Rare-Earth Elements as Natural Tracers for In Situ Remediation of Groundwater.

The utility of rare-earth elements (REEs) as natural geochemical tracers for the analysis of groundwater remediation was examined in several example permeable reactive barriers (PRBs). The PRBs utilize zero-valent iron and organic carbon plus limestone mixtures for contaminant treatment. Zero-valent iron removed REEs from groundwater to below detection levels (2-4 ng/L) and subsequent rebound of REE concentrations in regions down-gradient of the treatment zones was not observed. In addition, REE concentrations within and down-gradient of an organic carbon/limestone PRB were significantly reduced to <1% of influent levels. Thus, REEs are sensitive tracers for evaluating the interaction of groundwater with materials placed in the subsurface for contaminant remediation. Analysis of geochemical tracers for understanding in situ remediation becomes important in situations where down-gradient contaminant concentrations fail to decrease within expected timeframes. The field data indicated that increased solid-phase partitioning of REEs occurred with increasing pH and heavy REEs were preferentially removed compared to light REEs in ZVI systems. In the organic carbon PRB, unexpected negative europium anomalies were observed, revealing new information about redox conditions within the treatment zone. REE concentrations and shale-normalized profiles can be used as natural tracers to better understand in situ technologies for groundwater remediation.

Geochemical and Isotope Study of Trichloroethene Degradation in a Zero-Valent Iron Permeable Reactive Barrier: A Twenty-Two-Year Performance Evaluation.

This study provides a twenty-two-year record of in situ degradation of chlorinated organic compounds by a granular iron permeable reactive barrier (PRB). Groundwater concentrations of trichloroethene (TCE) entering the PRB were as high as 10670 µg/L. Treatment efficiency ranged from 81 to >99%, and TCE concentrations from <1 µg/L to 165 µg/L were detected within and hydraulically down-gradient of the PRB. After 18 years, effluent TCE concentrations were above the maximum contaminant level (MCL) along segments of the PRB exhibiting upward trending influent TCE. Degradation products included cis-dichloroethene ( cis-DCE), vinyl chloride (VC), ethene, ethane, >C4 compounds, and possibly CO2(aq) and methane. Abiotic patterns of TCE degradation were indicated by compound-specific stable isotope data and the distribution of degradation products. δ13C values of methane within and down-gradient of the PRB varied widely from -94‰ to -16‰; these values cover most of the isotopic range encountered in natural methanogenic systems. Methanogenesis is a sink for inorganic carbon in zerovalent iron PRBs that competes with carbonate mineralization, and this process is important for understanding pore-space clogging and longevity of iron-based PRBs. The carbon isotope signatures of methane and inorganic carbon were consistent with open-system behavior and 22% molar conversion of CO2(aq) to methane.

Groundwater co-contaminant behavior of arsenic and selenium at a lead and zinc smelting facility.

Co-contaminant behavior of arsenic (As) and selenium (Se) in groundwater is examined in this study at a former lead and zinc smelting facility. We collected water quality data, including concentrations of trace metals, major ions, and metalloid speciation, over a 15-year period to document long-term trends and relationships between As, Se, geochemical parameters, and other redox-sensitive trace metals. Concentrations of dissolved As and Se were negatively correlated (Kendall's Tau B correlation coefficient, r = -0.72) and showed a distinctive L-shaped relationship. High-concentration arsenic wells (>5 mg L-1) were characterized by intermediate oxidation-reduction conditions (75 < Eh < 275 mV), near-neutral pH (6.1-7.9), low Ca/Na ratios, elevated Fe and Mn concentrations, and high proportions of As(III) relative to total dissolved As. High-concentration Se wells (>500 µg L-1) were characterized by more positive Eh (305-500 mV), low Fe concentrations, and high proportions of As(V). Batch micocosm experiments showed that aquifer solids contain mineral surfaces and/or microbial communities capable of removing selenate from groundwater. Electron microprobe and Se K-edge X-ray absorption near-edge spectroscopic analyses demonstrated that Se was predominantly associated with elemental Se in the reduced aquifer solids. Factor analysis revealed three discernible groupings of trace metals. Group I includes U, Se, and nitrate-N, all of which are mobile under oxygenated to moderately oxygenated conditions. Group II includes elements that are mobile under Fe(III)-reducing conditions: Fe, total dissolved As, As(III), and ammonium-N. Group III elements (Mo, Sb, and V) showed mobility across the entire range of redox conditions encountered in site groundwater; As(V) clustered with this group of elements. Geochemical modeling suggests that As and Se species were in a state of disequilibrium with respect to measured parameters indicative of redox conditions, although predicted patterns of redox-controlled mobility and attenuation were confirmed. This analysis is important to better understand groundwater contaminant behavior in response to redox conditions ranging from oxic/suboxic to Fe(III)-reducing, but excluding sulfate-reducing conditions.

Fifteen-year assessment of a permeable reactive barrier for treatment of chromate and trichloroethylene in groundwater.

The fifteen-year performance of a granular iron, permeable reactive barrier (PRB; Elizabeth City, North Carolina) is reviewed with respect to contaminant treatment (hexavalent chromium and trichloroethylene) and hydraulic performance. Due to in-situ treatment of the chromium source zone, reactive and hydraulic longevity of the PRB has outlived the mobile chromate plume. Chromium concentrations exceeding 3 µg/L have not been detected in regions located hydraulically down-gradient of the PRB. Trichloroethylene treatment has also been effective, although non-constant influent concentrations of trichloroethylene have at times resulted in incomplete dechlorination. Daughter products: cis-1,2-dichloroethylene, vinyl chloride, ethene, and ethane have been observed within and down-gradient of the PRB at levels <10% of the influent trichloroethylene. Analysis of potentiometric surfaces up-gradient and across the PRB suggests that the PRB may currently represent a zone of reduced hydraulic conductivity; however, measurements of the in-situ hydraulic conductivity provide values in excess of 200 m/d in some intervals and indicate no discernible loss of bulk hydraulic conductivity within the PRB. The results presented here are particularly significant because they provide the longest available record of performance of a PRB. The longevity of the Elizabeth City PRB is principally the result of favorable groundwater geochemistry and hydrologic properties of the site.

Iron hydroxy carbonate formation in zerovalent iron permeable reactive barriers: characterization and evaluation of phase stability.

Predicting the long-term potential of permeable reactive barriers for treating contaminated groundwater relies on understanding the endpoints of biogeochemical reactions between influent groundwater and the reactive medium. Iron hydroxy carbonate (chukanovite) is frequently observed as a secondary mineral precipitate in granular iron PRBs. Mineralogical characterization was carried out using X-ray diffraction, scanning electron microscopy, thermogravimetric analysis, and X-ray absorption spectroscopy on materials collected from three field-based PRBs in the US (East Helena, MT; Elizabeth City, NC; Denver Federal Center, CO). These PRBs were installed to treat a range of contaminants, including chlorinated organics, hexavalent chromium, and arsenic. Results obtained indicate that chukanovite is a prevalent secondary precipitate in the PRBs. Laboratory experiments on high-purity chukanovite separates were carried out to constrain the room-temperature solubility for this mineral. An estimated Gibbs energy of formation (Delta(f)G degrees) for chukanovite is -1174.4 +/- 6 kJ/mol. A mineral stability diagram is consistent with observations from the field. Water chemistry from the three reactive barriers falls inside the predicted stability field for chukanovite, at inorganic carbon concentrations intermediate to the stability fields of siderite and ferrous hydroxide. These new data will aid in developing better predictive models of mineral accumulation in zerovalent iron PRBs.

Performance of a zerovalent iron reactive barrier for the treatment of arsenic in groundwater: Part 1. Hydrogeochemical studies.

Developments and improvements of remedial technologies are needed to effectively manage arsenic contamination in groundwater at hazardous waste sites. In June 2005, a 9.1 m long, 14 m deep, and 1.8 to 2.4 m wide (in the direction of groundwater flow) pilot-scale permeable reactive barrier (PRB) was installed at a former lead smelting facility, located near Helena, Montana (USA). The reactive barrier was designed to treat groundwater contaminated with moderately high concentrations of both As(III) and As(V). The reactive barrier was installed over a 3-day period using bio-polymer slurry methods and modified excavating equipment for deep trenching. The reactive medium was composed entirely of granular iron which was selected based on long-term laboratory column experiments. A monitoring network of approximately 40 groundwater sampling points was installed in July 2005. Monitoring results indicate arsenic concentrations >25 mg L(-1) in wells located hydraulically upgradient of the PRB. Of 80 groundwater samples collected from the pilot-PRB, 11 samples exceeded 0.50 mg As L(-1); 62 samples had concentrations of arsenic at or below 0.50 mg L(-1); and, 24 samples were at or below the maximum contaminant level (MCL) for arsenic of 0.01 mg L(-1). After 2 years of operation, monitoring points located within 1 m of the downgradient edge of the PRB showed significant decreases in arsenic concentrations at depth intervals impacted by the emplaced zerovalent iron. This study indicates that zerovalent iron can be effectively used to treat groundwater contaminated with arsenic given appropriate groundwater geochemistry and hydrology. The study also further demonstrates the shortcomings of hanging-wall designs. Detailed subsurface characterization data that capture geochemical and hydrogeologic variability, including a flux-based analysis, are needed for successful applications of PRB technology for arsenic remediation.

In situ chemical reduction of Cr(VI) in groundwater using a combination of ferrous sulfate and sodium dithionite: a field investigation.

A field study was conducted to evaluate the performance of a ferrous iron based in situ redox zone for the treatment of a dissolved phase Cr(VI) plume at a former industrial site. The ferrous iron based in situ redox zone was created by injecting a blend of 0.2 M ferrous sulfate and 0.2 M sodium dithionite into the path of a dissolved Cr(VI) plume within a shallow medium to fine sand unconfined aquifer formation. Monitoring data collected over a period of 1020 days after more than 100 m of linear groundwater flow through the treatment zone indicated sustained treatment of dissolved phase Cr(VI) from initial concentrations between 4 and 8 mg/L to less than 0.015 mg/L. Sustained treatment is assumed to be primarily due to the reduction of Cr(VI) to Cr(III) by ferrous iron adsorbed to, precipitated on, and/or incorporated into aquifer iron (hydr)oxide solid surfaces within the treatment zone. Precipitated phases likely include FeCO3 and FeS based on saturation index considerations and SEM/EDS analysis. The detection of solid phase sulfites and thiosulfates in aquifer sediments collected from the treatment zone more than 2 years following injection suggests dithionite decomposition products may also play a significant role in the long-term treatment of the dissolved phase Cr(VI).

Iron optimization for Fenton-driven oxidation of MTBE-spent granular activated carbon.

Fenton-driven chemical oxidation of methyl tert-butyl ether (MTBE)-spent granular activated carbon (GAC) was accomplished through the addition of iron (Fe) and hydrogen peroxide (H2O2) (15.9 g/L; pH 3). The Fe concentration in GAC was incrementally varied (1020-25 660 mg/kg) by the addition of increasing concentrations of Fe solution (FeSO4-7H2O). MTBE degradation in Fe-amended GAC increased by an order of magnitude over Fe-unamended GAC and H2O2 reaction was predominantly (99%) attributed to GAC-bound Fe within the porous structure of the GAC. Imaging and microanalysis of GAC particles indicated limited penetration of Fe into GAC. The optimal Fe concentration was 6710 mg/kg (1020 mg/kg background; 5690 mg/kg amended Fe) and resulted in the greatest MTBE removal and maximum Fe loading oxidation efficiency (MTBE oxidized (microg)/ Fe loaded to GAC (mg/Kg)). At lower Fe concentrations, the H2O2 reaction was Fe limited. At higher Fe concentrations, the H2O2 reaction was not entirely Fe limited, and reductions in GAC surface area, GAC pore volume, MTBE adsorption, and Fe loading oxidation efficiency were measured. Results are consistent with nonuniform distribution of Fe, pore blockage in H2O2 transport, unavailable Fe, and limitations in H2O2 diffusive transport, and emphasize the importance of optimal Fe loading.

Enhanced removal of DNAPL trapped in porous media using simultaneous injection of cosolvent with air: influencing factors and removal mechanisms.

Factors influencing dense non-aqueous phase liquid (DNAPL) removal by concurrent injection of cosolvent and air were evaluated using micromodels and visualization techniques. Cosolvent (ethanol/water) was injected simultaneously with air into glass micromodels containing residual perchloroethylene (PCE). Impacts of the air flow rates and PCE solubility in the remedial fluid on PCE removal processes were examined. Although two major processes, immiscible displacement and dissolution, may contribute PCE removal from porous media during cosolvent-air (CA) flooding, PCE displacement occurred only in the initial flooding period and was independent of the air flow rate and ethanol content. However, faster airflow through the porous medium improved remedial fluid distribution and dynamics and resulted in enhanced dissolution of the DNAPL. Dissolution rates were directly related to PCE solubility in the remedial fluid. Enhanced contact between cosolvent and DNAPL during CA flooding was observed in a non-homogeneous micromodel with random flow paths.

Effects of pure and dyed PCE on physical and interfacial properties of remedial solutions.

Hydrophobic dyes have been used to visually distinguish dense non-aqueous phase liquid (DNAPL) contaminants from background aqueous phases and soils. The objective of this study was to evaluate the effects of a dyed DNAPL, 0.5 g Oil-Red-O/l of PCE, on the physical properties of remedial solutions: water, co-solvents (50, 70, and 90% (v/v) ethanol), and surfactants (4% (w) sodium dihexyl sulfosuccinate). This study compared the densities, viscosities, and interfacial tensions (IFTs) of the remedial solutions in contact with both dyed and undyed PCE. The presence of the dye in PCE substantially alters the IFTs of water and ethanol solutions, while there is no apparent difference in IFTs of surfactant solutions. The remedial solutions saturated with PCE showed higher viscosities and densities than pure remedial solutions. Solutions with high ethanol content exhibited the largest increases in liquid density. Because physical properties affect the flow of the remedial solutions in porous media, experiments using dyed DNAPLs should assess the influence of dyes on fluid and interfacial properties prior to remediation process analysis.

Enhanced contact of cosolvent and DNAPL in porous media by concurrent injection of cosolvent and air.

Dense nonaqueous phase liquid (DNAPL) contamination is a major environmental problem. Cosolvent flooding is proposed as a remedial alternative to water flooding. The efficacy of cosolvent flooding is a function of the degree of contact between the injected remedial fluid and the resident DNAPL Poor contact may result from remedial fluids traveling in preferential flow paths which bypass trapped DNAPL Thus, the motivation for this study was to use the preferential flow of air in porous media to enhance contact between the injected cosolvent and resident DNAPL The study evaluated concurrent injection of cosolvent and air to improve the spatial extent of DNAPL removal in porous media. A 70% ethanol/30% water (v/v) cosolvent was injected simultaneously with air into a micromodel containing residual tetrachloroethylene (PCE). Double drainage displacement was observed as a dominant DNAPL removal mechanism in the initial period of the cosolvent-air flooding (i.e., gas displaced PCE that displaced water). The residual PCE residing in the preferential paths traversed by air was readily displaced. In addition to this initial PCE mobilization, air flowing through the preferential flow paths displaced cosolvent from these paths into other flow paths and facilitated dissolution of PCE.