Effect of Geochemical and Physical Heterogeneity on the Hanford 100D Area In Situ Redox Manipulation Barrier Longevity

The purpose of this study was to quantify the influence of physical and/or geochemical heterogeneities in the Hanford 100D area In Situ Redox Manipulation (ISRM) barrier, which may be contributing to the discontinuous chromate breakthrough locations along the 65-well (2,300 ft long) barrier. Possible causes of chromate breakthrough that were investigated during this study include: (1) high hydraulic conductivity zones; (2) zones of low reducible iron; and (3) high hydraulic conductivity zones with low reducible iron. This laboratory-scale investigation utilized geochemical and physical characterization data collected on 0.5 to 1 foot intervals from four borehole locations. Results of this laboratory study did not provide definitive support any of the proposed hypotheses for explaining chromate breakthrough at the Hanford 100-D Area ISRM barrier. While site characterization data indicate a significant degree of vertical variability in both physical and geochemical properties in the four boreholes investigated, lateral continuity of high conductivity/low reductive capacity zones was not observed. The one exception was at the water table, where low reductive capacity and high-K zones were observed in 3 of four boreholes. Laterally continuous high permeability zones that contain oxic sediment near the water table is the most likely explanation for high concentration chromium breakthrough responses observed at various locations along the barrier. A mechanism that could explain partial chromate breakthrough in the ISRM barrier is the relationship between the field reductive capacity and the rate of chromate oxidation. Subsurface zones with low reductive capacity still have sufficient ferrous iron mass to reduce considerable chromate, but the rate of chromate reduction slows by 1 to 2 orders of magnitude relative to sediments with moderate to high reductive capacity. The original barrier longevity estimate of 160 pore volumes for homogeneous reduced sediment, or approximately 20 years, (with 5 mg/L dissolved oxygen and 2 ppm chromate) is reduced to 85 pore volumes (10 years) when the wide spread 60 ppm nitrate plume is included in the calculation. However, this reduction in barrier lifetime is not as great for high permeability channels, as there is insufficient time to reduce nitrate (and consume ferrous iron). If the cause of laterally discontinuous breakthrough of chromate along the ISRM barrier is due to oxic transport of chromate near the water table, additional dithionite treatment in these zones will not be effective. Treatment near the water table with a technology that emplaces considerable reductive capacity is needed, such as injectable zero valent iron

Treatability Study of In Situ Technologies for Remediation of Hexavalent Chromium in Groundwater at the Puchack Well Field Superfund Site, New Jersey

This treatability study was conducted by Pacific Northwest National Laboratory (PNNL), at the request of the U. S. Environmental Protection Agency (EPA) Region 2, to evaluate the feasibility of using in situ treatment technologies for chromate reduction and immobilization at the Puchack Well Field Superfund Site in Pennsauken Township, New Jersey. In addition to in situ reductive treatments, which included the evaluation of both abiotic and biotic reduction of Puchack aquifer sediments, natural attenuation mechanisms were evaluated (i.e., chromate adsorption and reduction). Chromate exhibited typical anionic adsorption behavior, with greater adsorption at lower pH, at lower chromate concentration, and at lower concentrations of other competing anions. In particular, sulfate (at 50 mg/L) suppressed chromate adsorption by up to 50%. Chromate adsorption was not influenced by inorganic colloids

SERDP ER-1376 Enhancement of In Situ Bioremediation of Energetic Compounds by Coupled Abiotic/Biotic Processes:Final Report for 2004 - 2006

This project was initiated by SERDP to quantify processes and determine the effectiveness of abiotic/biotic mineralization of energetics (RDX, HMX, TNT) in aquifer sediments by combinations of biostimulation (carbon, trace nutrient additions) and chemical reduction of sediment to create a reducing environment. Initially it was hypothesized that a balance of chemical reduction of sediment and biostimulation would increase the RDX, HMX, and TNT mineralization rate significantly (by a combination of abiotic and biotic processes) so that this abiotic/biotic treatment may be a more efficient for remediation than biotic treatment alone in some cases. Because both abiotic and biotic processes are involved in energetic mineralization in sediments, it was further hypothesized that consideration for both abiotic reduction and microbial growth was need to optimize the sediment system for the most rapid mineralization rate. Results show that there are separate optimal abiotic/biostimulation aquifer sediment treatments for RDX/HMX and for TNT. Optimal sediment treatment for RDX and HMX (which have chemical similarities and similar degradation pathways) is mainly chemical reduction of sediment, which increased the RDX/HMX mineralization rate 100 to150 times (relative to untreated sediment), with additional carbon or trace nutrient addition, which increased the RDX/HMX mineralization rate an additional 3 to 4 times. In contrast, the optimal aquifer sediment treatment for TNT involves mainly biostimulation (glucose addition), which stimulates a TNT/glucose cometabolic degradation pathway (6.8 times more rapid than untreated sediment), degrading TNT to amino-intermediates that irreversibly sorb (i.e., end product is not CO2). The TNT mass migration risk is minimized by these transformation reactions, as the triaminotoluene and 2,4- and 2,6-diaminonitrotoluene products that irreversibly sorb are no longer mobile in the subsurface environment. These transformation rates are increased 13 times further by chemical reduction of sediment. Dithionite reduction alone is not an effective treatment for TNT (intermediates that irreversibly sorb are not produced), even though the TNT degradation rate (to 2- or 4-aminodinitrotoluene) increases

SERDP ER-1421 Abiotic and Biotic Mechanisms Controlling In Situ Remediation of NDMA: Final Report

This laboratory-scale project was initiated to investigate in situ abiotic/biotic mineralization of NDMA. Under iron-reducing conditions, aquifer sediments showed rapid abiotic NDMA degradation to dimethylamine (DMA), nitrate, formate, and finally, CO2. These are the first reported experiments of abiotic NDMA mineralization. The NDMA reactivity of these different iron phases showed that adsorbed ferrous iron was the dominant reactive phase that promoted NDMA reduction, and other ferrous phases present (siderite, iron sulfide, magnetite, structural ferrous iron in 2:1 clays) did not promote NDMA degradation. In contrast, oxic sediments that were biostimulated with propane promoted biomineralization of NDMA by a cometabolic monooxygenase enzyme process. Other monooxygenase enzyme processes were not stimulated with methane or toluene additions, and acetylene addition did not block mineralization. Although NDMA mineralization extent was the highest in oxic, biostimulated sediments (30 to 82%, compared to 10 to 26% for abiotic mineralization in reduced sediments), large 1-D column studies (high sediment/water ratio of aquifers) showed 5.6 times higher NDMA mineralization rates in reduced sediment (half-life 410 ± 147 h) than oxic biomineralization (half life 2293 ± 1866 h). Sequential reduced/oxic biostimulated sediment mineralization (half-life 3180 ± 1094 h) was also inefficient compared to reduced sediment. These promising laboratory-scale results for NDMA mineralization should be investigated at field scale. Future studies of NDMA remediation should focus on the comparison of this in situ abiotic NDMA mineralization (iron-reducing environments) to ex situ biomineralization, which has been shown successful in other studies

Factors Effecting the Fate and Transport of CL-20 in the Vadose Zone and Groundwater: Final Report 2002 - 2004 SERDP Project CP-1255

This SERDP-funded project was initiated to investigate the fate of CL-20 in the subsurface environment, with a focus on identification and quantification of geochemical and microbial reactions of CL-20. CL-20 can be released to the surface and subsurface terrestrial environment by: a) manufacturing processes, b) munition storage, and c) use with low order detonation or unexploded ordnance. The risk of far-field subsurface migration was assessed through labora-tory experiments with a variety of sediments and subsurface materials to quantify processes that control CL-20 sorption-limited migration and degradation. Results of this study show that CL-20 will exhibit differing behavior in the subsurface terrestrial environment: 1. CL-20 on the sediment surface will photodegrade and interact with plants/animals (described in other SERDP projects CU 1254, 1256). CL-20 will exhibit greater sorption in humid sediments to organic matter. Transport will be solubility limited (i.e., low CL-20 aqueous solubility). 2. CL-20 infiltration into soils (<2 m) from spills will be subject to sorption to soil organic matter (if present), and low to high biodegradation rates (weeks to years) depending on the microbial population (greater in humid environment). 3. CL-20 in the vadose zone (>2 m) will be, in most cases, subject to low sorption and low degradation rates, so would persist in the subsurface environment and be at risk for deep migration. Low water content in arid regions will result in a decrease in both sorption and the degradation rate. Measured degradation rates in unsaturated sediments of years would result in significant subsurface migration distances. 4. CL-20 in groundwater will be subject to some sorption but likely very slow degradation rates. CL-20 sorption will be greater than RDX. Most CL-20 degradation will be abiotic (ferrous iron and other transition metals), because most deep subsurface systems have extremely low natural microbial populations. Degradation rates will range from weeks (iron reducing systems) to years. Although CL-20 will move rapidly through most sediments in the terrestrial environment, subsurface remediation can be utilized for cleanup. Transformation of CL-20 to intermediates can be rapidly accomplished under: a) reducing conditions (CL-20 4.1 min. half-life, RDX 18 min. half-life), b) alkaline (pH >10) conditions, and c) bioremediation with added nutrients. CL-20 degradation to intermediates may be insufficient to mitigate environmental impact, as the toxicity of many of these compounds is unknown. Biostimulation in oxic to reducing systems by carbon and nutrient addition can mineralize CL-20, with the most rapid rates occurring under reducing conditions