A Study of Vadose Zone Transport Model VLEACH

Application of vadose zone transport models has been hampered by lack of model validation. Difficulties to validate vadose zone models using field data not only come from model assumptions that are uncertain to the subsurface transport processes but also from the uncertainties associated with soil contaminants’ release time and quantity, soil sampling, sample transport, and analytical procedures. This article first conducts a test of a popularly used vadose zone transport VLEACH by comparing model results with a set of laboratory soil column infiltration and volatilization study data. The comparison shows a close agreement between the VLEACH model results and the laboratory data. Second, the sorption coefficient K_d calculated in VLEACH is compared with field data. The comparison indicates that VLEACH may overestimate the mass leached from soil to groundwater. The article also discusses the selection of the model simulation timestep, the vertical dimension increment, the Courant criterion, and the lower boundary condition using the sensitivity analysis method based on a case study of soil remediation for trichloroethylene. The procedures presented in this paper are important to practical model application and modification. This level of work should be routinely conducted for any new or modified version of vadose zone models.     

Estimation of effective cleanup radius for soil‐vapor extraction systems

Soil‐vapor extraction (SVE) is a standard and effective in situ treatment for the removal of volatile contaminants from vadose‐zone soil. The duration of SVE operation required to reach site closure is quite variable, however, ranging up to several years or more. An understanding of the contaminant recovery rate as a function of distance from each vapor‐extraction well allows SVE systems to be designed so that cleanup goals can be achieved within a specified time frame.

A simple one‐dimensional model has been developed that provides a rough estimate of the effective cleanup radius (defined as “the maximum distance from a vapor extraction point through which sufficient air is drawn to remove the required fraction of contamination in the desired time") for SVE systems. Because the model uses analytical rather than numerical methods, it has advantages over more sophisticated, multidimensional models, including simplicity, speed, versatility, and robustness.

The contaminant removal rate at a given distance from the vapor‐extraction point is assumed to be a function of the local rate of soil‐gas flow, the contaminant soil concentration, and the contaminant volatility. Soil‐gas flow rate as a function of distance from the vapor‐extraction point is estimated from pilot test data by assuming that the infiltration of atmospheric air through the soil surface is related to the vacuum in the soil. Although widely applicable, the model should be used with some caution when the vadose zone is highly stratified or when venting contaminated soil greater than 30 ft below grade. Since 1992, Groundwater Technology, Inc. has been using this model routinely as a design tool for SVE systems.     

A Comparison of Hydrocarbon Vapor Attenuation in the Field with Predictions from Vapor Diffusion Models

This study used field data from three sites in Southern California to evaluate vapor phase transport from: (1) free product (die-sel and gasoline spill) on groundwater; (2) dissolved benzene (gasoline spill) in groundwater; and (3) hydrocarbon-impacted soil (gasoline spill) in the vadose zone. A sampling program to evaluate the vapor pathway included the following: vertical profile data, minimal purging prior to sample collection, field analysis of data, confirmation of field data using a fixed laboratory analysis, and soil physical property data. Comparison of hydrocarbon vapor concentrations measured in this field study with those calculated using vapor diffusion models suggest that an additional attenuation factor of between 500 and 35,000 is needed to account for observed concentrations. Comparison of hydrocarbon profiles with oxygen, carbon dioxide, and methane values is consistent with the interpretation that biodegradation is primarily responsible for the observed attenuation. Therefore, vapor pathway models that do not account for bioattenuation will result in a large overesti-mation of the risk at spill sites and will not be consistent with field data.     

Biofiltration of ethylbenzene vapours: influence of the packing material

In order to investigate suitable packing materials, a soil amendment composed of granular high mineralized peat (35% organic content) locally available has been evaluated as carrier material for biofiltration of volatile organic compounds in air by comparison with a fibrous peat (95% organic content). Both supports were tested to eliminate ethylbenzene from air streams in laboratory-scale reactors inoculated with a two-month conditioned culture. In pseudo-steady state operation, experiments at various ethylbenzene inlet loads (ILs) were carried out. Maximum elimination capacity of about 120 g m(-3) h(-1) for an IL of 135 g m(-3) h(-1) was obtained for the fibrous peat. The soil amendment reactor achieved a maximum elimination capacity of about 45 g m(-3) h(-1) for an inlet load of 55 g m(-3) h(-1). Ottengraf-van den Oever model was applied to the prediction of the performance of both biofilters. The influence of gas flow rate was also studied: the fibrous peat reactor kept near complete removal efficiency for empty bed residence times greater than 1 min. For the soil amendment reactor, an empty bed residence time greater than 2 min was needed to achieve adequate removal efficiency. Concentration profiles along the biofilter were also compared: elimination occurred in the whole fibrous peat biofilter, while in the soil amendment reactor the biodegradation only occurred in the first 65% part of the biofilter. Results indicated that soil amendment material, previously selected to increase the organic content, would have potential application as biofilter carrier to treat moderate VOC inlet loads.     

Biodegradation of trichloroethylene and toluene by indigenous microbial populations in vadose sediments

The unsaturated subsurface (vadose zone) receives significant amounts of hazardous chemicals, yet little is known about its microbial communities and their capacity to biodegrade pollutants. Trichloroethylene (TCE) biodegradation occurs readily in surface soils; however, the process usually requires enzyme induction by aromatic compounds, methane, or other cosubstrates. The aerobic biodegradation of toluene and TCE by indigenous microbial populations was measured in samples collected from the vadose zone at unpolluted and gasoline-contaminated sites. Incubation at field moisture levels showed little activity on either TCE or toluene, so samples were tested in soil suspensions. No degradation occurred in samples suspended in water or phosphate buffer solution; however, both toluene and TCE were degraded in samples suspended in mineral salts medium. TCE degradation depended on toluene degradation, and little loss occurred under sterile conditions. Studies with specific nutrients showed that addition of ammonium sulfate was essential for degradation, and addition of other mineral nutrients further enhanced the rate. Additional studies with vadose sediments amended with nutrients showed similar trends to those observed in sediment suspensions. Initial rates of biodegradation in suspensions were faster in uncontaminated samples than in gasolinecontaminated samples, but the same percentages of chemicals were degraded. Biodegradation was slower and less extensive in shallower samples than deeper samples from the uncontaminated site. Two toluene-degrading organisms isolated from a gasoline-contaminated sample were identified as Corynebacterium variabilis SVB74 and Acinetobacter radioresistens SVB65. Inoculation with 10⁶ cells of C. variabilis ml^–1 of soil solution did not enhance the rate of degradation above that of the indigenous population. These results indicate that mineral nutrients limited the rate of TCE and toluene degradation by indigenous populations and that no additional benefit was derived from inoculation with a toluene-degrading bacterial strain. Correspondence to: K.M. Scow     

Distribution and mobility of lead in soils at an outdoor shooting range

The distribution of total Pb in surface and subsurface soil horizons at an outdoor shooting range in southeastern Michigan was determined by single extraction elemental analysis (AAS and ICP‐AES). Significant Pb enrichment of the site's soils coincides closely with Pb vapor and particulate matter produced from shot shell primers and the downfall of Pb/Sb pellets associated with the recreational shooting of skeet and trap. Surface concentrations in these locations are 10 to 100 times greater than the background concentration found on adjacent properties. The distribution of Pb in the subsurface soil horizons corresponds to the distribution of Pb at the surface, which suggests the Pb is mobilizing and migrating downward through the vadose zone. This mobilization appears to be occurring despite the clay‐rich nature of the soils, and may be due to the transformation of metallic Pb into soluble Pb compounds of carbonate and sulfate: Both compounds appear to be present in crust material found coating many of the pellets found at the site. The downward migration of soluble Pb is a potential threat to groundwater that is present at the site at a depth of less than 1 m. The protection of surface water quality is also a concern because Pb pellets from the shooting range have been found in the bed sediments of a nearby stream.     

A decision framework for selecting remediation technologies at hydrocarbon‐contaminated sites

A variety of remediation technologies are available to address hydrocarbon contamination, including free product recovery, soil venting, air sparging, groundwater recovery and treatment, and in situ bioremediation. These technologies address hydrocarbon contamination distributed between free, adsorbed, and dissolved phases in both the vadose and saturated zones. Selection of appropriate technologies is dependent on a number of factors, including contaminants, site‐specific characteristics, clean‐up goals, technology feasibility, cost, and regulatory and time requirements. This article describes a decision framework for selecting appropriate remediation technologies at hydrocarbon‐contaminated sites in a structured and tiered manner. Decision modules include (1) site characterization and product recovery; (2) vadosezone treatment: soil venting, bioremediation, and excavation; (3) saturated zone treatment: sparging, bioremediation, groundwater recovery, and excavation; and (4) groundwater treatment: carbon, air stripping, advanced oxidation, and bioreactors. Selection criteria for treatment technologies that address vadose‐ and saturated‐zone soils, as well as recovered groundwater, are described. The decision framework provides a systematic process to formulate solutions to complex problems and documents the rationale for selecting remediation systems designed to achieve closure at hydrocarbon‐contaminated sites.     

干旱区包气带土壤水分运移能量关系及驱动力研究评述

包气带土壤能量和水分平衡及其驱动因子是维系地下水-土壤-植物-大气连续体(GSPAC)系统中水分运移发生的关键因素。在降水稀少、水资源短缺的干旱地区,开展包气带土壤水分形态、运移过程与能量的耦合规律研究对揭示区域水资源形成和转化机理具有极其重要的现实意义。文章总结了土壤水分运移理论研究进展,探讨了水分参与水文循环过程及干旱环境下土壤水分可能表现形态及其降雨入渗、再分布、渗漏、蒸发、毛管水上升等过程驱动机制,评述了包气带土壤水分与能量过程在不同空间尺度上生态水分效应。在一个非饱和土壤系统中,水分运移受包气带结构,土壤物理特征,植物根系和土壤生化环境的综合控制,物质和能量平衡改变是驱动水分循环的源动力,而土壤环境变化是导致水分运移形态的发生变化根本原因。因此,在气候变化背景下,研究干旱区土壤与大气界面以及包气带与饱和带界面水、汽、热耦合转化形式与能量驱动过程,能够提升我们对包气带土壤水分运移规律机理的深入理解,丰富对区域气候和水文变化认知。为干旱区生态植被恢复建设和水资源精细化管理提供理论向导。     

Bioventing soils contaminated with petroleum hydrocarbons

Summary Bioventing combines the capabilities of soil venting and enhanced bioremediation to cost-effectively remove light and middle distillate hydrocarbons from vadose zone soils and the groundwater table. Soil venting removes the more volatile fuel components from unsaturated soil and promotes aerobic biodegradation by driving large volumes of air into the subsurface. In theory, air is several thousand times more effective than water in penetrating and aerating fuel-saturated and low permeability soil horizons. Aerobic microbial degradation can mitigate both residual and vapor phase hydrocarbon concentrations. Soil venting is being evaluated at a number of U.S. military sites contaminated with middle distillate fuels to determine its potential to stimulate in situ aerobic biodegradation and to develop techniques to promote in situ vapor phase degradation. In situ respirometric evaluations and field pilot studies at sites with varying soil conditions indicate that bioventing is a cost-effective method to treat soils contaminated with jet fuels and diesel.     

Removal of dimethyl disulfide by the peat seeded with night soil sludge

The removal characteristics of dimethyl disulfide (DMDS) with a fibrous peat biofilter were studied. The peat itself did not remove DMDS. The peat inoculated with aerobically-digested night soil sludge as a source of microorganisms showed an efficient removal of DMDS with the maximum removal rate, 0.68 g-S·kg-dry peat⁻¹·d⁻¹ and the saturation constant, 1 ppm. The removal rate of DMDS by the biofilter decreased when pH was below 5.5. The number of microorganisms isolated on thiosulfate-agar plates (pH 7) remarkably increased in DMDS-acclimated peat. Similar removal characteristics and the change in microflora were observed in methanethiol (MT)- and dimethyl sulfide (DMS)-acclimated peat. These results indicated that some chemolithotrophic and non-acidophilic sulfur-oxidizing microorganisms such as Thiobacilli, originating from night soil sludge, were responsible for degradation of these organosulfur compounds in the peat biofilter.     

Volatile organic compound fate in phytoremediation applications: natural and engineered systems

Unique sampling techniques have generated a new understanding regarding the fate of volatile organic compounds (VOCs) in phytoremediation systems. Tissue sampling and diffusion traps were used to determine how VOCs are transported in and diffuse from vegetation, particularly woody species. These techniques were then utilized to observe how plants interact with different contaminated media, showing transport of contaminants occurs from the vadose zone (vapor phase) as well as the saturated zone (aqueous phase). Data was gathered in laboratory studies, in native vegetation, and in engineered phytoremediation systems. The findings reveal that diffusion from the xylem tissues to the atmosphere is a major fate for VOCs in phytoremediation applications. Linking VOCs' fate with groundwater hydraulics, mass removal rates from contaminant plumes can be estimated. These techniques were also utilized to observe the impact of engineered plant/microbe systems, which utilize recombinant, root-colonizing organisms to selectively degrade compounds and subsequently alter the fate of VOCs and other organic compounds. The genetically enhanced rhizoremediation methods pose a novel approach that may allow for biodegradation of compounds that formerly were considered recalcitrant.     

Functional diversity changes of microbial communities along a soil aquifer for reclaimed water recharge

The physiochemical and functional diversity of soil-attached microorganisms was investigated using a stabilized laboratory-scale soil aquifer treatment (SAT) system. In this system, reclaimed water after ozonation was used as the feed water, and 60% dissolved organic carbon was removed by the unsaturated vadose layer in 0.8?days. Soil biomass (volatile solids, phospholipid extraction) and functional diversity significantly decreased from the unsaturated vadose layer to the saturated aquifer, where they maintained the same level. Using principal components analysis based on substrate utilization pattern, the vadose layer soil sample was clearly separated from the saturated layer samples. Exceptionally, the oxidation rates of esters remained stable during SAT, indicating the purification potential on certain recalcitrant organic compounds in the saturated aquifer given an adequate retention time. Correlation analysis revealed that organic carbon was the key limiting factor for microbial biomass and activity, especially for tyrosine-like aromatic proteins and soluble microbial byproduct-like materials.     

Microbial abundance and activities in relation to water potential in the vadose zones of arid and semiarid sites

Numbers and activities of microorganisms were measured in the vadose zones of three arid and semiarid areas of the western United States, and the influence of water availability was determined. These low-moisture environments have vadose zones that are commonly hundreds of meters thick. The specific sampling locations chosen were on or near U.S. Department of Energy facilities: the Nevada Test Site (NTS), the Idaho National Engineering Laboratory (INEL), and the Hanford Site (HS) in southcentral Washington State. Most of the sampling locations were uncontaminated, but geologically representative of nearby locations with storage and/or leakage of waste compounds in the vadose zone. Lithologies of samples included volcanic tuff, basalt, glaciofluvial and fluvial sediments, and paleosols (buried soils). Samples were collected aseptically, either by drilling bore-holes (INEL and HS), or by excavation within tunnels (NTS) and outcrop faces (paleosols near the HS). Total numbers of microorganisms were counted using direct microscopy, and numbers of culturable microorganisms were determined using plate-count methods. Desiccation-tolerant microorganisms were quantified by plate counts performed after 24 h desiccation of the samples. Mineralization of ¹⁴C-labeled glucose and acetate was quantified in samples at their ambient moisture contents, in dried samples, and in moistened samples, to test the hypothesis that water limits microbial activities in vadose zones. Total numbers of microorganisms ranged from log 4.5 to 7.1 cells g^-1 dry wt. Culturable counts ranged from log <2 to 6.7 CFU g^-1 dry wt, with the highest densities occurring in paleosol (buried soil) samples. Culturable cells appeared to be desiccation-tolerant in nearly all samples that had detectable viable heterotrophs. Water limited mineralization in some, but not all samples, suggesting that an inorganic nutrient or other factor may limit microbial activities in some vadose zone environments. Offprint requests to: T.L. Kieft     

Adsorption of RDX to Soil with Low Organic Carbon: Laboratory Results,Field Observations,Remedial Implications

The purpose of this article is to review both laboratory and field observations of RDX adsorption to soils and to use those results to estimate the effects of a planned remedial action. Adsorption isotherms for RDX are generally observed to be linear and reversible. Statistical tests were performed to determine the relationship between K_d and various soil characteristics. A linear relationship between Kd and soil organic carbon was observed, as expected, but regression of K_d to organic carbon content indicated a non-zero intercept, suggesting that other sorbents may also be significant at low OC (e.g., > 0.5 %). No other soil properties were significantly related to Kd so the mechanism of adsorption at low organic carbon was not determined. These results were used to interpret observations of RDX in the vadose zone at Milan Army Ammunition Plant (MAAP), TN. MAAP exhibits widespread soil contamination by RDX. Depth to groundwater ranges from 40 to 80?ft. Unsaturated soils are fine grained near the surface, and sandy near the water table. RDX is concentrated in the upper 2?ft, where concentrations in some places exceed 1 %. Subsurface concentrations are generally less than 50?mg/kg. The distribution of RDX in soil, soil moisture and groundwater, and soil physical testing data were interpreted using simple models. The distribution of RDX is consistent with the following conceptual model: ??Water containing RDX was dis charged to the land surface (prior to 1983); ??Crystalline RDX remains in surface soil (remedial activities are ongo ing); ??Infiltrating rainwater leaches RDX from surface soils; ??This leachate carries RDX through the deeper vadose zone, resulting in significant soil contamination through out the full thickness of the vadose zone; these soils can generate leachate and adversely affect ground- water quality for many years to come. Field results were consistent with the adsorption studies. Simple models consistent with the field and laboratory observations indicate that deeper soils that are not planned to be remediated may continue to leach unacceptable concentrations to groundwater for approximately 180 years. The Army intends to evaluate whether it will be most cost-effective to address this continuing source by treating soils or groundwater.     

Pore Water Quality in the Upper Part of the Vadose Zone under an Operating Canadian Small Arms Firing Range Backstop Berm

Canadian military small arms firing range (SAFR) backstop berm soils contain high concentrations of Pb, Cu, Sb, and Zn. Three Teflon® cylindrical lysimeters were installed in the vadose zone of the backstop berm in order to characterize the pore water quality. Copper-Zn concentrations were below their respective Québec drinking water thresholds, and Pb-Sb concentrations were above the criteria in many cases, indicating that a metal vertical migration occurs in the vadose zone. Metal concentrations in pore water were, in decreasing order, Zn > Pb > Sb > Cu. Calculated annual metal leaching rates showed that a rather small portion of the metals in the soil were mobilized in the vadose zone, and that metals were a potential source of contamination for extremely long periods of time, highlighting the importance of finding ways to remediate such soils in order to limit metal mobility in SAFR backstop berms.     

Gasoline Vapor Biofiltration

While gasoline vapor emissions are common sources of air pollution, very few results have been published on the biofilter biodegradation of gasoline vapors in flowing waste gases. This investigation reports on a bench‐scale biofilter of an ID of 50 mm and a bed height of 850 mm with an inexpensive fire clay chip medium as a packing material. The biofilter was inoculated with a concentrate of a mixed culture of the common microflora. After an acclimatization period of three weeks, loading tests were carried out at increasing gasoline inlet concentrations at a constant Empty Bed Retention Time (EBRT) of 16 min. Evaluating the removal rate and efficiency of aliphatic and aromatic fractions of the gasoline vapor, it was found that in a range of overall organic loading (OL_TPH) up to 33.6 g/m³ h the removal efficiency of aromatic hydrocarbons decreased from 90 to 70 %, while that of the aliphatic components decreased much more significantly from 60 to 10 % after six months of operation. The removal rate and efficiency achieved for total petroleum hydrocarbons were 13 g/m³ h and 45 %, respectively. The microbial strains and genera of culturable cells in the inoculum and in the biofilm after six months of gasoline degradation were evaluated.     

Plants as Bio-Indicators of Subsurface Conditions: Impact of Groundwater Level on BTEX Concentrations in Trees

Numerous studies have demonstrated trees’ ability to extract and translocate moderately hydrophobic contaminants, and sampling trees for compounds such as BTEX can help delineate plumes in the field. However, when BTEX is detected in the groundwater, detection in nearby trees is not as reliable an indicator of subsurface contamination as other compounds such as chlorinated solvents. Aerobic rhizospheric and bulk soil degradation is a potential explanation for the observed variability of BTEX in trees as compared to groundwater concentrations. The goal of this study was to determine the effect of groundwater level on BTEX concentrations in tree tissue. The central hypothesis was increased vadose zone thickness promotes biodegradation of BTEX leading to lower BTEX concentrations in overlying trees. Storage methods for tree core samples were also investigated as a possible reason for tree cores revealing lower than expected BTEX levels in some sampling efforts. The water level hypothesis was supported in a greenhouse study, where water table level was found to significantly affect tree BTEX concentrations, indicating that the influx of oxygen coupled with the presence of the tree facilitates aerobic biodegradation of BTEX in the vadose zone.     

Plants as Bio-Indicators of Subsurface Conditions: Impact of Groundwater Level on Btex Concentrations in Trees

Numerous studies have demonstrated trees’ ability to extract and translocate moderately hydrophobic contaminants, and sampling trees for compounds such as BTEX can help delineate plumes in the field. However, when BTEX is detected in the groundwater, detection in nearby trees is not as reliable an indicator of subsurface contamination as other compounds such as chlorinated solvents. Aerobic rhizospheric and bulk soil degradation is a potential explanation for the observed variability of BTEX in trees as compared to groundwater concentrations. The goal of this study was to determine the effect of groundwater level on BTEX concentrations in tree tissue. The central hypothesis was increased vadose zone thickness promotes biodegradation of BTEX leading to lower BTEX concentrations in overlying trees. Storage methods for tree core samples were also investigated as a possible reason for tree cores revealing lower than expected BTEX levels in some sampling efforts. The water level hypothesis was supported in a greenhouse study, where water table level was found to significantly affect tree BTEX concentrations, indicating that the influx of oxygen coupled with the presence of the tree facilitates aerobic biodegradation of BTEX in the vadose zone.     

Reduction of perchlorate and nitrate by microbial communities in vadose soil

Perchlorate contamination is a concern because of the increasing frequency of its detection in soils and groundwater and its presumed inhibitory effect on human thyroid hormone production. Although significant perchlorate contamination occurs in the vadose (unsaturated) zone, little is known about perchlorate biodegradation potential by indigenous microorganisms in these soils. We measured the effects of electron donor (acetate and hydrogen) and nitrate addition on perchlorate reduction rates and microbial community composition in microcosm incubations of vadose soil. Acetate and hydrogen addition enhanced perchlorate reduction, and a longer lag period was observed for hydrogen (41 days) than for acetate (14 days). Initially, nitrate suppressed perchlorate reduction, but once perchlorate started to be degraded, the process was stimulated by nitrate. Changes in the bacterial community composition were observed in microcosms enriched with perchlorate and either acetate or hydrogen. Denaturing gradient gel electrophoresis analysis and partial sequencing of 16S rRNA genes recovered from these microcosms indicated that formerly reported perchlorate-reducing bacteria were present in the soil and that microbial community compositions were different between acetate- and hydrogen-amended microcosms. These results indicate that there is potential for perchlorate bioremediation by native microbial communities in vadose soil.     

Development of a treatment solution for reductive dechlorination of hexachloro-1,3-butadiene in vadose zone soil

The biodegradation of chlorinated organics in vadose zone soils is challenging owing to the presence of oxygen, which inhibits reductive dehalogenation reactions and consequently the growth of dehalorespiring microbes. In addition, the hydraulic conductivity of vadose zone soils is typically high, hence attempts to remediate such zones with biostimulation solutions are often unsuccessful due to the short residence times for these solutions to act upon the native bacterial community. In this study we have identified sodium alginate as a hydrogel polymer that can be used to increase the residence time of a nutrient solution in an unsaturated sandy soil. Additionally we have identified neutral red as a redox active compound that can catalyse the reductive dechlorination of the chlorinated organic hexachloro-1,3-butadiene by activated sludge fed with lactate and acetate. Finally we have shown that a nutrient solution amended with neutral red and sodium alginate can lower the redox potential and reduce hexachloro-1,3-butadiene concentrations in a contaminated vadose zone soil.