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Perchlorate (ClO4−) contamination has received increased attention the past two decades because of health concerns from its impact on thyroid function coupled with its environmental ubiquity and persistence. Here we demonstrate the detection of ClO4− below micromolar (

Techniques for rapid and sensitive detection of energetics such as cyclotrimethylenetrinitramine (RDX) are needed both for environmental and security screening applications. Here we report the use of surface enhanced Raman spectroscopy (SERS) to detect traces of RDX with good sensitivity and reproducibility. Using gold (Au) nanoparticles (~90-100 nm in diameter) as SERS substrates, RDX was detectable at concentrations as low as 0.15 mg/L in a contaminated groundwater sample. This detection limit is about two orders of magnitude lower than those reported previously using SERS techniques. A surface enhancement factor of ~6x104 was obtained. This research further demonstrates the potential for using SERS as a rapid, in-situ field screening tool for energetics detection when coupled with a portable Raman spectrometer.

A bench-scale study was conducted to assess the effectiveness of biological treatment of comingled perchlorate and hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) in ground water using fluidized bed reactors (FBRs). In addition, the ability of FBRs to treat low concentrations of perchlorate was examined. Pilot-scale FBRs were fed either acetic acid or molasses as an electron donor to facilitate simultaneous perchlorate and RDX reduction. The acetic acid-fed FBR consistently removed perchlorate from an influent level of 100 lg/L to below 6 lg/L, and values below the method detection limit of 1 lg/L occurred approximately 70% of the time. RDX breakthrough from all FBRs was minimal due to sorption of the explosive on the granulated activated carbon media, but mass balance calculations indicated that more than 99.5% of the total RDX entering the acetic acid-fed FBR was biologically degraded. Approximately 80% of the RDX fed to the control FBR (i.e., no substrate addition) was accounted for at the end of the study; the remainder was assumed to have been degraded. Molasses was much less effective than acetic acid as an electron donor for treatment of perchlorate and RDX. This work demonstrates that combined treatment of perchlorate and RDX is feasible using FBR technology, and that very low levels of perchlorate (less than 100 lg/L) can be effectively treated in an FBR.

Perchlorate has been identified as a water contaminant in 14 states, including California, Nevada, New Mexico, Arizona, Utah, and Texas, and current estimates suggest that the compound may affect the drinking water of as many as 15 million people. Biological treatment represents the most-favorable technology for the effective and economical removal of perchlorate from water. Biological fluidized bed reactors (FBRs) have been tested successfully at the pilot scale for perchlorate treatment at several sites, and two full-scale FBR systems are currently treating perchlorate-contaminated groundwater in California and Texas. A third full-scale treatment system is scheduled for start-up in early 2002. The in-situ treatment of perchlorate through addition of specific electron donors to groundwater also appears to hold promise as a bioremediation technology. Recent studies suggest that perchlorate-reducing bacteria are widely occurring in nature, including in groundwater aquifers, and that these organisms can be stimulated to degrade perchlorate to below the current analytical reporting limit (< 4 μg/l) in many instances. In this article, in-situ and ex-situ options for biological treatment of perchlorate-contaminated groundwater are discussed and results from laboratory and field experiments are presented. © 2002 Wiley Periodicals, Inc.

A study was conducted using model solids to determine whether the time-dependent decline in availability for biodegradation of organic pollutants in soil might result from the entrapment of these compounds in porous or nonporous solids. A strain of Pseudomonas mineralized phenanthrene in solid alkanes containing 18 to 32 carbons, three waxes, and low-molecular-weight polycaprolactone, polyethylene, and polypropylene. The rates were appreciably slower than when the substrate was not initially present within these nonporous solids. From 1.4 to 63.4% of the polycyclic aromatic hydrocarbon added to the solids was mineralized in 90 d. The rates and extents of partitioning of phenanthrene varied markedly among the solids. The rates of partitioning and biodegradation of phenanthrene initially present in the alkanes were positively correlated. The bacterium rapidly and extensively mineralized phenanthrene provided in calcium alginate beads containing varying amounts of soluble soil organic matter. The rates and extents of phenanthrene mineralization declined as the percentage of the substrate in the nanopores within silica particles increased, but the reductions in rate, extent, or both were less pronounced than with nonporous solids. The rate of 4-nitrophenol biodegradation also declined with increasing percentages of the compound in these nanopores. The data are consistent with hypotheses that the sequestration and consequent decrease in bioavailability of organic compounds that persist in soil result from their partitioning into organic matter or their presence within nanopores in soil.

A study was conducted to determine factors affecting the sequestration and changes in bioavailability as phenanthrene persists in soils. Phenanthrene became sequestered in seven soils differing appreciably in organic matter and clay content as measured by earthworm uptake, bacterial mineralization, or extractability. Phenanthrene also became sequestered as it aged in soil aggregates of various sizes as measured by decline in availability to a bacterium, a mild extractant, or both. Wetting and drying a soil during aging reduced the amount of phenanthrene recovered by a mild extractant and the rate and extent of bacterial mineralization of the hydrocarbon. After biodegradation of phenanthrene added to the soil, more of the compound remained if it had been aged than if it had not been aged. Wetting and drying the soil during aging further increased the amount of phenanthrene remaining after biodegradation. The rate and extent of bacterial mineralization of phenanthrene were less in leached than in unleached soil. Aging/sequestration is thus markedly affected by soil properties and environmental factors.

The primary objective of the present study was to develop inexpensive soil amendments that can be applied to enhance the adsorption of energetic compounds on military training ranges, thus limiting the potential for these compounds to migrate to groundwater. Adsorption and desorption isotherms were determined for 2,4,6-trinitrotoluene (TNT), hexahydro-1,3,5-trinitro-1,3,5- triazine (RDX), and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine with a wide variety of natural and man-made adsorbents, in- cluding wheat straw, sawdust, peat moss, ground rubber tires, and clays. Among the various adsorbents tested, peat moss proved to be the most effective sorbent for the three explosives. The adsorption coefficients ( ) for TNT and RDX with peat (310 and s Kd 87 L/kg, respectively) were at least two orders of magnitude higher than that determined for adsorption of these energetics with two surface soils. The adsorption-desorption isotherms for the explosives showed considerable hysteresis ( , ) with some of sd KK dd the solid adsorbents, suggesting that the sorption process is not readily reversible but, rather, that some fraction of the adsorbed contaminant is either irreversibly bound or present as a slowly desorbed fraction. The data indicate that the application of specific adsorbents to soils at military impact ranges may significantly improve the protection of local groundwater resources.