Long-term recovery of PCB-contaminated surface sediments at the Sangamo-westonl Twelvemile Creek/lake Hartwell Superfund Site

Natural recovery of contaminated sediments relies on burial of contaminated sediments with increasingly clean sediments over time (i.e., natural capping). Natural capping reduces the risk of resuspension of contaminated surface sediments, and it reduces the potential for contaminant transport into the food chain by limiting bioturbation of contaminated surface or near-surface sediments. This study evaluated the natural recovery of surface sediments contaminated with polychlorinated biphenyls (PCBs) at the Sangamo-Weston/Twelvemile Creek/Lake Hartwell Superfund Site (Lake Hartwell), Pickens County, SC. The primary focus was on sediment recovery resulting from natural capping processes. Total PCB (t-PCB), lead-210 (210Pb), and cesium-137 (137Cs) sediment core profiles were used to establish vertical t-PCB concentration profiles, age date sediments, and determine surface sedimentation and surface sediment recovery rates in 18 cores collected along 10 transects. Four upgradient transects in the headwaters of Lake Hartwell were impacted by historical sediment releases from three upgradient sediment impoundments. These transects were characterized by silt/ clay and sand layering. The highest PCB concentrations were associated with silt/clay layers (1.8-3.5% total organic carbon (TOC)), while sand layers (0.05-0.32% TOC) contained much lower PCB concentrations. The historical sediment releases resulted in substantial burial of PCB-contaminated sediment in the vicinity of these four cores; each core contained less than 1 mg/kg t-PCBs in the surface sand layers. Cores collected from six downgradient Lake Hartwell transects consisted primarily of silt and clay (0.91-5.1% TOC) and were less noticeably impacted by the release of sand from the impoundments. Vertical t-PCB concentration profiles in these cores began with relatively low PCB concentrations at the sediment-water interface and increased in concentration with depth until maximum PCB concentrations were measured at approximately 30-60 cm below the sediment-water interface, ca. 1960-1980. Maximum t-PCB concentrations were followed by progressively decreasing concentrations with depth until the t-PCB concentrations approached the detection limit, where sediments were likely deposited before the onset of PCB use at the Sangamo-Weston plant. The sediments containing the maximum PCB concentrations are associated with the period of maximum PCB release into the watershed. Sedimentation rates averaged 2.1 +/- 1.5 g/(cm2 yr) for 12 of 18 cores collected. The 1994 Record of Decision cleanup requirement is 1.0 mg/kg; two more goals (0.4 and 0.05 mg/kg t-PCBs) also were identified. Average surface sedimentation requirements to meet the three goals were 1.4 +/- 3.7, 11 +/- 4.2, and 33 +/- 11 cm, respectively. Using the age dating results, the average recovery dates to meet these goals were 2000.6 +/- 2.7, 2007.4 +/- 3.5, and 2022.7 +/- 11 yr, respectively. (The 95% prediction limits for these values also are provided.) Despite the reduction in surface sediment PCB concentrations, PCB concentrations measured in largemouth bass and hybrid bass filets continue to exceed the 2.0 mg/kg FDA fish tolerance level.     

Assessing the effectiveness of thin-layer sand caps for contaminated sediment management through passive sampling

The effectiveness of thin-layer sand capping for contaminated sediment management (capping with a layer of thickness comparable to the depth of benthic interactions) is explored through experiments with laboratory-scale microcosms populated with the deposit-feeding oligochaete, Ilyodilus templetoni. Passive sampling of pore water concentrations in the microcosms using polydimethylsiloxane (PDMS)-coated fibers enabled quantification of high-resolution vertical concentration profiles that were used to infer contaminant migration rates and mechanisms. Observed concentration profiles were consistent with models that combine traditional contaminant transport processes (sorption-retarded diffusion) with bioturbation. Predictions of bioaccumulation based on contaminant pore water concentrations within the surface layer of the cap correlated well with observed bioaccumulation (correlation coefficient of 0.92). The results of this study show that thin-layer sand caps of contaminated sediments can be effective at reducing the bioaccumulation of polycyclic aromatic hydrocarbons (PAHs) provided the thickness of the cap layer exceeds the depth of organism interaction with the sediments and the pore water concentrations within the biologically active zone remain low (e.g., when molecular diffusion controls transport from the underlying sediment layer).     

Landfill-stimulated iron reduction and arsenic release at the Coakley Superfund Site (NH)

Arsenic is a contaminant at more than one-third of all Superfund Sites in the United States. Frequently this contamination appearsto resultfrom geochemical processes rather than the presence of a well-defined arsenic source. Here we examine the geochemical processes that regulate arsenic levels at the Coakley Landfill Superfund Site (NH), a site contaminated with As, Cr, Pb, Ni, Zn, and aromatic hydrocarbons. Long-term field observations indicate that the concentrations of most of these contaminants have diminished as a result of treatment by monitored natural attenuation begun in 1998; however, dissolved arsenic levels increased modestly over the same interval. We attribute this increase to the reductive release of arsenic associated with poorly crystalline iron hydroxides within a glaciomarine clay layer within the overburden underlying the former landfill. Anaerobic batch incubations that stimulated iron reduction in the glaciomarine clay released appreciable dissolved arsenic and iron. Field observations also suggest that iron reduction associated with biodegradation of organic waste are partly responsible for arsenic release; over the five-year study period since a cap was emplaced to prevent water flow through the site, decreases in groundwater dissolved benzene concentrations at the landfill are correlated with increases in dissolved arsenic concentrations, consistent with the microbial decomposition of both benzene and other organics, and reduction of arsenic-bearing iron oxides. Treatment of contaminated groundwater increasingly is based on stimulating natural biogeochemical processes to degrade the contaminants. These results indicate that reducing environments created within organic contaminant plumes may release arsenic. In fact, the strong correlation (>80%) between elevated arsenic levels and organic contamination in groundwater systems at Superfund Sites across the United States suggests that arsenic contamination caused by natural degradation of organic contaminants may be widespread.     

Electrolyte management for effective long-term electro-osmotic transport in low-permeability soils

Electro-osmosis, a coupled-flow phenomenon in which an applied electrical potential gradient drives water flow, may be used to induce water flow through fine-grained sediments. Test cell measurements of electro-osmotic transport in clayey cores extracted from the 27-31 m depth range of the Lawrence Livermore National Laboratory site indicate the importance of pH control within the anode and cathode reservoirs. In our first experiment, pH was not controlled. As a result, carbonate precipitation and metals precipitation occurred near the cathode end of the core, with acidification near the anode. The combination of these acid and base reactions led to the decline of electro-osmotic flow by a factor of 2 in less than one pore volume. In a second experiment, long-term water transport (>21 pore volumes) at stable electro-osmotic conductivity (k(eo) approximately 1 x 10(-9) m2/s-V) was effected with anode reservoir pH > 8, and cathode reservoir pH < 6. Hydraulic conductivity (k(h)) of the same core was 4 x 10(-10) m/s under a 0.07 MPa hydraulic gradient without electro-osmosis. Stable electro-osmotic flow was measured at a velocity of 4 x 10(-7) m/s under a 4 V/cm voltage gradient, and no hydraulic gradient-3 orders of magnitude greater than the hydraulic flow. We also observed chloroform production in the anode reservoir, resulting from electrochemical production of chlorine gas reacting with trace organics. The chloroform was transported electro-osmotically to the cathode, without measurable loss to adsorption, volatilization, or degradation.     

Characterization and quantification of pneumatic fracturing effects at a clay till site

Environmental fracturing offers assistance to remediation efforts at contaminated, low-permeability sites via creation of active fracture networks, and hence, reduction of mass transport limitations set by diffusion in low-permeability matrices. A pilot study of pneumatic fracturing, focusing on direct documentation of fracture propagation patterns and spacing, was performed at a typical basal clay till site. The study applied a novel package of documentation methods, including injection of five tracers with different characteristics (bromide, uvitex, fluorescein, rhodamine WT, and brilliant blue), subsequent tracer-filled fracture documentation via direct and indirect methods, and geological characterization of the fractured site. The direct documentation methods consisted of Geoprobe coring, augering, and excavation. A mass balance and conceptual model have been established for the distribution of the injected tracers in the subsurface. They reveal that tracer was distributed within 2 m of the fracturing well, mainly in existing fractures above the redox boundary (2 to 4 m.b.s.; 5 to 10 cm spacing). Spacing of observed tracer-filled fractures was large (>1 m) at greater depths. The number of fractures induced/activated could possibly be increased via adjustments to the fracturing equipment design.     

Direct measurement of VOC diffusivities in tree tissues: impacts on tree-based phytoremediation and plant contamination

Recent discoveries in the phytoremediation of volatile organic compounds (VOCs) show that vapor-phase transport into roots leads to VOC removal from the vadose zone and diffusion and volatilization out of plants is an important fate following uptake. Volatilization to the atmosphere constitutes one fundamental terminal fate processes for VOCs that have been translocated from contaminated soil or groundwater, and diffusion constitutes the mass transfer mechanism to the plant-atmosphere interface. Therefore, VOC diffusion through woody plant tissues, that is, xylem, has a direct impact on contaminant fate in numerous vegetation-VOC interactions, including the phytoremediation of soil vapors and dissolved aqueous-phase contaminants. The diffusion of VOCs through freshly excised tree tissue was directly measured for common groundwater contaminants, chlorinated compounds such as trichloroethylene, perchloroethene, and tetrachloroethane and aromatic hydrocarbons such as benzene, toluene, and methyl tert-butyl ether. All compounds tested are currently being treated at full scale with tree-based phytoremediation. Diffusivities were determined by modeling the diffusive transport data with a one-dimensional diffusive flux model, developed to mimic the experimental arrangement. Wood-water partition coefficients were also determined as needed for the model application. Diffusivities in xylem tissues were found to be inversely related to molecular weight, and values determined herein were compared to previous modeling on the basis of a tortuous diffusion path in woody tissues. The comparison validates the predictive model for the first time and allows prediction for other compounds on the basis of chemical molecular weight and specific plant properties such as water, lignin, and gas contents. This research provides new insight into phytoremediation efforts and into potential fruit contamination for fruit-bearing trees, specifically establishing diffusion rates from the transpiration stream and modeling volatilization along the transpiration path, including the trunk and branches. This work also has importance in other plant-VOC interactions, such as potential uptake from the atmosphere for hydrophobic compounds and also uptake from vapor-phase soil contaminants.     

Conductivity reduction due to emulsification during surfactant enhanced-aquifer remediation. 1. Emulsion transport

Surfactant-enhanced aquifer remediation (SEAR) is a promising technology for the remediation of subsurface zones contaminated with organic liquids. To ensure the success of SEAR, the potential reduction in hydraulic conductivity must be evaluated. The objective of this study was to examine the process of conductivity reduction due to the transport of an emulsion, generated by mixing tetrachloroethylene with 4% solutions of two nonionic surfactants, in packed beds of sand-sized silica particles. The injection of the emulsion resulted in a 75-85% reduction in conductivity, depending on the properties of the surfactant and the porous medium. The greater viscosity of the emulsion relative to that of water accounted for about 25% of the reduction. The remainder was attributed to the clogging of the porous medium by the emulsion. The relative sizes of the emulsion droplets and the packed bed's pores, coupled with measurements of zeta potential of the emulsion droplets and silica particles, suggested that multilayer deposition was the principal mechanism of clogging. This hypothesis was corroborated by direct observation of the emulsion transport process in a micromodel. To simulate the reduction in hydraulic conductivity in these systems accurately, it was necessary to modify the emulsion transport model by Soo and Radke to include the phenomena of viscosity variation and multilayering.     

Facilitated transport of dioxins in soil following unintentional release of pesticide-surfactant formulations

Colloids such as surfactant micelles can act as transport facilitators for highly lipophilic, generally immobile contaminants in soil. Following a fire at a pesticide facility, this study investigated vertical and lateral migration of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in heterogeneous soil beneath bunded ponds, where contaminated wastewater containing high surfactant loads was stored until remediation. Initially, surface and subsurface soil was obtained during excavation, and subsequently intact cores to 5.7 m were collected. ΣPCDD/F concentrations were elevated in the wastewater (15-81 ng/L) and correspondingly in pond surface soils (6.1-61 ng/g). Maximum ΣPCDD/F concentrations were, however, observed at 2-2.5 m depth (68-130 ng/g), far below their expected mobility range based on physicochemical properties. Congener specific analysis further indicated that PCDD/F mobility was reversed, with the least water-soluble congener migrating to the greatest extent. The presence of higher chlorinated PCDD/Fs throughout a core collected in the direction of groundwater flow indicated subsequent lateral transport. These results provide field evidence for rapid vertical migration (2.4 m in <4 months) of highly lipophilic PCDD/Fs and suggest surfactant facilitated transport as the dominant transport mechanism. Quantification and evaluation of such fundamental changes in contaminant transport and fate in the presence of surfactants is required to identify areas at risk of groundwater contamination.     

Ferrographic tracking of bacterial transport in the field at the narrow channel focus area, Oyster, VA

The first results from an innovative bacterial tracking technique, ferrographic capture, applied to bacterial transport in groundwater are reported in this paper. Ferrographic capture was used to analyze samples during an October 1999 bacterial injection experiment at the Narrow Channel focus area of the South Oyster site, VA. Data obtained using this method showed that the timing of bacterial breakthrough was controlled by physical (hydraulic conductivity) heterogeneity in the vertical dimension as opposed to variation in sedimentsurface or aqueous chemical properties. Ferrographic tracking yielded results that compared well with results from other tracking techniques over a concentration range of 8 orders of magnitude and provided a low detection limit relative to most other bacterial tracking techniques. The low quantitation limit of this method (approximately 20 cells/mL) allowed observation of transport of an adhesion-deficient bacterium over distances greater than 20 m in the fine sand aquifer underlying this site.     

Review: Technical and policy challenges in deep vadose zone remediation of metals and radionuclides

Contamination in deep vadose zone environments is isolated from exposure so direct contact is not a factor in its risk to human health and the environment. Instead, movement of contamination to the groundwater creates the potential for exposure and risk to receptors. Limiting flux from contaminated vadose zone is key for protection of groundwater resources, thus the deep vadose zone is not necessarily considered a resource requiring restoration. Contaminant discharge to the groundwater must be maintained low enough by natural attenuation (e.g., adsorption processes or radioactive decay) or through remedial actions (e.g., contaminant mass reduction or mobility reduction) to meet the groundwater concentration goals. This paper reviews the major processes for deep vadose zone metal and radionuclide remediation that form the practical constraints on remedial actions. Remediation of metal and radionuclide contamination in the deep vadose zone is complicated by heterogeneous contaminant distribution and the saturation-dependent preferential flow in heterogeneous sediments. Thus, efforts to remove contaminants have generally been unsuccessful although partial removal may reduce downward flux. Contaminant mobility may be reduced through abiotic and biotic reactions or through physical encapsulation. Hydraulic controls may limit aqueous transport. Delivering amendments to the contaminated zone and verifying performance are challenges for remediation.     

Characterization of hydrocarbon emissions from green sand foundry core binders by analytical pyrolysis

Analytical pyrolysis was conducted to study a relative comparison of the hydrocarbon and greenhouse gas emissions of three foundry sand binders as follows: (a) conventional phenolic urethane resin, (b) biodiesel phenolic urethane resin, and (c) collagen-based binder. These binders are used in the metal casting industry for making cores that are used to create internal cavities within castings. In this study, the core samples were flash pyrolyzed in a Curie-point pyrolyzer at 920 degrees C with a heating rate of about 3000 degrees C/sec. This simulated some key features of the fast heating conditions that the core binders would experience at the metal-core interface when molten metal is poured into green sand molds. The core samples were also pyrolyzed in a thermogravimetric analyzer (TGA) from ambient temperature to 1000 degrees C with a heating rate of 30 degrees C/min, and this simulated key features of the slow heating conditions that the core binders would experience at distances that are further away from the metal-core interface during casting cooling. Hydrocarbon emissions from flash pyrolysis were analyzed with a gas chromatography-flame ionization detector, while hydrocarbon and greenhouse gas (CO and CO2) emissions from TGA pyrolysis were monitored with mass spectrometry. The prominent hazardous air pollutant emissions during pyrolysis of the three binders were phenol, cresols, benzene, and toluene for the conventional phenolic urethane resin and biodiesel resin, and they were benzene and toluene for the collagen-based binder. It was also found that volatile organic compound and polycyclic aromatic hydrocarbon emissions considerably decreased in order from conventional phenolic urethane resin to biodiesel resin to collagen-based binder. These results have shown some similarity with those for stack emission testing conducted at demonstration scale and/or full-scale foundries, and the similar trends in the two sets of results offered promise that bench-scale analytical pyrolysis techniques could be a useful screening tool for the foundries to compare the relative emissions of alternative core binders and to choose proper materials in order to comply with air-emission regulations.     

Surfactant-enhanced air sparging in saturated sand

Air sparging as a subsurface remedial technique can be enhanced bythe addition of a surfactant. The effect of reduced surface tension of water on the extent of air intrusion and air saturation during air sparging in porous media was investigated. A sand column and a two-dimensional sand box were used for the experiments. The surface tension was controlled using an anionic surfactant, sodium dodecyl benzene sulfonate, and the concentration used was below the critical micelle concentration. Using the sand column, the air saturation was measured at different surface tensions and at different airflow rates. Initially water-saturated, the air saturation achieved in the column by air sparging at a surface tension of 3.42 x 10(-2) N/m was up to 5 times larger than that of water with no surfactant. Atthe same time, the rate at which the air saturation increased as a function of airflow rate was greater at reduced surface tensions. For box experiments with homogeneous sand, reduction of the surface tension caused a dramatic increase in the sparging area up to 5.2 times of that generated using water with no surfactant. A sand box experiment containing a vertical channel produced preferential flow of the air phase injected at the bottom of the channel when the surfactant was not applied. However, reducing the surface tension was found to promote airflow through the preferential channel and the finer sand surrounding the channel. These observations support the use of low concentration surfactants to improve air sparging swept zones.     

Laboratory evaluation of custom-designed surfactants to remediate NAPL source zones

Laboratory column studies were conducted using custom-designed anionic surfactants, the branched alcohol propoxylated sulfates, to evaluate their effectiveness in removing nonaqueous phase liquids (NAPLs) from both Ottawa sand and field alluvium. Surfactant efficacy was tested at temperatures ranging between 11 and 50 degrees C for contaminants such as tetrachloroethene (PCE), weathered gasoline, and Naval Special Fuel Oil. It has been shown that use of branched alcohol propoxylated sulfates can achieve very low final NAPL saturations even with recalcitrant NAPLs, while exhibiting low induced hydraulic gradients, low microemulsion viscosity, and minimal sorption on contaminated field soils. These custom-designed surfactants are effective with both dense NAPLs (DNAPLs) and light NAPLs. Finally, these surfactants were used to create neutrally buoyant microemulsions with a PCE DNAPL. The laboratory experiments show that these custom-designed, high-performance surfactants can be tailored to optimize contaminant solubility for specific field NAPLs.     

Experimental visualization of solute transport and mass transfer processes in two-dimensional conductivity fields with connected regions of high conductivity

Solute transport displaying mass transfer behavior (i.e., tailing) occurs in many aquifers and soils. Spatial patterns of hydraulic conductivity may play a role because of both advection and diffusion through isolated low conductivity areas. We demonstrated such processes in laboratory experiments designed to visualize solute transport through a thin chamber (40 cm x 20 cm x 0.64 cm thick) packed with glass beads and containing circular emplacements of smaller glass beads with lower conductivity. The experiments used three different contrasts of conductivity between the large-bead matrix and the emplacements, targeting three different regimes of solute transport: low contrast, targeting macrodispersion; intermediate contrast, targeting advection-dominated mass transfer between the high-conductivity regions and the emplacements; and high contrast, targeting diffusion-dominated mass transfer. Use of a strong light source, a high-resolution CCD camera, and a colorimetric dye produced images with a spatial resolution of about 400 microm and a concentration range of approximately 2 orders of magnitude. These images confirm the existence of the three different regimes, and we observed tailing driven by both advection and diffusion. Outflow concentration measured by spectrophotometer achieved 3 orders of magnitude in concentration range and showed good agreement with known models in the case of dispersion and diffusive mass transfer, with estimated parameters close to a priori predictions. Existing models for diffusive mass transfer did notfitthe breakthrough curves from the intermediate-contrast chamber, but a model of slow advection through cylinders did. Thus, both breakthrough curves and chamber images confirm that different contrasts in small-scale K lead to different regimes of solute transport and thus require different models of upscaled solute transport.     

Colloid transport in a heterogeneous partially saturated sand column

Colloid transport was studied in heterogeneous sand columns under unsaturated steady-state conditions, using two sizes of acid-cleaned sand to pack the column. Heterogeneity was created by placing three continuous tubes of fine sand (3.6% of the total volume) within a column of coarse sand (mean grain diameters 0.36 and 1.2 mm, respectively). Experiments were performed under three flow rates (0.1, 0.2, and 0.4 cm/ min) applied by a rain simulator atthe top of the column. Constant water-content profile in the coarse sand was achieved by applying corresponding suction at the column bottom. Three sizes of latex microspheres (1, 0.2, and 0.02 microm) and soluble tracers (LiBr), diluted in a weak base (pH 7.3, ionic strength 0.0023 M) solution, were used simultaneously. Introduction of preferential pathways reduced front-arrival time about 2-fold and increased colloid recovery which, at the 0.2 cm/min flow rate, was higher than at 0.4 and 0.1 cm/min. Maximum solution flux from coarse to fine sand (due to differences in matric pressure) at 0.2 cm/min, verified by hydrodynamic modeling, could explain this phenomenon. Results suggest that in heterogeneous soil, maximum colloid recovery does not necessarily occur at maximum water content. This has clear implications for colloid transport in natural soils, many of which are heterogeneous.     

Subsurface biobarrier formation by microorganism injection for contaminant plume control

The concept of an in situ mixture of residual soil and aerobic microorganisms as a biobarrier for controlling contaminant plume was evaluated in this study. Azotobacter chroococcum was inoculated into soil with oxygen as the electron acceptor and appropriate substrate to induce biofilm clog soil pores. The hydraulic conductivity of soil decreased by 1/8000 while substrate and oxygen were provided to the injected microorganism, and increased by 400% when no substrate was provided. A series of column experiments were carried out to measure the hydraulic conductivity of soil specimens. The results showed that the highest hydraulic conductivity reduction occurred when the substrate and electron acceptors were first introduced, and this reduction increased toward the outlet of the column. The substrate was consumed mostly at the inlet and was distributed with time. The analysis of volatile substances after the test showed that the inlet had a high organic content and the outlet had a low organic content.     

Gas-phase and transpiration-driven mechanisms for volatilization through wetland macrophytes

Natural and constructed wetlands have gained attention as potential tools for remediation of shallow sediments and groundwater contaminated with volatile organic compounds (VOCs). Wetland macrophytes are known to enhance rates of contaminant removal via volatilization, but the magnitude of different volatilization mechanisms, and the relationship between volatilization rates and contaminant physiochemical properties, remain poorly understood. Greenhouse mesocosm experiments using the volatile tracer sulfur hexafluoride were conducted to determine the relative magnitudes of gas-phase and transpiration-driven volatilization mechanisms. A numerical model for vegetation-mediated volatilization was developed, calibrated with tracer measurements, and used to predict plant-mediated volatilization of common VOCs as well as quantify the contribution of different volatilization pathways. Model simulations agree with conclusions from previous work that transpiration is the main driver for volatilization of VOCs, but also demonstrate that vapor-phase transport in wetland plants is significant, and can represent up to 50% of the total flux for compounds with greater volatility like vinyl chloride.     

Salt conditions and the effectiveness of poly(vinyl alcohol) in reclamation of saline-sodic soils

Fully hydrolysed poly (vinyl alcohol) (PVA) with molecular weight 14000 was effective in reducing or preventing clay dispersion when columns of mixed sand/Na-soil aggregates containing a wide range of NaCl salt contents were leached with distilled water. The maximum effect was obtained over a range of soil salt contents in which the applied polymer remained soluble. Above this range, because of polymer precipitation, effectiveness was inversely related to salt content. For soil aggregates with different exchangeable sodium percentage (ESPs), PVA was also effective in reducing or preventing dispersion in water and maintaining the relative hydraulic conductivity of soil columns leached successively with diluted solutions. However, a further relationship was found which showed that the polymer was more effectively incorporated in soils with higher ESP. This was reflected in measurements of dispersion and may be explained by the greater effect of drying (at 70°C) and by the greater adsorption of PVA in the presence of exchangeable sodium than exchangeable calcium.