Determination of Small Dialkyl Organophosphonates at Microgram/L Concentrations in Contaminated Groundwaters Using Multiple Extraction Membrane Disks

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Abstract
Di-isopropyl methylphosphonate (DIMP) and dimethyl methylphosphonate (DMMP), which are manufacturing by-products of. and surrogate compounds for, the nerve agents Sarin (GB) and VX, respectively, are readily quantitated at microgram per liter concentrations in contaminated groundwaters. Aqueous samples (typically 1 L) are first fortified with triethylphosphate (TEP) as a surrogate, then passed through a “sandwiched” set of three preconditioned extraction disks consisting of the following (in filtration order): (a) glass fiber filter, to remove unwanted particulate matter; (b) C18-based extraction disk, to collect DIMP; and (c) carbon-based extraction disk, to collect DMMP. The glass fiber filter is discarded; the two extraction disks are dried and extracted with a small volume of methanol. After the extract is fortified with diethyl ethylphosphonate (DEEP) internal standard, it is analyzed using a gas chromatograph equipped with a nitrogen-phosphorus detector (NPD). Quantitation of DMMP, DIMP, and TEP is performed using the method of internal standards. The procedure was used to obtain statistically-unbiased reporting limits for a “regulatory” criterion of 0.39 μg/L and a “pump and treat” criterion of 2 μg/L for both analytes. Two standardized protocols were used to validate a detection limit of 0.20 μg/L for DMMP and 0.48 μg/L for DIMP when the regulatory criterion was used as the “target concentration.” When the “pump and treat” criterion was used as the “target concentration,” the detection limits for both DMMP and DIMP were both 2 μg/L using the same protocols as for the “regulatory” criterion. The method recovery is approximately 40–50%, based on synthetic groundwaters containing between 0.2–50 μg/L of each analyte. DIMP and DMMP are cleanly resolved from each other, the internal standard, the surrogate, and the potential interference trimethylphosphate (TMP).