Zero-valent Iron Permeable Reactive Barrier Research Articles

A lumped parameter approach to model the treatment of organic contaminants by a granular iron filled fracture

Zero-valent iron permeable reactive barriers (Fe 0-PRBs) have been widely used in unconsolidated media to treat certain dissolved phase organic contaminants, but little attention has been given to their application in fractured porous media. In principle, it is possible to create a Fe 0-PRB in a fractured porous medium by injecting an iron slurry mixture into the fracture network. This emplacement method likely results in a complicated system of incompletely iron filled fractures. To aid in the design and performance assessment of such complex systems, representative models must be used that capture the essence of the controlling processes; however, existing models cannot directly account for the complex processes dominating treatment in a partly iron-filled fracture at the required spatial scale. As a first step to address this need, we have developed a modelling approach for an idealized single partly iron filled fracture wherein the physical and chemical processes are represented by a first-order lumped rate parameter. The performance of the developed lumped rate parameter model was examined over a range of conditions by comparing simulation results to those produced by a more comprehensive analytical solution and a numerical model. While some deviations were observed, the lumped parameter model was shown to be valid for a range of iron grain sizes, iron layer thicknesses, open fracture apertures, flow velocities, and reaction rate coefficients. We also demonstrated that the developed lumped parameter approach can represent situations where the system is initially contaminated, and can be used to optimize the thickness of the iron layer. The advantage of this first-order lumped rate parameter model is that it can be used directly in existing discrete fracture models without modifications to their computational framework, and hence will make it possible to approximate the field-scale treatment performance of Fe 0-PRBs in fractured porous media.

Impact of Mineral Fouling on Hydraulic Behavior of Permeable Reactive Barriers

This paper describes reactive transport simulations conducted to assess the impact of mineral fouling on the hydraulic behavior of continuous-wall permeable reactive barriers (PRBs) employing granular zero-valent iron (ZVI) in carbonate-rich alluvial aquifers. The reactive transport model included a geochemical algorithm for simulating corrosion and mineral precipitation reactions that have been observed in ZVI PRBs. Results of simulations show that porosity and hydraulic conductivity of the ZVI decrease over time and that flows are redistributed throughout the PRB in response to fouling of the pore space. Under typical conditions, only subtle changes occur within the first 10 years (i.e., duration of the current field experience record with PRBs), and the most significant changes do not occur until the PRB has operated for at least 30 years. However, changes can occur sooner (or later) if the rate at which mineral-forming ions are delivered to the PRB is higher (or lower) than that expected under typical conditions (i.e., due to higher/lower flow rate or inflowing ground water that has higher/lower ionic strength). When the PRB is more permeable than the aquifer, the median Darcy flux in the PRB does not change appreciably over time because the aquifer controls the rate of flow through the PRB. However, seepage velocities in the PRB increase, and residence times decrease, due to porosity reductions caused by accumulation of minerals in the pore space. When fouling becomes extensive, bypassing and reductions in flow rate in the PRB occur.

Chromium-Removal Processes during Groundwater Remediation by a Zerovalent Iron Permeable Reactive Barrier

Solid-phase associations of chromium were examined in core materials collected from a full-scale, zerovalent iron permeable reactive barrier (PRB) at the U.S. Coast Guard Support Center located near Elizabeth City, NC. The PRB was installed in 1996 to treat groundwater contaminated with hexavalent chromium. After eight years of operation, the PRB remains effective at reducing concentrations of Cr from average values >1500 microg L(-1) in groundwater hydraulically upgradient of the PRB to values <1 microg L(-1) in groundwater within and hydraulically downgradient of the PRB. Chromium removal from groundwater occurs at the leading edge of the PRB and also within the aquifer immediately upgradient of the PRB. These regions also witness the greatest amount of secondary mineral formation due to steep geochemical gradients that result from the corrosion of zerovalent iron. X-ray absorption near-edge structure (XANES) spectroscopy indicated that chromium is predominantly in the trivalent oxidation state, confirming that reductive processes are responsible for Cr sequestration. XANES spectra and microscopy results suggest that Cr is, in part, associated with iron sulfide grains formed as a consequence of microbially mediated sulfate reduction in and around the PRB. Results of this study provide evidence that secondary iron-bearing mineral products may enhance the capacity of zerovalent iron systems to remediate Cr in groundwater, either through redox reactions at the mineral-water interface or by the release of Fe(II) to solution via mineral dissolution and/or metal corrosion.

Site characterization to support permeable reactive barrier design

Careful design studies and selection of an effective technique for the installation of permeable reactive barriers (PRBs) are important contributors to the overall success of zero-valent iron PRBs. This article provides a case study summarizing the successful design and construction of a PRB installed at the former Carswell Air Force Base located in Fort Worth, Texas. Expedited site characterization using a cone penetrometer rig equipped with a mass spectrometer was employed to provide real-time characterization and lithologic data. These data proved to be invaluable for the design of the PRB and allowed for the development of an accurate preconstruction cost estimate. Field data gained from the expedited water quality and geologic characterization along with aquifer testing and a bench-scale treatability study provided a comprehensive basis for the design. The biopolymer slurry construction technique provided additional unanticipated benefits to the designed zero- valent iron treatment by promoting the development of anaerobic conditions favorable for microbial degradation of trichloroethene. Postconstruction monitoring data are discussed to illustrate the successful performance of the PRB. © 2005 Wiley Periodicals, Inc.

Potential artifacts in interpretation of differential breakthrough of colloids and dissolved tracers in the context of transport in a zero-valent iron permeable reactive barrier.

Many published studies have used visual comparison of the timing of peak breakthrough of colloids versus conservative dissolved tracers (hereafter referred to as dissolved tracers or tracers) in subsurface media to determine whether they are advected differently, and to elucidate the mechanisms of differential advection. This purely visual approach of determining differential advection may have artifacts, however, due to the attachment of colloids to subsurface media. The attachment of colloids to subsurface media may shift the colloidal peak breakthrough to earlier times, causing an apparent "faster" peak breakthrough of colloids relative to dissolve tracers even though the transport velocities for the colloids and the dissolved tracers may actually be equivalent. In this paper, a peak shift analysis was presented to illustrate the artifacts associated with the purely visual approach in determining differential advection, and to quantify the peak shift due to colloid attachment. This peak shift analysis was described within the context of microsphere and bromide transport within a zero-valent iron (ZVI) permeable reactive barrier (PRB) located in Fry Canyon, Utah. Application of the peak shift analysis to the field microsphere and bromide breakthrough data indicated that differential advection of the microspheres relative to the bromide occurred in the monitoring wells closest to the injection well in the PRB. It was hypothesized that the physical heterogeneity at the grain scale, presumably arising from differences in inter- versus intra-particle porosity, contributed to the differential advection of the microspheres versus the bromide in the PRB. The relative breakthrough (RB) of microspheres at different wells was inversely related to the ionic strength of ground water at these wells, in agreement with numerous studies showing that colloid attachment is directly related to solution ionic strength.