Remediation of DNAPL source zones with granular iron: laboratory and field tests

Degradation of dissolved chlorinated solvents using granular iron is an established in situ technology. This paper reports on investigations into mixing iron and bentonite with contaminated soil for in situ containment and degradation of dense nonaqueous phase liquid source zones. In the laboratory, hypovials containing soil, water, bentonite, iron, and free-phase trichloroethene (TCE) were assembled. Periodic measurement of TCE, chloride, and degradation products showed progressive degradation of TCE to nondetectable levels. Subsequently, a demonstration was conducted at Canadian Forces Base Borden near Alliston, Ontario, Canada, where, in 1991, a portion of the surficial aquifer was isolated and free-phase tetrachloroethene (PCE) was introduced. Using a drill rig equipped with large-diameter mixing blades, three mixed zones were prepared containing 0%, 5%, and 10% granular iron by volume. The bentonite was added to serve as a lubricant to facilitate injection of the iron and to isolate the contaminated zone. Analysis of core samples showed reasonably uniform distributions of iron through the mixed zones. Monitoring over a 13-month period following installation showed, relative to the control, a decline in PCE concentrations to virtually nondetectable values. Reaction rates in the laboratory tests were similar to those reported in the literature, while the rate in the field test was substantially lower. The lower rate may be a consequence of mass transfer limitations under the static conditions of the field test. Results indicate that mixing iron and bentonite into source zones may be an effective means of source-zone remediation, with the particular advantage of being relatively immune to effects of geologic heterogeneity.     

The Effect of the CO32- to Ca2+ Ion activity ratio on calcite precipitation kinetics and Sr2+ partitioning

Background  

A proposed strategy for immobilizing trace metals in the subsurface is to stimulate calcium carbonate precipitation and incorporate contaminants by co-precipitation. Such an approach will require injecting chemical amendments into the subsurface to generate supersaturated conditions that promote mineral precipitation. However, the formation of reactant mixing zones will create gradients in both the saturation state and ion activity ratios (i.e., ). To better understand the effect of ion activity ratios on CaCO₃ precipitation kinetics and Sr²⁺ co-precipitation, experiments were conducted under constant composition conditions where the supersaturation state (Ω) for calcite was held constant at 9.4, but the ion activity ratio was varied between 0.0032 and 4.15.     

There is no 1954 in that core! Interpreting sedimentation rates and contaminant trends in marine sediment cores

Marine sediment preserves a useful archive for contaminants and other properties that associate with particles. However, biomixing of sediments can smear the record on a scale of years to thousands of years, depending on sedimentation rate and on the depth and vigour of mixing within a particular sediment. Where such mixing occurs, dates can no longer be associated with discrete sediment depths. Nevertheless, much can still be learned from biomixed profiles, provided that mixing is accounted for. With no modelling at all, it is possible to calculate an inventory of a contaminant at a site and a maximum possible sedimentation rate, and to determine whether the contaminant has increased or decreased over time. Radiodating the core with (210)Pb permits the estimation of sedimentation and mixing rates, which can be combined with the surface contaminant concentration to estimate an approximate flux of the contaminant. Numerical models that incorporate sedimentation and mixing rates (determined using (210)Pb and other transient signals with known deposition histories) can provide the basis to propose plausible histories for contaminant fluxes.     

Conservative models: parametric entropy vs. temporal entropy in outcomes

The geologic architecture in aquifer systems affects the behavior of fluid flow and the dispersion of mass. The spatial distribution and connectivity of higher-permeability facies play an important role. Models that represent this geologic structure have reduced entropy in the spatial distribution of permeability relative to models without structure. The literature shows that the stochastic model with the greatest variance in the distribution of predictions (i.e., the most conservative model) will not simply be the model representing maximum disorder in the permeability field. This principle is further explored using the Shannon entropy as a single metric to quantify and compare model parametric spatial disorder to the temporal distribution of mass residence times in model predictions. The principle is most pronounced when geologic structure manifests as preferential-flow pathways through the system via connected high-permeability sediments. As per percolation theory, at certain volume fractions the full connectivity of the high-permeability sediments will not be represented unless the model is three-dimensional. At these volume fractions, two-dimensional models can profoundly underrepresent the entropy in the real, three-dimensional, aquifer system. Thus to be conservative, stochastic models must be three-dimensional and include geologic structure.     

Bacterial transport experiments in fractured crystalline bedrock

The efficiency of contaminant biodegradation in ground water depends, in part, on the transport properties of the degrading bacteria. Few data exist concerning the transport of bacteria in saturated bedrock, particularly at the field scale. Bacteria and microsphere tracer experiments were conducted in a fractured crystalline bedrock under forced-gradient conditions over a distance of 36 m. Bacteria isolated from the local ground water were chosen on the basis of physicochemical and physiological differences (shape, cell-wall type, motility), and were differentially stained so that their transport behavior could be compared. No two bacterial strains transported in an identical manner, and microspheres produced distinctly different breakthrough curves than bacteria. Although there was insufficient control in this field experiment to completely separate the effects of bacteria shape, reaction to Gram staining, cell size, and motility on transport efficiency, it was observed that (1) the nonmotile, mutant strain exhibited better fractional recovery than the motile parent strain; (2) Gram-negative rod-shaped bacteria exhibited higher fractional recovery relative to the Gram-positive rod-shaped strain of similar size; and (3) coccoidal (spherical-shaped) bacteria transported better than all but one strain of the rod-shaped bacteria. The field experiment must be interpreted in the context of the specific bacterial strains and ground water environment in which they were conducted, but experimental results suggest that minor differences in the physical properties of bacteria can lead to major differences in transport behavior at the field scale.     

Long-term performance of permeable reactive barriers using zero-valent iron: geochemical and microbiological effects

Geochemical and microbiological factors that control long-term performance of subsurface permeable reactive barriers were evaluated at the Elizabeth City, North Carolina, and the Denver Federal Center, Colorado, sites. These ground water treatment systems use zero-valent iron filings (Peerless Metal Powders Inc.) to intercept and remediate chlorinated hydrocarbon compounds at the Denver Federal Center (funnel-and-gate system) and overlapping plumes of hexavalent chromium and chlorinated hydrocarbons at Elizabeth City (continuous wall system). Zero-valent iron at both sites is a long-term sink for carbon, sulfur, calcium, silicon, nitrogen, and magnesium. After about four years of operation, the average rates of inorganic carbon (IC) and sulfur (S) accumulation are 0.09 and 0.02 kg/m2/year, respectively, at Elizabeth City where upgradient waters contain <400 mg/L of total dissolved solids (TDS). At the Denver Federal Center site, upgradient ground water contains 1000 to 1200 mg/L TDS and rates of IC and S accumulation are as high as 2.16 and 0.80 kg/m2/year, respectively. At both sites, consistent patterns of spatially variable mineral precipitation and microbial activity are observed. Mineral precipitates and microbial biomass accumulate the fastest near the upgradient aquifer-Fe0 interface. Maximum net reductions in porosity due to the accumulation of sulfur and inorganic carbon precipitates range from 0.032 at Elizabeth City to 0.062 at the Denver Federal Center (gate 2) after about four years. Although pore space has been lost due the accumulation of authigenic components, neither site shows evidence of pervasive pore clogging after four years of operation.     

Explaining the thinness of the fresh water lens in the Pleistocene carbonate aquifer on Andros Island, Bahamas

Two hypotheses are explored to explain the thinness of the fresh water lens on Andros Island, Bahamas. The lens is an order of magnitude thinner than predicted by the Ghyben-Herzberg theory. One hypothesis previously posed in the literature is that the base of the lens is governed by the contact between the Lucayan Formation and the pre-Lucayan limestones. An alternate hypothesis, posed here, is that thinning is caused by the hydraulic influence of low-permeability paleosols in the Lucayan Formation. These hypotheses were explored, along with the influence of recharge and other factors, using a numerical model for variable-density flow and salt transport. In the layered system of grainstones/packstones and paleosols within the Lucayan Formation itself, the velocity vectors are nearly horizontal in the grainstones/packstones, and they are nearly vertical in the paleosols. These strata above the pre-Lucayan, all lower than it in permeability, draw the base of the lens upward to a position well above the contact by significantly reducing pressure within and below the strata relative to hydrostatic pressure. It is the loss of pressure across the paleosols that dramatically thins the fresh water lens, and thus the predominant hydraulic control on lens thickness arises from the existence of paleosols.