Monitoring trichloroethene remediation at an iron permeable reactive barrier using stable carbon isotopic analysis

Stable carbon isotopic analysis, in combination with compositional analysis, was used to evaluate the performance of an iron permeable reactive barrier (PRB) for the remediation of ground water contaminated with trichloroethene (TCE) at Spill Site 7 (SS7), F.E. Warren Air Force Base, Wyoming. Compositional data indicated that although the PRB appeared to be reducing TCE to concentrations below treatment goals within and immediately downgradient of the PRB, concentrations remained higher than expected at wells further downgradient (i.e. >9 m) of the PRB. At two wells downgradient of the PRB, TCE concentrations were comparable to upgradient values, and delta13C values of TCE at these wells were not significantly different than upgradient values. Since the process of sorption/desorption does not significantly fractionate carbon isotope values, this suggests that the TCE observed at these wells is desorbing from local aquifer materials and was present before the PRB was installed. In contrast, three other downgradient wells show significantly more enriched delta13C values compared to the upgradient mean. In addition, delta13C values for the degradation products of TCE, cis-dichloroethene and vinyl chloride, show fractionation patterns expected for the products of the reductive dechlorination of TCE. Since concentrations of both TCE and degradation products drop to below detection limit in wells within the PRB and directly below it, these downgradient chlorinated hydrocarbon concentrations are attributed to desorption from local aquifer material. The carbon isotope values indicate that this dissolved contaminant is subject to local degradation, likely due to in situ microbial activity.     

Biogeochemistry of two types of permeable reactive barriers, organic carbon and iron-bearing organic carbon for mine drainage treatment: Column experiments

Permeable reactive barriers (PRBs) are an alternative technology to treat mine drainage containing sulfate and heavy metals. Two column experiments were conducted to assess the suitability of an organic carbon (OC) based reactive mixture and an Fe⁰-bearing organic carbon (FeOC) based reactive mixture, under controlled groundwater flow conditions. The organic carbon mixture contains about 30% (volume) organic carbon (composted leaf mulch) and 70% (volume) sand and gravel. The Fe⁰-bearing organic carbon mixture contains 10% (volume) zero-valent iron, 20% (volume) organic carbon, 10% (volume) limestone, and 60% (volume) sand and gravel. Simulated groundwater containing 380 ppm sulfate, 5 ppm As, and 0.5 ppm Sb was passed through the columns at flow rates of 64 (the OC column) and 62 (the FeOC column) ml d^− 1, which are equivalent to 0.79 (the OC column) and 0.78 (the FeOC column) pore volumes (PVs) per week or 0.046 m d^− 1 for both columns. The OC column showed an initial sulfate reduction rate of 0.4 µmol g (OC)^− 1 d^− 1 and exhausted its capacity to promote sulfate reduction after 30 PVs, or 9 months of flow. The FeOC column sustained a relatively constant sulfate reduction rate of 0.9 µmol g (OC)^− 1 d^− 1 for at least 65 PVs (17 months). In the FeOC column, the δ³⁴S values increase with the decreasing sulfate concentration. The δ³⁴S fractionation follows a Rayleigh fractionation model with an enrichment factor of 21.6‰. The performance decline of the OC column was caused by the depletion of substrate or electron donor. The cathodic production of H₂ by anaerobic corrosion of Fe probably sustained a higher level of SRB activity in the FeOC column. These results suggest that zero-valent iron can be used to provide an electron donor in sulfate reducing PRBs. A sharp increase in the δ¹³C value of the dissolved inorganic carbon and a decrease in the concentration of HCO₃⁻ indicate that hydrogenotrophic methanogenesis is occurring in the first 15 cm of the FeOC column.     

Influence of hydrogeochemical processes on zero-valent iron reactive barrier performance: a field investigation

Geochemical and mineralogical changes were evaluated at a field Fe0-PRB at the Oak Ridge Y-12 site concerning operation performance during the treatment of U in high NO3- groundwater. In the 5-year study period, the Fe0 remained reactive as shown in pore-water monitoring data, where increases in pH and the removal of certain ionic species persisted. However, coring revealed varying degrees of cementation. After 3.8-year treatment, porosity reduction of up to 41.7% was obtained from mineralogical analysis on core samples collected at the upgradient gravel-Fe0 interface. Elsewhere, Fe0 filings were loose with some cementation. Fe0 corrosion and pore volume reduction at this site are more severe due to the presence of NO3- at a high level. Tracer tests indicate that hydraulic performance deteriorated: the flow distribution was heterogeneous and under the influence of interfacial cementation a large portion of water was diverted around the Fe0 and transported outside the PRB. Based on the equilibrium reductions of NO3- and SO4(2-) by Fe0 and mineral precipitation, geochemical modeling predicted a maximum of 49% porosity loss for 5 years of operation. Additionally, modeling showed a spatial distribution of mineral precipitate volumes, with the maximum advancing from the interface toward downgradient with time. This study suggests that water quality monitoring, coupled with hydraulic monitoring and geochemical modeling, can provide a low-cost method for assessing PRB performance.     

Predictions of long-term performance of granular iron permeable reactive barriers: field-scale evaluation

Long-term performance is a key consideration for the granular iron permeable reactive barrier (PRB) technology because the economic benefit relies on sustainable operation for substantial periods of time. However, predictions on the long-term performance have been limited mainly because of the lack of reliable modeling tools. This study evaluated the predictive capability of a recently-developed reactive transport model at two field-scale PRBs, both having relatively high concentrations of dissolved carbonate in the native groundwater. The first site, with 8 years of available monitoring data, was a funnel-and-gate installation, with a low groundwater velocity through the gate (about 0.12 m d(-1)). The loss in iron reactivity caused by secondary mineral precipitation was small, maintaining relatively high removal rates for chlorinated organics. The simulated concentrations for most constituents in the groundwater were within the range of the monitoring data. The second site, with monitoring data available for 5 years, was a continuous wall PRB, designed for a groundwater velocity of 0.9 m d(-1). A comparison of measured and simulated aqueous concentrations suggested that the average groundwater velocity through the PRB could be lower than the design value by a factor of two or more. The distribution and amounts of carbonate minerals measured in core samples supported the decreased groundwater velocity used in the simulation. The generally good agreement between the simulated and measured aqueous and solid-phase data suggest that the model could be an effective tool for predicting long-term performance of granular iron PRBs, particularly in groundwater with high concentrations of carbonate.     

污染土壤及地下水修复的PRB技术及展望

PRB技术是一类就地修复污染土壤及地下水的新型技术 ,主要由注入井、浸提井和监测井3部分所组成。污染地区的水文地质学研究 ,是实施该技术的关键 ;化学活性物质的筛选、注入的部位、浓度、速率以及是否均匀分布 ,是该技术是否有效的关键要素。胶态零价铁PRB技术 ,被证明是一项修复由卤代烃、卤代芳烃和有机氯农药以及一些有毒金属 (如铬、硒、铀、砷和锝等 )引起的土壤及地下水污染的有效技术。尽管这些技术存在一定的弊病 ,但与传统的处理方法相比 ,其技术上的优势是十分明显的。可以预料 ,这一技术在我国有良好的应用前景