Characterization and optimization of long-term controlled release system for groundwater remediation: a generalized modeling approach

A well-based reactive barrier system using controlled-release KMnO4 has been recently developed as a long-term in situ treatment option for plumes of dense and non-aqueous phase liquids in groundwater. In order to take advantage of the merits of controlled release systems (CRS) in environmental remediation, the release behavior needs to be optimized for the hydrologic and environmental conditions of target treatment zone. Where release systems are expected to be operated over long times, like for the reactive barriers, it may only be practical to describe the long-term behavior numerically. We developed a numerical model capable of describing release characteristics associated with variable forms and structures of long-term CRS. Sensitivity analyses and illustrative simulations showed that the release kinetics and durations would be constrained by changes in agent solubility, bulk diffusion coefficients, or structures of the release devices. The generality of the numerical model was demonstrated through simulations for CRS with monolithic and double-layered matrices. The generalized model was then used for actual design and analyses of an encapsulated-matrix CRS, which can yield constant release kinetics for several years. A well-based reactive barrier system (4.05 x 10(3)m3) using the encapsulated-matrix CRS can release approximately 1.65 kg of active agent (here MnO4(-)) daily over the next 6.6 yr, creating prolonged reaction zone in the subsurface. The generalized model-based, target-specific approach using the long-term CRS could provide practical tool for improving the efficacy of advanced in situ remediation schemes such as in situ chemical oxidation, bioremediation, or in situ redox manipulation. Development of techniques for adjusting the bulk diffusion coefficients of the release matrices and facilitating the lateral spreading of the released agent is warranted.     

Modeling of flow and contaminant transport in coupled stream-aquifer systems

This paper describes an integrated approach for modeling flow and contaminant transport in hydraulically connected stream-aquifer systems. The code, FTSTREAM, extended the capabilities of the ground-water model, FTWORK, to incorporate chemical fate and transport in streams. Flow in the stream network is modeled as an unsteady, spatially varying flow, while transport modeling is based on a one-dimensional advection-dispersion equation. In addition to sorption and decay during transport in ground water, the model incorporates volatilization, settling and decay during transport in surface water. The interaction between surface water and ground water is accommodated by a leakage term and is implemented in the model using an iterative Picard-type procedure to ensure mass conservation across the interface between the two systems. The modeling approach is used to simulate contaminant transport in the Mad River, Ohio, which is hydraulically connected to a buried valley aquifer of sand and gravel outwash. The river is a receiving stream in the upstream part of the modeled area. Downstream, heavy pumping from a municipal well field causes the river to become a loosing stream. Induced infiltration from the river is responsible for a considerable portion of the well yield. The flow and transport model, developed for this study, simulates coupling between flow in the aquifer and the river. Hypothetical sources of contamination are introduced at selected locations in the upstream portion of the aquifer. The model is then used to simulate the expected transport in both the aquifer and the stream. A series of simulations elucidates the role of the river in facilitating the transport of the hypothetical contaminants in ground water and surface water. Effect of sorption, retardation and volatilization on contaminant transport is also examined for the case of the volatile organic compounds.     

Ozone measurements in South Carolina using passive samplers

Passive samplers with two different collection substrates were used to obtain an average ozone concentration for 1 month during the summer of 2002 for each South Carolina county. One sampler contained a filter coated with indigo carmine, whose color fades when exposed to ozone. The fading was measured by reflectance spectroscopy. The other sampler contained filters that were coated with nitrite, which is oxidized to nitrate when exposed to ozone. The nitrate was measured by ion chromatography. Calibration curves were developed for the two methods by comparing color fading from indigo carmine and nitrate ion concentration from the nitrite filter with ambient ozone concentration measured by a co-located reference continuous UV ozone analyzer. These curves were used to calculate integrated ozone concentrations for samplers distributed across South Carolina. Using the indigo carmine method, the average ozone concentrations ranged from 21 to 64 ppb (average = 46 +/- 7.9 ppb, n = 58) across the 46 counties in the state during one summer month of 2002. Concentrations for the same time period from the nitrite-coated filters ranged from 23 to 62 ppb (average = 41 +/- 8.1 ppb, n = 58). Also for the same time period, the 23 continuous UV photometric ozone monitors operated by the South Carolina Department of Health and Environmental Control at sites within 10 miles of some of the passive monitors showed ozone concentrations ranging from 28 to 50 ppb (average = 39 +/- 6.3 ppb, n = 22).     

Relationship between the ATP content of subsurface material and the rate of biodegradation of alkylbenzenes and chlorobenzene

The rate of biotransformation of toluene in unconsolidated subsurface material from sites at Lula, Oklahoma, and Conroe, Texas, was compared to the ATP (adenosine triphosphate) content of these materials. The rate of toluene degradation decreased with decreasing ATP content. When ATP contents were at or less than 0.05 ng g⁻¹, biotransformation of toluene could not be detected (less than 1% of the initial concentration was degraded per week). At intermediate concentrations of ATP, 0.37 and 0.16 ngvg⁻¹, the rates of toluene degradation were 18 ± 4.5% and 25 ± 10% of the initial concentration per week. At ATP concentrations above 1 ng g⁻¹, the rates of toluene degradation exceeded 90% of the initial concentration per week. There was no simple relationship between ATP content and chlorobenzene degradation. Subsurface material that had been exposed to creosote wastes, and which degraded toluene rapidly, also degraded benzene, o-xylene, and m-xylene.     

Effects of consolidated tailings water on red-osier dogwood (Cornus stolonifera Michx) seedlings

As part of their tailings management, the oil sand industries plan on producing consolidated (composite) tailings (CT), in which an inorganic coagulant aid (gypsum) is added to create a non-segregating deposit. The water associated with this treatment contains potentially phytotoxic levels of sodium, sulfate, chloride, boron, aluminum, fluoride and strontium. Since CT water is expected to saturate deposits in the reclamation areas, it may affect successful reclamation of these sites. Red-osier dogwood (Cornus stolonifera Michx) was demonstrated to be relatively salt resistant and to have high potential for the reclamation of mining areas. In the present study, we used red-osier dogwood to examine the effects of CT water on the accumulation of ions within plant tissue, growth, gas exchange, water potentials and chlorophyll concentration. CT water reduced shoot lengths and dry weights in treated plants. The roots of treated plants accumulated higher concentrations of sodium and chloride than did shoots. The accumulation of sodium and chloride was accompanied by an increase in magnesium and calcium and a decrease in potassium in the roots, while the levels of potassium increased in the leaves. CT water altered gas exchange and water potentials in seedlings, and resulted in a decrease in chlorophyll's a and b. The results suggest that the mechanisms of salt resistance in red-osier dogwood seedlings involve the restriction of sodium transport from roots to shoots.     

Similarities and differences of metal distributions in the tissues of molluscs by using multivariate analyses

Multivariate analysis including correlation, multiple stepwise linear regression, and cluster analyses were applied to investigate the heavy metal concentrations (Cd, Cu, Fe, Ni, Pb, and Zn) in the different parts of bivalves and gastropods. It was also aimed to distinguish statistically the differences between the marine bivalves and the gastropods with regards to the accumulation of heavy metals in the different tissues. The different parts of four species of bivalves and four species of gastropods were obtained and analyzed for heavy metals. The multivariate analyses were then applied on the data. From the multivariate analyses conducted, there were correlations found between the soft tissues of bivalves and gastropods, but none was found between the shells and the soft tissues of most of the molluscs (except for Cerithidea obtusa and Puglina cochlidium). The significant correlations (P < 0.05) found between the soft tissues were further complemented by the multiple stepwise linear regressions where heavy metals in the total soft tissues were influenced by the accumulation in the different types of soft tissues. The present study found that the distributions of heavy metals in the different parts of molluscs were related to their feeding habits and living habitats. The statistical approaches proposed in this study are recommended for use in biomonitoring studies, since multivariate analyses can reduce the cost and time involved in identifying an effective tissue to monitor the heavy metal(s) bioavailability and contamination in tropical coastal waters.