Effect of soil texture on surfactant-based remediation of hydrophobic organic-contaminated soil

Surfactants may be used in remediation of subsoil and aquifer contaminated with hydrophobic compounds. The objectives of this study were to examine the effect of soil texture on hydrophobic organic contaminant (HOC; toluene, or 1,2,4-trichlorobenzene [TCB]) removal from six soils and to evaluate the optimal composition of soil texture for maximum HOC removal using aqueous surfactant solution. Selected surfactants were 4% (vol/vol) sodium diphenyl oxide disulfonate (DOSL) and 4% (wt/vol) sodium lauryl sulfate (LS). Toluene and TCB were selected as the lighter-than-water nonaqueous phase liquid (LNAPL) and denser-than-water nonaqueous phase liquid (DNAPL) model substances, respectively. Soil types used for this study were Ottawa sand and five Iowa soils (Fruitfield, Keomah, Crippin, Webster, and Galvar). The greatest recovery of toluene and TCB in batch tests was 73% and 84%, respectively, which was obtained with DOSL surfactant in Ottawa sand. The toluene removal of 95% in column tests has been achieved in the Ottawa sand and three Iowa soils (Fruitfield, Keomah, Crippin) with DOSL after effluent volume of 3750 ml (about 32 pore volume) passed. TCB removal of 98% in column tests has been achieved in Ottawa sand and three Iowa soils (Fruitfield, Keomah, Crippin) with DOSL after effluent volume of 2500 ml (about 21 pore volume) passed. These results were related with soil texture (clay content 30%), clay mineralogy (kaolinite and smectite), as a function of transported pore volume.     

Public and occupational risks of the Nevada (USA) Test Site

The Nevada Test Site (NTS), north of Las Vegas, was the scene of hundreds of nuclear weapons tests over four decades, both above- and belowground. There is considerable interest, both in neighboring communities and elsewhere, in the risks it poses. Overall, the greatest risks are nonradioactive in origin, with occupational risks to employees and accident risks in transporting low-level nuclear wastes to the NTS from other Department of Energy (DOE) sites ranking highest. For radiation risks, that to workers handling radioactive materials is much higher than that to the surrounding population, either present or future. Overall, annual risks are small, with all fatalities approximately 0.008% of total Nevada deaths. At the NTS, the government spends about 5000 times more on radiation as opposed to nonradiation deaths. This suggests that at least some resources may be misallocated towards cleanup of public risks and that the occupational risk of cleanup may be much higher than the public risk. Thus risk may be multiplied by well-meaning programs.     

Integrating long-term stewardship goals into the remediation process: natural resource damages and the Department of Energy

The United States and other developed countries are faced with restoring and managing degraded ecosystems. Evaluations of the degradation of ecological resources can be used for determining ecological risk, making remediation or restoration decisions, aiding stakeholders with future land use decisions, and assessing natural resource damages. Department of Energy (DOE) lands provide a useful case study for examining degradation of ecological resources in light of past or present land uses and natural resource damage assessment (NRDA). We suggest that past site history should be incorporated into the cleanup and restoration phase to reduce the ultimate NRDA costs, and hasten resource recovery. The lands that DOE purchased over 50 years ago ranged from relatively undisturbed to heavily impacted farmland, and the impact that occurred from DOE occupation varies from regeneration of natural ecosystems (benefits) to increased exposure to several stressors (negative effects). During the time of the DOE releases, other changes occurred on the lands, including recovery from the disturbance effects of farming, grazing, and residential occupation, and the cessation of human disturbance. Thus, the injury to natural resources that occurred as a result of chemical and radiological releases occurred on top of recovery of already degraded systems. Both spatial (size and dispersion of patch types) and temporal (past/present/future land use and ecological condition) components are critical aspects of resource evaluation, restoration, and NRDA. For many DOE sites, integrating natural resource restoration with remediation to reduce or eliminate the need for NRDA could be a win-win situation for both responsible parties and natural resource trustees by eliminating costly NRDAs by both sides, and by restoring natural resources to a level that satisfies the trustees, while being cost-effective for the responsible parties. It requires integration of remediation, restoration, and end-state planning to a greater degree than is currently done at most DOE sites.     

A stochastic-advective transport model for NAPL dissolution and degradation in non-uniform flows in porous media

Remediation schemes for contaminated sites are often evaluated to assess their potential for source zone reduction of mass, or treatment of the contaminant between the source and a control plane (CP) to achieve regulatory limits. In this study, we utilize a stochastic stream tube model to explain the behavior of breakthrough curves (BTCs) across a CP. At the local scale, mass dissolution at the source is combined with an advection model with first-order decay for the dissolved plume. Field-scale averaging is then employed to account for spatial variation in mass within the source zone, and variation in the velocity field. Under the assumption of instantaneous mass transfer from the source to the moving liquid, semi-analytical expressions for the BTC and temporal moments are developed, followed by derivation of expressions for effective velocity, dispersion, and degradation coefficients using the method of moments. It is found that degradation strongly influences the behavior of moments and the effective parameters. While increased heterogeneity in the velocity field results in increased dispersion, degradation causes the center of mass of the plume to shift to earlier times, and reduces the dispersion of the BTC by lowering the concentrations in the tail. Modified definitions of effective parameters are presented for degrading solutes to account for the normalization constant (zeroth moment) that keeps changing with time or distance to the CP. It is shown that anomalous dispersion can result for high degradation rates combined with wide variation in velocity fluctuations. Implications of model results on estimating cleanup times and fulfillment of regulatory limits are discussed. Relating mass removal at the source to flux reductions past a control plane is confounded by many factors. Increased heterogeneity in velocity fields causes mass fluxes past a control plane to persist, however, aggressive remediation between the source and CP can reduce these fluxes.     

Reduction of Cr(VI) by peat and coal humic substances

The reduction of Cr(VI) by humic substances from leonardite and peat was investigated by capillary zone electrophoresis at various pHs. Both humic materials reduced Cr(VI) at pH 5.4, but not at basic pH. The capacity of leonardite humic substances to reduce Cr(VI) was lower than that of peat humic substances. Fe(III) accelerated the reduction of Cr(VI) by peat humic substances, but not by leonardite humic substances. Cr(VI) reduction mechanisms are proposed. The coal humic substances seem more suitable for remediation of Cr(VI)-contaminated sites.     

Effect of soil layering on NAPL removal behavior in soil-heated vapor extraction

Soil heating has been proposed as a method to enhance the vapor extraction of NAPLs from contaminated soils. Three-dimensional fluid flow and heat transfer simulations have been performed for soil-heated vapor extraction to determine the transient system performance for a hypothetical configuration. Soil layering has been considered in evaluation of the initial non-aqueous phase liquid (NAPL) distribution and in evaporation and transport to the vapor extraction location. Results from this layered model are compared with results for a homogeneous system with an initially uniform NAPL, indicating the influence of layering, the initial NAPL distribution, the type of NAPL, and the possibility of enhanced vapor diffusion. Not only is the NAPL removal time reduced significantly with the addition of heat, but the uncertainty in the removal time owing to a number of difficult to characterize in situ factors, such as layering and the initial NAPL distribution, is much less than for standard soil vapor extraction without heating, owing to the rise in temperature and increase in NAPL vapor pressure with time.     

Surfactant enhanced recovery of tetrachloroethylene from a porous medium containing low permeability lenses. 1. Experimental studies

A matrix of batch, column and two-dimensional (2-D) box experiments was conducted to investigate the coupled effects of rate-limited solubilization and layering on the entrapment and subsequent recovery of a representative dense NAPL, tetrachloroethylene (PCE), during surfactant flushing. Batch experiments were performed to determine the equilibrium solubilization capacity of the surfactant, polyoxyethylene (20) sorbitan monooleate (Tween 80), and to measure fluid viscosity, density and interfacial tension. Results of one-dimensional column studies indicated that micellar solubilization of residual PCE was rate-limited at Darcy velocities ranging from 0.8 to 8.2 cm/h and during periods of flow interruption. Effluent concentration data were used to develop effective mass transfer coefficient (Ke) expressions that were dependent upon the Darcy velocity and duration of flow interruption. To simulate subsurface heterogeneity, 2-D boxes were packed with layers of F-70 Ottawa sand and Wurtsmith aquifer material within 20-30 mesh Ottawa sand. A 4% Tween 80 solution was then flushed through PCE-contaminated boxes at several flow velocities, with periods of flow interruption. Effluent concentration data and visual observations indicated that both rate-limited solubilization and pooling of PCE above the fine layers reduced PCE recovery to levels below those anticipated from batch and column measurements. These experimental results demonstrate the potential impact of both mass transfer limitations and subsurface layering on the recovery of PCE during surfactant enhanced aquifer remediation.     

A theoretical model of air and steam co-injection to prevent the downward migration of DNAPLs during steam-enhanced extraction

When steam is injected into soil containing a dense volatile non-aqueous phase liquid contaminant the DNAPL vaporized within the heated soil region condenses and accumulates ahead of the steam condensation front. If enough DNAPL accumulates, gravitational forces can overcome trapping forces allowing the liquid contaminant to flow downward. By injecting air with steam, a portion of the DNAPL vapor remains suspended in equilibrium with the air, decreasing liquid contaminant accumulation ahead of the steam condensation front, and thus reducing the possibility of downward migration. In this work, a one-dimensional theoretical model is developed to predict the injection ratio of air to steam that will prevent the accumulation of volatile DNAPLs. The contaminated region is modeled as a one-dimensional homogeneous porous medium with an initially uniform distribution of a single component contaminant. Mass and energy balances are combined to determine the injection ratio of air to steam that eliminates accumulation of the contaminant ahead of the steam condensation front, and hence reduces the possibility of downward migration. The minimum injection ratio that eliminates accumulation is defined as the optimum injection ratio. Example calculations are presented for three DNAPLs, carbon tetrachloride (CCl4), trichloroethylene (TCE), and perchloroethylene (PCE). The optimum injection ratio of air to steam is shown to depend on the initial saturation and the volatility of the liquid contaminant. Numerical simulation results are presented to validate the model, and to illustrate downward migration for ratios less than optimum. Optimum injection ratios determined from numerical simulations are shown to be in good agreement with the theoretical model.     

柱淋洗法修复铬污染土壤的效果研究

以铬渣污染土壤为供试土壤,采用土柱淋洗法研究柠檬酸、草酸和盐酸单一淋洗以及复合淋洗对铬去除动态和修复效果的影响,并对淋洗前后土壤中铬形态进行分析,探讨修复机理。结果表明,各淋洗方案中,以10体积0.5 mol/L草酸溶液为淋洗剂时的修复效果最好,总Cr累计淋出量为2 304 mg/kg,上层、中层和下层土壤总Cr去除率分别为79.6%、78.1%和69.6%,Cr(VI)去除率为87.8%、86.2%和75%,且土壤Cr(VI)和总Cr随着土壤深度的增加而升高,有在底部积累的可能;淋洗后土壤明显酸化,p H值从10.5降至3左右;以酸作为淋洗剂能有效降低土壤可氧化态铬含量,将其转化为移动性较强的酸可提取态,这有助于达到预期修复效果。     

A new concept: the use of neutrally-buoyant microemulsions for DNAPL remediation

Even in the absence of mobilization of dense nonaqueous phase liquid (DNAPL), the microemulsion that forms when the surfactant solubilizes a dense contaminant such as trichloroethylene will be more dense than water and tends to migrate downward. This paper addresses the issue of migration with a new concept: surfactant enhanced aquifer remediation at neutral buoyancy. Laboratory results of surfactant remediation in two-dimensional model aquifers show that downward migration of microemulsion containing solubilized dense contaminants can be reduced to an acceptable level, even in the absence of capillary barriers in the aquifer. One model experiment was designed to exhibit a small degree of vertical migration and full capture of the microemulsion at the extraction well. The second experiment was designed to demonstrate the effect of large buoyancy forces that lead to excessive downward migration of the microemulsion. Density measurements of aqueous solutions containing sodium dihexyl sulfosuccinate surfactant, isopropanol, trichloroethylene, and sodium chloride are presented. A companion paper presents the results of the flow and transport calculations needed for this approach to surfactant flooding.