Performance assessment of NAPL remediation in heterogeneous alluvium

Over the last few years, more than 40 partitioning interwell tracer tests (PITTs) have been conducted at many different sites to measure nonaqueous phase liquid (NAPL) saturations in the subsurface. While the main goal of these PITTs was to estimate the NAPL volume in the subsurface, some were specifically conducted to assess the performance of remedial actions involving NAPL removal. In this paper, we present a quantitative approach to assess the performance of remedial actions to recover NAPL that can be used to assess any NAPL removal technology. It combines the use of PITTs (to estimate the NAPL volume in the swept pore volume between injection and extraction wells of a test area) with the use of several cores to determine the vertical NAPL distribution in the subsurface. We illustrate the effectiveness of such an approach by assessing the performance of a surfactant/foam flood conducted at Hill Air Force Base, UT, to remove a TCE-rich NAPL from alluvium with permeability contrasts as high as one order of magnitude. In addition, we compare the NAPL volumes determined by the PITTs with volumes estimated through geostatistical interpolation of aquifer sediment core data collected with a vertical frequency of 5-10 cm and a lateral borehole spacing of 0.15 m. We demonstrate the use of several innovations including the explicit estimation of not only the errors associated with NAPL volumes and saturations derived from PITTs but also the heterogeneity of the aquifer sediments based upon permeability estimates. Most importantly, we demonstrate the reliability of the     

Using polymer mats to biodegrade atrazine in groundwater: laboratory column experiments

Large-scale column experiments were undertaken to evaluate the potential of in situ polymer mats to deliver oxygen into groundwater to induce biodegradation of the pesticides atrazine, terbutryn and fenamiphos contaminating groundwater in Perth, Western Australia. The polymer mats, composed of woven silicone (dimethylsiloxane) tubes and purged with air, were installed in 2-m-long flow-through soil columns. The polymer mats proved efficient in delivering dissolved oxygen to anaerobic groundwater. Dissolved oxygen concentrations increased from <0.2 mg l(-1) to approximately 4 mg l(-1). Degradation rates of atrazine in oxygenated groundwater were relatively high with a zero-order rate of 240-380 microg l(-1) or a first-order half-life of 0.35 days. Amendment with an additional carbon source showed no significant improvement in biodegradation rates, suggesting that organic carbon was not limiting biodegradation. Atrazine degradation rates estimated in the column experiments were similar to rates determined in laboratory culture experiments, using pure cultures of atrazine-mineralising bacteria. No significant degradation of terbutryn or fenamiphos was observed under the experimental conditions within the time frames of the study. Results from these experiments indicate that remediation of atrazine in a contaminated aquifer may be achievable by delivery of oxygen using an in situ polymer mat system.     

Toxicity of methyl tert-butyl ether to marine organisms: ambient water quality criteria calculation

In response to increasing concerns over the detection of methyl tert-butyl ether (MTBE) in groundwater and surface water and its potential effects in aquatic ecosystems, industry and the United States Environmental Protection Agency (USEPA) began to collaborate in 1997 to develop aquatic toxicity databases sufficient to derive ambient water quality criteria for MTBE consistent with USEPA requirements. Acute toxicity data for seven marine species, chronic toxicity data for an invertebrate, and plant toxicity data were developed to complete the saltwater database. The species tested were Cyprinodon variegatus, Gasterosteus aculeatus, Callinectes sapidus, Mytilus galloprovincialis, Palaemonetes pugio, Rhepoxynius abronius, Americamysis bahia, and Skeletonema costatum. The toxicity tests were conducted in accordance with USEPA and American Society for Testing and Materials testing procedures and Good Laboratory Practice guidelines. Data developed from this study were consistent with existing data and showed that MTBE has low acute and chronic toxicity to the marine species tested. Based upon measured MTBE concentrations, acute effects were found to range from 166 mg MTBE/l for the grass shrimp to 1950 mg MTBE/l for marine mussel. The no-observed effect concentration for the reproduction and growth of mysids was 26 mg MTBE/l during the life cycle test. The toxicity of MTBE to saltwater organisms is comparable to its toxicity to the freshwater species tested. Reported MTBE concentrations in coastal waters are several orders of magnitude lower than concentrations observed to cause effects in marine organisms.     

Induction of PAH-catabolism in mushroom compost and its use in the biodegradation of soil-associated phenanthrene

This paper describes the induction of phenanthrene-catabolism within Phase II mushroom compost resulting from its incubation with (1) phenanthrene, and (2) PAH-contaminated soil. Respirometers measuring mineralization of freshly added 14C-9-phenanthere were used to evaluate induction of phenanthrene-catabolism. Where pure phenanthrene (spiked at a concentration of 400 mg kg(-1) wet wt.) was used to induce phenanthrene-catabolism in compost, induction was measurable, with maximal mineralization observed after 7 weeks phenanthrene-compost contact time. Where PAH-contaminated soil was used to induce phenanthrene-catabolism in un-induced compost, induction was observed after 5 weeks soil-compost contact time. Microcosm-scale amelioration of soil contaminated with 14C-phenanthrene (aged in soil for 516 days prior to incubation with compost) indicated that both induced (using pure phenanthrene) and uninduced Phase II mushroom composts were equally able to promote degradation of this soil-associated contaminant. After 111 days incubation time, 42.7 +/- 6.3% loss of soil-associated phenanthrene was observed in the induced-compost soil mixture, while 36.7 +/- 2.9% loss of soil-associated phenanthrene was observed in the uninduced-compost soil mixture. These results are notable as they indicate that while pre-induction of phenanthrene-catabolism within compost is possible, it does not significantly increase the extent of degradation when the compost is used to ameliorate phenanthrene-contaminated soil. Thus, compost could be used directly in the amelioration of contaminated land i.e. without pre-induction of catabolism.     

Potential role of fire retardant-treated polyurethane foam as a source of brominated diphenyl ethers to the US environment

Five tetra- to hexabrominated diphenyl ether (BDE) congeners (BDE-47, -99, -100, -153 and -154) are the most frequently reported in wildlife and humans. The commercial penta-BDE product, used predominantly to flame-retard polyurethane foam, consists primarily of these same congeners. In 1999, North American demand accounted for 98% of the total global penta-market of 8500 metric tons. Frogs, housed with flame retardant-treated polyurethane foam as a dry substrate, accumulated 10,100 microg/kg (wet weight) of the above BDEs. Crickets kept therein as food contained 14,400 microg/kg. The crickets are believed to have browsed directly on the foam and, in turn, were consumed by the frogs. BDE congener composition in all three matrices matched that of the penta-commercial product. Similar congeners were also observed in soil and stream sediments collected near a polyurethane foam manufacturing plant. Summed concentrations of BDE-47, -99 and -100, the dominant congeners observed in these samples, ranged from < 1 to 132 microg/kg (dry weight basis). Sunfish fillets obtained from a nearby, off-site pond contained a total of 624 microg/kg (lipid basis). Sewage treatment plant (STP) sludge exhibited these same congeners at 1370 microg/kg (dry weight). BDE-209, the fully brominated congener predominant in the commercial deca-BDE product, was also present at 1470 microg/kg. While no known polyurethane foam manufacturers discharged to this plant, the distribution pattern of the low brominated congeners in the sludge matched that of the penta-product. After four weeks of exposure to ambient outdoor conditions, the surface of flame-retarded polyurethane foam became brittle and began to disintegrate. Subsequent dispersal of these penta-containing foam fragments may be one mechanism by which these BDEs reach the environment.     

Tolerance to,and avoidance of,hypoxia by the penaeid shrimp (Metapenaeus ensis)

Aquatic hypoxia caused by eutrophication may lead to mass mortality of valuable living resources such as fish and shrimp. However, there is little information on the hypoxic tolerance of penaeid shrimp, and whether they are able to avoid hypoxia. In laboratory experiments, LC50, LT50 and heart beats per minute were determined for juvenile Metapenaeus ensis at 0.5, 1.0, 2.0 and 6.0 mg O2 l(-1). The 8-h LC50, for DO was 0.77 mg O2 l(-1), while the LT50 at 0.5 mg O2 l(-1) was 399 min. Heart beat rate significantly declined when DO fell below 1.0 mg O2 l(-1). When confronted with a gradient of dissolved oxygen, M. ensis were able to avoid hypoxic areas and move to oxygenated water. M. ensis appeared to be sensitive to hypoxia, and their ability to detect and avoid hypoxia may enhance their survival in habitats where hypoxia may occur.     

Variation in CO2 assimilation rate induced by simulated dew waters with different sources of hydroxyl radical (*OH) on the needle surfaces of Japanese red pine (Pinus densifora Sieb. et Zucc.)

The hydroxyl radical (*OH) is generated in polluted dew on the needle surfaces of Japanese red pine (Pinus densiflora Sieb. et Zucc.). This free radical, which is a potent oxidant, is assumed to be a cause of ecophysiological disorders of declining trees on the urban-facing side of Mt. Gokurakuji, western Japan. Mists of *OH-generating N(III) (HNO2 and NO2-) and HOOH + Fe + oxalate solutions (50 and 100 microM, pH 5.1-5.4) simulating the dew water were applied to the foliage of pine seedlings grown in open-top chambers in the early morning. Needles treated with 100 microM N(III) tended to have a greater maximum CO2 assimilation rate (Amax), a greater stomatal conductance (g(s)) and a greater needle nitrogen content (Nneedle), suggesting that N(III) mist acts as a fertilizer rather than as a phytotoxin. On the other hand, needles treated with 100 microM HOOH + Fe + oxalate solution showed the smallest Amax, g(s), and Nneedle, suggesting that the combination of HOOH + Fe + oxalate caused a decrease in needle productivity. The effects of HOOH + Fe + oxalate mist on pine needles were very similar to the symptoms of declining trees at Mt. Gokurakuji.     

Concentration and size distribution of ultrafine particles near a major highway

Motor vehicle emissions usually constitute the most significant source of ultrafine particles (diameter <0.1 microm) in an urban environment, yet little is known about the concentration and size distribution of ultrafine particles in the vicinity of major highways. In the present study, particle number concentration and size distribution in the size range from 6 to 220 nm were measured by a condensation particle counter (CPC) and a scanning mobility particle sizer (SMPS), respectively. Measurements were taken 30, 60, 90, 150, and 300 m downwind, and 300 m upwind, from Interstate 405 at the Los Angeles National Cemetery. At each sampling location, concentrations of CO, black carbon (BC), and particle mass were also measured by a Dasibi CO monitor, an aethalometer, and a DataRam, respectively. The range of average concentration of CO, BC, total particle number, and mass concentration at 30 m was 1.7-2.2 ppm, 3.4-10.0 microg/m3, 1.3-2.0 x 10(5)/cm3, and 30.2-64.6 microg/m3, respectively. For the conditions of these measurements, relative concentrations of CO, BC, and particle number tracked each other well as distance from the freeway increased. Particle number concentration (6-220 nm) decreased exponentially with downwind distance from the freeway. Data showed that both atmospheric dispersion and coagulation contributed to the rapid decrease in particle number concentration and change in particle size distribution with increasing distance from the freeway. Average traffic flow during the sampling periods was 13,900 vehicles/hr. Ninety-three percent of vehicles were gasoline-powered cars or light trucks. The measured number concentration tracked traffic flow well. Thirty meters downwind from the freeway, three distinct ultrafine modes were observed with geometric mean diameters of 13, 27, and 65 nm. The smallest mode, with a peak concentration of 1.6 x 10(5)/cm3, disappeared at distances greater than 90 m from the freeway. Ultrafine particle number concentration measured 300 m downwind from the freeway was indistinguishable from upwind background concentration. These data may be used to estimate exposure to ultrafine particles in the vicinity of major highways.     

UV-VIS spectroscopy of 2,4,6-trinitrotoluene-hydroxide reaction

Contamination of groundwater, surface water and soil by explosives has occurred at military sites throughout the world as a result of manufacture of explosive compounds, assembly of munitions, and deployment of explosives containing devices. Due to the adverse effects of explosives on humans and other natural receptors, a low cost means of decontaminating these areas of contamination is needed. Base-induced transformation of explosives has shown promise as a rapid, low cost, and minimally resource-intensive technology for detoxifying explosives in soil and water. In order to understand the reaction mechanism, a reaction mixture of 2:1:1 (water:2,4,6-trinitrotoluene (TNT):1 N KOH) was analyzed by UV/VIS spectrometry from 190 to 1,100 nm. Time course measurements were conducted at 25, 20, 15, and 12 degrees C. A factor analysis program was used to analyze the spectral data. Principal component analysis indicated that six principal components explained the spectra to within experimental error, with four factors explaining the majority of the variance. Test spectral vectors for four components were developed, including TNT, two intermediates, and the final product, and were tested against the abstract vectors. Two possible reaction mechanisms were suggested and tested to explain the spectral data.     

Methods for collecting time/activity pattern information related to exposure to combustion products

Focus groups, surveys and questionnaires, diaries and observations can be used to gather information about people's exposure to a wide range of combustion products. Information about locations and durations of exposure, and sources of exposure can be obtained with these instruments. The types of instruments used must be fine tuned to meet the design characteristics of the community in which the study will be conducted.