Sung-Wook Jeen

Modeling gas formation and mineral precipitation in a granular iron column.

In granular iron permeable reactive barriers (PRBs), hydrogen gas formation, entrapment and release of gas bubbles, and secondary mineral precipitation have been known to affect the permeability and reactivity. The multicomponent reactive transport model MIN3P was enhanced to couple gas formation and release, secondary mineral precipitation, and the effects of these processes on hydraulic properties and iron reactivity. The enhanced model was applied to a granular iron column, which was studied for the treatment of trichloroethene (TCE) in the presence of dissolved CaCO(3). The simulation reasonably reproduced trends in gas formation, secondary mineral precipitation, permeability changes, and reactivity changes observed over time. The simulation showed that the accumulation of secondary minerals reduced the reactivity of the granular iron over time, which in turn decreased the rate of mineral accumulation, and also resulted in a gradual decrease in gas formation over time. This study provides a quantitative assessment of the evolving nature of geochemistry and permeability, resulting from coupled processes of gas formation and mineral precipitation, which leads to a better understanding of the processes controlling the granular iron reactivity, and represents an improved method for incorporating these factors into the design of granular iron PRBs.

Nitrate reduction and its effects on trichloroethylene degradation by granular iron

Laboratory column experiments and reactive transport modeling were performed to evaluate the reduction of nitrate and its effects on trichloroethylene (TCE) degradation by granular iron. In addition to determining degradation kinetics of TCE in the presence of nitrate, the columns used in this study were equipped with electrodes which allowed for in situ measurements of corrosion potentials of the iron material. Together with Raman spectroscopic measurements the mechanisms of decline in iron reactivity were examined. The experimental results showed that the presence of nitrate resulted in an increase in corrosion potential and the formation of thermodynamically stable passive films on the iron surface which impaired iron reactivity. The extent of the decline in iron reactivity was proportional to the nitrate concentration. Consequently, significant decreases in TCE and nitrate degradation rates and migration of degradation profiles for both compounds occurred. Furthermore, the TCE degradation kinetics deviated from the pseudo-first-order model. The results of reactive transport modeling, which related the amount of a passivating iron oxide, hematite (α-Fe2O3), to the reactivity of iron, were generally consistent with the patterns of migration of TCE and nitrate profiles observed in the column experiments. More encouragingly, the simulations successfully demonstrated the differences in performances of three columns without changing model parameters other than concentrations of nitrate in the influent. This study could be valuable in the design of iron permeable reactive barriers (PRBs) or in the development of effective maintenance procedures for PRBs treating TCE-contaminated groundwater with elevated nitrate concentrations.

Evaluation of layered and mixed passive treatment systems for acid mine drainage

ABSTRACT Laboratory column tests for passive treatment systems for mine drainage from a waste rock storage area were conducted to evaluate suitable reactive mixture, system configuration, effects of influent water chemistry, and required residence time. Five columns containing straw, chicken manure, mushroom compost, and limestone (LS), in either layered or mixed configurations, were set up to simulate the treatment system. The results showed that all of the five columns removed metals of concern (i.e. Al, Cd, Co, Cu, Fe, Ni, and Zn) with a residence time of 15 h and greater. Reaction mechanisms responsible for the removal of metals may include sulfate reduction and subsequent sulfide precipitation, precipitation of secondary carbonates and hydroxides, co-precipitation, and sorption on organic substrates and secondary precipitates. The results suggest that the mixed systems containing organic materials and LS perform better than the layered systems, sequentially treated by organic and LS layers, due to the enhanced pH adjustment, which is beneficial to bacterial activity and precipitation of secondary minerals. The column tests provide a basis for the design of a field-scale passive treatment system, such as a reducing and alkalinity producing system or a permeable reactive barrier.

Reactive transport modeling of 90Sr sorption in reactive sandpacks

Strontium-90 ((90)Sr) is one of the most problematic radioactive contaminants in groundwater at nuclear sites. Although (90)Sr is retarded relative to groundwater flow, it is sufficiently mobile and long-lived to require treatment in many hydrogeological settings. A detailed study was performed on the practicality of using granular clinoptilolite as a sandpack around groundwater wells where groundwater is contaminated with (90)Sr and the water table must be lowered. The effectiveness of the reactive sandpack concept and the mechanisms controlling (90)Sr attenuation was investigated by numerical analysis of data obtained from four in situ column experiments. The experiments spanned the range of pore-water velocities that would occur during radial flow through granular clinoptilolite sandpacks. A kinetic sorption model was required to adequately reproduce the experimentally observed (90)Sr behavior. Calibrated first-order kinetic rates were correlated with pore-water velocities. After calibration, three sorption models were used to simulate (90)Sr attenuation for four hypothetical pumping scenarios. Results show that a velocity-dependent kinetic model accurately simulates the observed early breakthrough for high pore-water velocities. The results indicate (1) that reactive sandpacks have good potential for in situ remediation and construction dewatering and (2) that quantitative modeling can aid in the design and application of this novel technique.

Degradation of chlorofluorocarbons using granular iron and bimetallic irons

Degradation of trichlorofluoromethane (CFC11) and 1,1,2-trichloro-1,2,2-trifluoroethane (CFC113) by granular iron and bimetallic (nickel- or palladium-enhanced) irons was studied in flow-through column tests. Both compounds were rapidly degraded, following pseudo-first-order kinetics with respect to the parent compounds. The average pseudo-first-order rate constants for CFC11 were similar among different materials, except for palladium-enhanced iron (PdFe), in which the rate of degradation was about two times faster than for the other materials. In the case of CFC113, the rate constants for bimetallic irons were about two to three times greater than for the regular iron material. The smaller than expected differences in degradation rate constants of chlorofluorocarbons (CFCs) between regular iron and bimetallic irons suggested little, if any, catalytic effect of the bimetallic materials in the initial degradation step. Subsequent degradation steps involved catalytic hydrogenation, however, playing a significant role in further degradation of reaction intermediates. The degradation intermediates and final products of CFC11 and CFC113 suggested that degradation proceeded through hydrogenolysis and α/β-elimination in the presence of regular iron (Fe) and nickel-enhanced iron (NiFe). Even though there is only minor benefit in the use of bimetallic iron in terms of degradation kinetics of the parent CFCs, enhanced degradation rates of intermediates such as chlorotriflouroethene (CTFE) in subsequent reaction steps could be beneficial.

Determination of rate constants and branching ratios for TCE degradation by zero-valent iron using a chain decay multispecies model

The applicability of a newly-developed chain-decay multispecies model (CMM) was validated by obtaining kinetic rate constants and branching ratios along the reaction pathways of trichloroethene (TCE) reduction by zero-valent iron (ZVI) from column experiments. Changes in rate constants and branching ratios for individual reactions for degradation products over time for two columns under different geochemical conditions were examined to provide ranges of those parameters expected over the long-term. As compared to the column receiving deionized water, the column receiving dissolved CaCO3 showed higher mean degradation rates for TCE and all of its degradation products. However, the column experienced faster reactivity loss toward TCE degradation due to precipitation of secondary carbonate minerals, as indicated by a higher value for the ratio of maximum to minimum TCE degradation rate observed over time. From the calculated branching ratios, it was found that TCE and cis-dichloroethene (cis-DCE) were dominantly dechlorinated to chloroacetylene and acetylene, respectively, through reductive elimination for both columns. The CMM model, validated by the column test data in this study, provides a convenient tool to determine simultaneously the critical design parameters for permeable reactive barriers and natural attenuation such as rate constants and branching ratios.

Geochemical interactions of mine seepage water with an aquifer: laboratory tests and reactive transport modeling

Laboratory tests and reactive transport modeling were conducted to evaluate the geochemical interactions between the seepage water from a mine waste rock dump and the nearby aquifer. In laboratory tests, the reaction of the mine seepage water with the aquifer materials increased pH, alkalinity, and dissolved Ca and Mg, whereas it decreased dissolved Fe, SO42−, and metals (Al, Zn, Cd, Cu, Cr, and Mn). Such results were mainly due to dissolution of carbonate minerals and precipitation of secondary minerals. The geochemical processes inferred from the laboratory tests (i.e., acid neutralization via dissolution of carbonates and retention of metals via precipitation of secondary minerals) were incorporated into a reactive transport model to predict the evolution of a mine seepage plume along a groundwater flow path below the waste rock dump site. The model simulations showed that dissolved metals within the plume were sequestered below non-detectable levels as a result of interactions with aquifer materials. The decreased mobility of metals was closely related to the neutralization of the acidic plume mostly due to dissolution of carbonate minerals, thus resulting in favorable geochemical conditions for the formation of secondary minerals incorporating metals (hydroxides, carbonates, and sulfides). This study helps to understand the geochemical processes governing the fate and transport of acid mine drainage in aquifers.

Bench-Scale Flushing Experiments for Remediation of Hg-Contaminated Groundwater

Bench-scale laboratory column experiments were conducted to determine the desorption characteristics of Hg in the aquifer material from an area of known elevated Hg concentrations in groundwater under flushing conditions. The experimental results showed that columns packed with perched aquifer material (PA) showed flushing of Hg, with the general decline of effluent Hg concentrations over time (from 0.05–0.1 mg/L in the beginning to 0.0001–0.003 mg/L at the end of the experiment). Columns with lower aquifer material (LA) showed nondetectable level of effluent Hg throughout the experiment. Possibility of redissolution/desorption of Hg after static condition (for the duration of 18 days) was tested, showing only slight rebound of Hg concentrations after equilibration. The results suggest that removal of up to 20% of Hg inventory in the sediment could be achievable for the duration of the experiments (about 10 pore volumes). The results also indicate that the treated water from the water treatment plant was more effective compared to deionized water, probably due to complexing agents contained in the treated water.

Modeling Geochemical and Reactivity Changes of Different Iron Materials

Including declining reactivity of iron, resulting from precipitation of secondary minerals, into reactive transport models is a key component for better estimation of longevity of iron permeable reactive barriers (PRBs). In this study, the accumulation of secondary minerals and reactivity loss were coupled using an empirically-derived relationship that was incorporated into an existing multi-component reactive transport code. The simulation results were compared to the observations from column experiments, which were designed to evaluate the changes of the reactivity of different iron materials for cis-dichloroethene (cis-DCE) treatment in the presence of dissolved CaCO3. The model provided a reasonable representation of the evolution of iron reactivity toward cis-DCE treatment and the changes in geochemical conditions for each material. The modeling results suggest that iron material having a high corrosion rate is not beneficial in the presence of a high concentration of dissolved CaCO3 because of a faster migration of cis-DCE profiles and greater porosity loss closer to the influent end. This study shows that declining reactivity of iron due to mineral precipitation should be considered at the design stage of iron PRB construction.