Studies of water velocity in the capillary fringe: the point velocity probe.

The point velocity probe (PVP) is a device that can measure groundwater velocity at the centimeter scale, and unlike devices that measure velocity within well screens, the PVP operates while in direct contact with the porous medium. Because of this feature, it was postulated that the PVP could be effective in measuring velocity within the capillary fringe. This hypothesis was tested using a laboratory flow-through cell filled with a medium-fine sand from Canadian Forces Base Borden. The cell was constructed to simulate conditions such that the PVP was positioned from 2.5 cm below the water table to 79 cm above the water table. As the water table was lowered, the PVP gave highly consistent values of velocity over the range equivalent to 2.5 cm below the water table to 44 cm above the water table, the approximate extent of the capillary fringe. The average measured velocity was 11.3 cm/d +/- 11.6%, somewhat higher than that calculated based on the measured discharge through the cell (7.5 cm/d +/- 5.5%). With a further decline in the water table there was a progressive decrease in the measured velocity values, consistent with the declining hydraulic conductivity as the sand material drained. Readings could not be made beyond about 57 cm, where the water content was approximately 75% of saturation. These experiments showed that the PVP is capable of measuring groundwater velocity within the saturated zone above the water table and possibly into the unsaturated zone. Currently, this is the only instrument available with this capability.

Degradation of RDX using granular iron and nickel-plated granular iron.

Using granular iron (Fe) and nickel-plated iron (Ni/Fe), this paper examines the effectiveness of these two types of reactive materials for the treatment of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), a common groundwater and soil contaminant at military facilities. RDX degraded very rapidly in the presence of both Fe and Ni/Fe in column and batch experiments. Enhancement by Ni/Fe did not prove to be effective as the half-lives of RDX ranged from 3 to 24 seconds and 3 to 11 seconds in the Fe and Ni/Fe columns, respectively. Reaction vessel experiments and estimation of the mass transfer coefficient in the column indicated that reaction kinetics was mass transfer limited. Detailed analyses of reaction intermediates and products suggest that RDX degradation proceeds through direct electron transfer processes and following to the same pathways in the presence of Fe and Ni/Fe. The formation of carbon-containing products, including formaldehyde (up to 60%), CO2 (up to 45%) and formic acid (1%) and the nitrogen containing products of ammonium (up to 48%) and N2O (up to 13%), provides convincing evidence that RDX was completely decomposed to non-toxic end products. CO2, previously reported to form only in biological or Fe-microbial combined systems, was detected as one of the main C-bearing end product. Therefore, this study shows that Fe is an effective material for remediating groundwater and industrial effluents containing RDX; and the use of additional enhancement, either biological or with Ni catalyst, does not provide additional advantages.

Influence of Na2S on the degradation kinetics of CCl4 in the presence of very pure iron.

This paper presents the results of kinetic studies to investigate the effect of FeS film formation on the degradation rate of CCl(4) by 99.99% pure metallic iron. The film was formed by submersing metallic iron grains in an oxygen free HCO(3)(-)/CO(3)(2-) electrolyte solution. When the grains had reached a quasi steady-state value of the corrosion potential, Na(2)S((aq)) was injected. Upon injection, a microm thick poorly crystalline FeS film formed immediately on the iron surface. Over time, the iron became strongly corroded and both the FeS film and the metallic iron grains began to crack leading to exposure of bare metallic iron to the solution. The effect of the surface film on the degradation rate of CCl(4) was investigated following four periods of aging, 1, 10, 30, and 60 days. Relative to the controls, the 1-day sulfide-aged iron showed a substantial decrease in rate of degradation of CCl(4.) However, over time, the rate of degradation increased and surpassed the degradation rate obtained in the controls. It has been proposed that CCl(4) is reduced to HCCl(3) by metallic iron by electron transfer. The FeS film is substantially less conducting than the bulk iron metal or non-stoichiometric magnetite and from the results of this study, greatly decreases the rate of CCl(4) degradation relative to iron that has not been exposed to Na(2)S. However, continued aging of the FeS film results in breakdown and stress-induced cracking of the film, followed by dissolution and cracking of the iron itself. The cracking of the bulk iron is believed to be a consequence of hydrogen embrittlement, which is promoted by sulfide. The increase in CCl(4) degradation rate, as the FeS films age, suggests that the process of hydrogen cracking increases the surface area available for charge transfer.

Probe for measuring groundwater velocity at the centimeter scale.

A novel method of measuring small-scale groundwater velocities in unconsolidated noncohesive media uses the travel time of a tracer pulse between an injection port and two detectors located on the surface of a cylindrical probe, called a point-velocity probe (PVP), as the basis for velocity estimation. The direction and magnitude of the water velocity vector were determined to within +/- 9% of magnitude and +/- 8 in direction, on average, in ten laboratory tank tests conducted with the PVP, when the velocities were between 5 and 98 cm/ day. Numerical simulations supported the accuracy of the underlying theory for interpretation of the PVP data and indicated that the technology is capable of measuring velocity at a very fine scale (0.5 cm around the circumference). The benchtop and modeling investigations indicated that the probe is moderately sensitive to the condition of the porous medium immediately next to the cylinder surface, suggesting that challenges exist for the deployment of the instrument in the field.

Laboratory evidence of natural remobilization of multicomponent DNAPL pools due to dissolution.

Mixtures of dense non-aqueous phase liquids (DNAPLs) trapped in the subsurface can act as long-term sources of contamination by dissolving into flowing groundwater. In general, the components of higher solubility are removed more quickly, thus altering the composition of the remaining DNAPL, and possibly leading to changes in its physical properties. Through the development of a simple compositional model, Roy et al. [J. Contam. Hydrol. 2002 (59) 163] showed that preferential dissolution of a mixed DNAPL could potentially result in changes in density and interfacial tension that could subsequently lead to remobilization of an initially static DNAPL pool. The laboratory experiments presented in this next paper provide a proof-of-concept for the previously presented theory, demonstrating and quantifying this process of remobilization. In addition, the experiments provide a data set for evaluation of the model presented by Roy et al. [J. Contam. Hydrol. 2002 (59) 163]. In the four experiments, a DNAPL pool comprised of tetrachloroethene and benzene was created as an open pool overlying glass beads within a water-saturated 2-D flow box. Experiments included rectangular and triangular pools. In each of the experiments, remobilization (as breakthrough) was observed more than 2 weeks after formation of the initial pool. During each experiment, the pool height declined as mass was lost by dissolution, while sampling indicated a decrease in the mole fraction of benzene, the more soluble component. Small protuberances formed along the bottom of the pool as its composition changed with time and the displacement pressure was achieved for various pore throats. Eventually one of the protuberances extended further, forming a finger (breakthrough). In general, the pool emptied as the finger proceeded further into the beads. It was also shown theoretically and experimentally that remobilization will occur sooner for pools with a triangular (pointing down), rather than rectangular, shape. The experimental results were simulated using the model developed by Roy et al. [J. Contam. Hydrol. 2002 (59) 163]. The model matched the observations well, suggesting that it accurately represents the primary mechanisms involved with natural remobilization under the conditions of the study.

A sequential zero valent iron and aerobic biodegradation treatment system for nitrobenzene.

The remediation of nitroaromatic contaminated groundwater is sometimes difficult because nitroaromatic compounds are resistant to biodegradation and, when they do transform, the degradation of the products may also be incomplete. A simple nitroaromatic compound, nitrobenzene, was chosen to assess the feasibility of an in situ multi-zone treatment system at the laboratory scale. The proposed treatment system consists of a zero valent granular iron zone to reduce nitrobenzene to aniline, followed by a passive oxygen release zone for the aerobic biodegradation of the aniline daughter product using pristine aquifer material from Canadian Forces Base (CFB) Borden, Ontario, as an initial microbial source. In laboratory batch experiments, nitrobenzene was found to reduce quickly in the presence of granular iron forming aniline, which was not further degraded but remained partially sorbed onto the granular iron surface. Aniline was found to be readily biodegraded with little metabolic lag under aerobic conditions using the pristine aquifer material. A sequential column experiment, containing a granular iron reducing zone and an aerobic biodegradation zone, successively degraded nitrobenzene and then aniline to below detection limits (0.5 microM) without any noticeable reduction in hydraulic conductivity from biofouling, or through the formation of precipitates.

An in situ study of the effect of nitrate on the reduction of trichloroethylene by granular iron.

The effect of nitrate on the reduction of TCE by commercial granular iron was investigated in column experiments designed to allow for the in situ monitoring of the iron surface film with Raman spectroscopy. Three column experiments were conducted; one with an influent solution of 100 mg/l nitrate+1.5 mg/l TCE, and two control columns, one saturated directly with 100 mg/l nitrate solution, the other pre-treated with Millipore water prior to the introduction of a 100 mg/l nitrate solution. In the presence of nitrate, TCE adsorbed onto the iron, but there was little TCE reduction to end-products ethene and ethane. The iron used (Connelly, GPM, Chicago) is a product typical of those used in permeable granular iron walls. The material is covered by an air-formed high-temperature oxidation film, consisting of an inner layer of Fe(3)O(4), and an outer, passive layer of Fe(2)O(3). In the control column pre-treated with Millipore water, the passive Fe(2)O(3) layer was removed upon contact with the water in a manner consistent with an autoreduction reaction. In the TCE+nitrate column and the direct nitrate saturation column, nitrate interfered with the removal of the passive layer and maintained conditions such that high valency protective corrosion species, including Fe(2)O(3) and FeOOH, were stable at the iron surface. The lack of TCE reduction is explained by the presence of these species, as they inhibit both mechanisms proposed for TCE reduction by iron, including catalytic hydrogenation, and direct electron transfer.

A fatal waterborne disease epidemic in Walkerton, Ontario: comparison with other waterborne outbreaks in the developed world.

An estimated 2,300 people became seriously ill and seven died from exposure to microbially contaminated drinking water in the town of Walkerton, Ontario, Canada in May 2000. The severity of this drinking water disaster resulted in the Government of Ontario calling a public inquiry by Mr. Justice Dennis O'Connor to address the cause of the outbreak, the role (if any) of government policies in contributing to this outbreak and, ultimately, the implications of this experience on the safety of drinking water across the Province of Ontario. The circumstances surrounding the Walkerton tragedy are an important reference source for those concerned with providing safe drinking water. Although some circumstances are obviously specific to this epidemic, others are uncomfortably reminiscent of waterborne outbreaks that have occurred elsewhere. These recurring themes suggested the need for attention to broad issues of drinking water security and they present the challenge for how drinking water safety can be managed to prevent such tragedies in the future.

Natural remobilization of multicomponent DNAPL pools due to dissolution.

Mixtures of dense nonaqueous phase liquids (DNAPLs) trapped in the subsurface can act as long-term sources of contamination by dissolving into flowing groundwater. If the components have different solubilities then dissolution will alter the composition of the remaining DNAPL. We theorized that a multicomponent DNAPL pool may become mobile due to the natural dissolution process. In this study, we focused on two scenarios: (1) a DNAPL losing light component(s), with the potential for downward migration; and (2) a DNAPL losing dense component(s), with the potential for upward migration following transformation into a less dense than water nonaqueous phase liquid (LNAPL). We considered three binary mixtures of common groundwater contaminants: benzene and tetrachloroethylene (PCE), PCE and dichloromethane (DCM), and DCM and toluene. A number of physical properties that control the retention and transport of DNAPL in porous media were measured for the mixtures, namely: density, interfacial tension, effective solubility, and viscosity. All properties except density exhibited nonlinear relationships with changing molar ratio of the DNAPL. To illustrate the potential for natural remobilization, we modelled the following two primary mechanisms: the reduction in pool height as mass is lost by dissolution, and the changes in fluid properties with changing molar ratio of the DNAPL. The first mechanism always reduces the capillary pressure in the pool, while the second mechanism may increase the capillary pressure or alter the direction of the driving force. The difference between the rate of change of each determines whether the potential for remobilization increases or decreases. Static conditions and horizontal layering were assumed along with a one-dimensional, compositional modelling approach. Our results indicated that for initial benzene/PCE ratios greater than 25:75, the change in density was sufficiently faster than the decline in pool height to promote DNAPL breakthrough into the adjacent porous medium. In contrast, there was no potential for natural remobilization of a PCE-DCM mixture, primarily because the densities of the components are not sufficiently different. Dissolution of a DCM-toluene mixture decreased the density, reducing the tendency for downward displacement. However, the ultimate transformation from a DNAPL to an LNAPL may induce upward displacement. These results suggest that at sites with DNAPL pools containing a mix of components of sufficiently different densities and relative solubilities, natural remobilization may be an active mechanism, with implications for site evaluation and remediation.

An in situ study of the role of surface films on granular iron in the permeable iron wall technology.

Permeable walls of granular iron are a new technology developed for the treatment of groundwater contaminated with dissolved chlorinated solvents. Degradation ofthe chlorinated solvents involves a charge transfer process in which they are reductively dechlorinated, and the iron is oxidized. The iron used in the walls is an impure commercial material that is covered with a passive layer of Fe2O3, formed as a result of a high-temperature oxidation process used in the production of iron. Understanding the behaviour of this layer upon contact with solution is important, because Fe2O3 inhibits mechanisms involved in contaminant reduction, including electron transfer and catalytic hydrogenation. Using a glass column specially designed to allow for in situ Raman spectroscopic and open circuit potential measurements, the passive layer of Fe2O3 was observed to be largely removed from the commercial product, Connelly iron, upon contact with Millipore water and with a solution of Millipore water containing 1.5 mg/l trichloroethylene (TCE). It has been previously shown that Fe2O3 is removed from iron surfaces upon contact with solution by an autoreduction reaction; however, prior to this work, the reaction has not been shown to occur on the impure commercial iron products used in permeable granular iron walls. The rate of removal was sufficiently rapid such that the initial presence of Fe2O3 at the iron surface would have no consequence with respect to the performance of an in situ wall. Subsequent to the removal of Fe2O3 layer, magnetite and green rust formed at the iron surface as a result of corrosion in both the Millipore water and the solution containing TCE. The formation of these two species, rather than higher valency iron oxides and oxyhydroxides, is significant for the technology. The former can interfere with contaminant degradation because they inhibit electron transfer and catalytic hydrogenation. Magnetite and green rust, in contrast, will not inhibit the mechanisms involved in contaminant reduction, and hence their formation is beneficial to the long-term performance of the iron material.

Long-term performance monitoring for a permeable reactive barrier at the U.S. Coast Guard Support Center, Elizabeth City, North Carolina.

A continuous hanging iron wall was installed in June, 1996, at the U. S. Coast Guard (USCG) Support Center near Elizabeth City, NC, United States, to treat overlapping plumes of chromate and chlorinated solvent compounds. The wall was emplaced using a continuous trenching machine whereby native soil and aquifer sediment was removed and the iron simultaneously emplaced in one continuous excavation and fill operation. To date, there have been seven rounds (November 1996, March 1997, June 1997, September 1997, December 1997, March 1998, and June 1998) of performance monitoring of the wall. At this time, this is the only full-scale continuous 'hanging' wall installed as a permeable reactive barrier to remediate both chlorinated solvent compounds and chromate in groundwater. Performance monitoring entails the following: sampling of 10-5 cm PVC compliance wells and 15 multi-level samplers for the following constituents: TCE, cis-dichloroethylene (c-DCE), vinyl chloride, ethane, ethene, acetylene, methane, major anions, metals, Cr(VI), Fe(II), total sulfides, dissolved H(2), Eh, pH, dissolved oxygen, specific conductance, alkalinity, and turbidity. Electrical conductivity profiles have been conducted using a Geoprobe to verify emplacement of the continuous wall as designed and to locate upgradient and downgradient wall interfaces for coring purposes. Coring has been conducted in November, 1996, in June and September, 1997, and March, 1998, to evaluate the rate of corrosion on the iron surfaces, precipitate buildup (particularly at the upgradient interface), and permeability changes due to wall emplacement. In addition to several continuous vertical cores, angled cores through the 0.6-m thick wall have been collected to capture upgradient and downgradient wall interfaces along approximate horizontal flow paths for mineralogic analyses.