Remediation with cyclodextrin: Recovery of the remedial agent by membrane filtration

Cyclodextrin‐enhanced flushing of contaminants from the subsurface is a promising innovative remediation technology. It will become more economically viable at more sites if methods can be developed to recover and reconcentrate the cyclodextrin solution after it has been flushed through an aquifer. The goal of this study was to determine if membrane technology is capable of meeting that need. Five membranes with different material properties were tested for this purpose in the laboratory. The results of these tests indicate that there are large differences both in the efficiency of these membranes to extract hydroxpropyl‐β‐cyclodextrin (HPCD) and their stability when exposed to trichloroethylene (TCE) at concentrations near aqueous solubility. Not only does the molecular weigh cutoff (MWCO) of a membrane determine if HPCD can be retained, but crucial selection criteria are the membrane's resistance and compatibility with TCE. Of the five membrane materials tested, only two (polymer composite membrane and polysulfone) met both these requirements. The polymer composite membrane (MPF‐44) showed reliable and stable HPCD recoveries (>95 percent) even when exposed to high TCE concentrations. The polysulfone membrane showed high HPCD recoveries, 88.5 ± 0.4 percent to 97 percent ±1 percent for ultrafiltration and nanofiltration membranes, respectively. However, membrane swelling and deterioration became a problem at high TCE concentrations (>1,000 mg/L). These problems diminished when the TCE concentration was less than 1 mg/L. Field tests demonstrated that batch mode treatment by ultrafiltration doubled the cyclodextrin concentration from 5 to 10 percent within three hours at a constant operating pressure of 13 psi. Under continuous single‐pass treatment conditions, cyclodextrin concentration also increased, although the rate of increase was much smaller than in batch mode. Overall, these tests showed that cyclodextrin recovery is possible under field conditions. © 2007 Wiley Periodicals, Inc.     

Tracer diffusion coefficients in sedimentary rocks: correlation to porosity and hydraulic conductivity

Matrix diffusion is an important transport process in geologic materials of low hydraulic conductivity. For predicting the fate and transport of contaminants, a detailed understanding of the diffusion processes in natural porous media is essential. In this study, diffusive tracer transport (iodide) was investigated in a variety of geologically different limestone and sandstone rocks. Porosity, structural and mineralogical composition, hydraulic conductivity, and other rock properties were determined. The effective diffusion coefficients were measured using the time-lag method. The results of the diffusion experiments indicate that there is a close relationship between total porosity and the effective diffusion coefficient of a rock (analogous to Archie's Law). Consequently, the tortousity factor can be expressed as a function of total porosity. The relationship fits best for thicker samples (> 1.0 cm) with high porosities (> 20%), because of the reduced influence of heterogeneity in larger samples. In general, these correlations appear to be a simple way to determine tortuosity and the effective diffusion coefficient from easy to determine rock porosity values.     

Removal of aqueous-phase polynuclear aromatic hydrocarbons using aspen wood fibers

Roadway runoff derived polynuclear aromatic hydrocarbons (PAHs) impact the quality of surface and ground water. Inexpensive aspen wood fibers have been investigated as a means to remove dissolved PAH under laboratory conditions. Our isotherm experiments demonstrated that the uptake of naphthalene, fluorene, anthracene, and pyrene required up to 12.5 days to reach equilibrium. Aspen wood-water sorption coefficients, Kww, were linearly correlated to octanol-water partition coefficients and the molecular weight of the studied PAH compounds. The correlation between Kww and molecular weight was the most significant. Column experiments were carried out to study the sorption and desorption of fluorene, anthracene, and pyrene under dynamic conditions. The results indicate linear sorption, but non-linear desorption behavior. The degree of desorption was inversely correlated to a compound's hydrophobicity. Flow interruption experiments showed that sorption and desorption was rate limited. A mass balance of the sorption and desorption tests indicated that sorptive uptake exceeded desorptive release over a given number of pore volumes. Further, absolute mass-removal efficiency increased with the molecular weight and hydrophobicity of the PAH compound. Batch and column studies demonstrated that aspen wood has the potential to become an effective remedial agent for PAH in stormwater runoff or other PAH contaminated waters.     

Cyclodextrin‐enhanced remediation of organic and metal contaminants in porous media and groundwater

Heavy metals and toxic organic contaminants are found at numerous industrial and military sites. The generally poor performance of conventional pump‐and‐treat schemes has made the development of improved methods for contaminated site remediation a significant environmental priority. One such innovative method is cyclodextrin‐enhanced flushing of the contaminated porous media and groundwater. Cyclodextrin is a glucose‐based molecule that is produced on industrial scales by microorganisms. Over the last years, several cyclodextrin derivatives have received extensive research interest. It was shown that cyclodextrins can significantly enhance the solubility of toxic organics, and in some cases, heavy metals and radioactive isotopes. As a sugar, cyclodextrin is considered relatively non‐toxic to humans, plants, and soil microbes. Thus, there are minimal health‐related concerns associated with the injection of cyclodextrin into the subsurface, which is an inherent advantage for use of cyclodextrins as a remediation agent. This paper provides a review of the available literature concerning use of cyclodextrin for remediation of groundwater and soil.     

The fate of the aqueous phase polycyclic aromatic hydrocarbon fraction in a detention pond system

The concentration of dissolved polycyclic aromatic hydrocarbons (PAH) in influent, effluent, and within a detention pond system was measured. The "soluble fraction" was operationally defined as the PAHs in solution that passed through a 1.2 μm filter. The results show that influent and effluent PAH concentrations were similar, indicating that dissolved PAH moved essentially unhindered through the detention pond system. In general, low molecular weight PAH were present at the highest concentrations and the highest PAH concentrations were measured in Summer. Also, year-to-year variations in PAH concentration were observed. At the end of sufficiently large storms, the pond was comparably unpolluted. During dry periods, the dissolved PAH concentration rose, possibly due to evapoconcentration and by partitioning of PAH from trapped contaminated sediment in the detention pond system. This study provides evidence that aqueous-phase PAH concentrations in runoff water were relatively unaffected by the passage through a conventional detention pond system.     

Long‐Term Contaminant Trends at the Picillo Farm Superfund Site in Rhode Island

Environmental disasters, such as the infamous Love Canal site or the Valley of Drums, have taken many years and consumed billions of dollars to investigate and remediate. In consequence, a large amount of geologic and hydrologic information has been gathered over the past few decades. Because of the difficulties involved with compiling this information, scientists and professionals rarely use the data to investigate the unique long‐term databases. This article presents for the first time the compilation of chemical fate and transport data from the Picillo Farm Superfund site in Rhode Island. The data cover a quarter of a century worth of geologic, hydrogeologic, and geochemical information and indicate significant changes in the contaminant inventory and the center of mass contaminant location over time. Many of these changes would have been missed if a data set of shorter duration were evaluated. Thus, compiling and evaluating data collected over many years can be extremely valuable in understanding the fate and transport of contaminants and determining the effectiveness of remediation. © 2002 Wiley Periodicals, Inc.     

Partitioning tracer tests as a remediation metric: Case study at naval amphibious base little creek,Virginia Beach,Virginia

The partitioning tracer test (PTT) is a characterization tool that can be used to quantify the porespace saturation (S_N) and spatial distribution of dense nonaqueous phase liquids (DNAPLs) in the subsurface. Because the method essentially eliminates data interpolation errors by directly measuring a relatively large subsurface volume, it offers significant promise as a remediation metric for DNAPL‐zone remediation efforts. This article presents, in detail, the design and results of field PTTs conducted before and after a DNAPL‐zone treatment at the Naval Amphibious Base Little Creek, Virginia Beach, Virginia. The results from different tracers yield a relatively large range in S_N estimates, indicating notable uncertainty and presenting significant challenges for meaningful interpretation. Several potential interpretation methods are presented, resulting in an estimated DNAPL removal range of 15 to 109 L. While this range is large, it is consistent with the DNAPL removal (～30 L) determined from analysis of effluent concentration measurements collected during the remediation efforts. At this site, the initial and final S_N values are low, and the relatively inconsistent performance of the various tracers indicates that these levels are near the lower practical quantification limit for these PTTs; however, the effective lower quantification limit for these tests is unknown. Generally, an understanding of lower quantification limits is particularly important for interpretation of post‐remediation PTTs because S_N values are likely to be low (due to remediation efforts) and the S_N estimated from the PTT may be used to predict long‐term dissolved plume behavior and assess associated environmental risk. Partitioning tracer test quantification limits are test‐specific, as they are dependent on a variety of factors including analytical uncertainty, tracer breakthrough characteristics, and tracer data integration techniques. The results of this case study indicate that methods for estimating lower quantification limits for field PTTs require further development. © 2004 Wiley Periodicals, Inc.     

Attenuation of polycyclic aromatic hydrocarbons from urban stormwater runoff by wood filters

A significant amount of contamination enters water bodies via stormwater runoff and, to reduce the amount of pollution, retention ponds are installed at many locations. While effective for treating suspended solids, retention ponds do not effectively remove dissolved constituents, such as polycyclic aromatic hydrocarbons (PAH). Previous laboratory studies demonstrates that aspen wood cuttings can be utilized to enhance the removal of dissolved contaminants. The objective of this pilot-scale field test was to determine if wood filters could effectively remove dissolved PAH from the runoff under field conditions. Four wood filter tests were conducted, lasting from 1 to 9 weeks, to determine the degree of PAH attenuation from the aqueous phase as a function of wood mass, residence times, and seasonable changes. The prototype wood filters removed on average between 18.5% and 35.6% (up to 66.5%) of the dissolved PAH contaminants. The PAH removal effectiveness of the wood was not affected by changes in water temperature or pH. The filter effectiveness increased with filter size and was highest in continuously submerged parts of the filter system. Also, heavier molecular weight PAH compounds (e.g. chrysene) were more effectively removed than lighter molecular weight compounds. Disassociation of weakly particle-bound PAH from the filter was identified as the most likely cause for a temporary drop of the wood filter's PAH load during intense storms. Simple filter design changes are likely to double the filter effectiveness and alleviate the disassociation problem.