=0.73) indicating emulsion injection did not result in appreciable clogging of the clayey sand. However, K loss was greater in column #3 (sludge+emulsion, K(final)/K(initial)=0.12) and column #4 (soluble substrate, K(final)/K(initial)=0.03) indicating clogging due to biomass and/or gas production can be significant.

Impact of edible oil injection on the permeability of aquifer sands.

Recent laboratory and field studies have shown that food-grade edible oils can be injected into the subsurface for installation of in-situ permeable reactive barriers. However to be effective, the oil must be distributed out away from the oil injection points without excessive permeability loss. In this work, we examine the distribution of soybean oil in representative aquifer sediments as non-aqueous phase liquid oil (NAPL oil) or as an oil-in-water emulsion. Laboratory columns packed with sands or clayey sands were flushed with either NAPL oil or a soybean emulsion followed by plain water, while monitoring permeability loss and the final oil residual saturation. NAPL oil can be injected into coarse-grained sands. However NAPL injection into finer grained sediments requires high injection pressures which may not be feasible at some sites. In addition, NAPL injection results in high oil residual saturations and moderate permeability losses. In contrast, properly prepared emulsions can be distributed through sands with varying clay content without excessive pressure buildup, low oil retention and very low to moderate permeability loss. For effective transport, the emulsion must be stable, the oil droplets must be significantly smaller than the mean pore size of the sediment and the oil droplets should have a low to moderate tendency to stick to each other and the aquifer sediments. In our work, oil retention and associated permeability loss increased with sediment clay content and with the ratio of droplet size to pore size. For sandy sediments, the permeability loss is modest (0-40% loss) and is proportional to the oil residual saturation.

MTBE and aromatic hydrocarbons in North Carolina stormwater runoff.

A total of 249 stormwater samples were collected from 46 different sampling locations in North Carolina over an approximate 1-year period and analyzed to identify land use types where fuel oxygenates and aromatic hydrocarbons may be present in higher concentrations and at greater frequency. Samples were analyzed by gas chromatography-mass spectrometry in ion selective mode to achieve a quantitation limit of 0.05 microg/l. m-,p-Xylene and toluene were detected in over half of all samples analyzed, followed by MTBE: o-xylene: 1,3,5-trimethylbenzene: ethylbenzene; and 1,2,4-trimethylbenzene. Benzene, DIPE, TAME and 1,2,3-trimethylbenzene were detected in < 10% of the samples analyzed. Median contaminant concentrations (when detected) varied from 0.07 microg/l for ethylbenzene to 0.11 microg/l for toluene. All of the locations with significantly higher contaminant concentrations were associated with direct runoff from a gas station or discharge of contaminated groundwater from a former leaking underground storage tank. For all of the aromatic hydrocarbons, the maximum observed contaminant concentrations were over an order of magnitude lower than current drinking water standards.