Inhibitor Report for: EMPA

The five-coordinate compound, Salen((t)Bu)Al(Ac), prepared in situ from Salen((t)Bu)AlBr and NH4Ac, forms Lewis acid-base adducts in aqueous solution with the G-type nerve agents, Sarin and Soman, and the VX hydrolysis product, ethylmethylphosphonate (EMPA). The resulting compounds, [Salen((t)Bu)Al(NA)](+)[Ac] (-) (with NA = Sarin, Soman, and EMPA) are sufficiently stable to be identified by ESI-MS. Molecular ion peaks were detected for every compound with little or no fragmentation. The distinctive MS signatures for the [Salen((t)Bu)Al(NA)](+) compounds provide a new technique for identifying nerve agents from aqueous solution. The energetics of the displacement of Ac(-) by the nerve agents to form [Salen((t)Bu)Al(NA)](+)[Ac](-) were determined computationally.

Among the chemical warfare agents, the extremely toxic nerve agent VX (O-ethyl S-2-(diisopropylamino)ethyl methylphosphonothioate) is a target of high importance in the development of decontamination methods, due to its indefinite persistence on common environmental surfaces. Liquid decontaminants are mostly characterized by high corrosivity, usually offer poor coverage, and tend to flow and accumulate in low areas. Therefore, the development of a noncorrosive decontaminant, sufficiently viscous to resist dripping from the contaminated surface, is necessary. In the present paper we studied different polysaccharides-thickened fluoride aqueous solutions as noncorrosive decontaminants for rapid and efficient VX degradation to the nontoxic product EMPA (ethyl methylphosphonic acid). Polysaccharides are environmentally benign, natural, and inexpensive. Other known decontaminants cannot be thickened by polysaccharides, due to the sensitivity of the latter toward basic or oxidizing agents. We found that the efficiency of VX degradation in these viscous solutions in terms of kinetics and product identity is similar to that of KF aqueous solutions. Guar gum (1.5 wt %) with 4 wt % KF was chosen for further evaluation. The benign nature, rheological properties, adhering capabilities to different surfaces, and decontamination from a porous matrix were examined. This formulation showed promising properties for implementation as a spray decontaminant for common and sensitive environmental surfaces.

This study examined the ability of activated sludge (AS) to sorb and biodegrade ethylmethylphosphonic acid (EMPA) and malathion, a degradation product and surrogate, respectively, for an organophosphate chemical warfare agent. Sorption equilibrium isotherm experiments indicate that sorption of EMPA and malathion to AS is negligible. EMPA at a concentration of 1 mg L(-1) degraded by approximately 30% with apparent first-order kinetics, possibly via co-metabolism from nitrification. Heterotrophic bacteria and abiotic mechanisms, however, are largely responsible for malathion degradation also with apparent first-order kinetics. EMPA did not inhibit chemical oxygen demand (COD) oxidation or nitrification activity, although malathion did appear to induce a stress response resulting in inhibition of COD oxidation. The study also included a 30-day experiment in which malathion, at a concentration of 5 mg L(-1), was repeatedly fed to AS in bench-scale sequencing batch reactors (SBRs) operating at different solids retention times (SRTs). Peak malathion concentrations occurred at day 4.5, with the longer SRTs yielding greater peak malathion concentrations. The AS reduced the malathion concentrations to nearly zero by day 10 for all SRTs, even when the malathion concentration in the influent increased to 20.8 mg L(-1). The data suggest a biodegradation pathway for malathion involving an oxygenase. Phylogenetic analyses revealed that all samples had an abundance of Zoogloea, though there was greater bacterial diversity in the SBR with the SRT of 50 days. The SBR with an SRT of 9.5 days had an apparent reduction in the diversity of the bacterial community.

The five-coordinate compound, Salen((t)Bu)Al(Ac), prepared in situ from Salen((t)Bu)AlBr and NH4Ac, forms Lewis acid-base adducts in aqueous solution with the G-type nerve agents, Sarin and Soman, and the VX hydrolysis product, ethylmethylphosphonate (EMPA). The resulting compounds, [Salen((t)Bu)Al(NA)](+)[Ac] (-) (with NA = Sarin, Soman, and EMPA) are sufficiently stable to be identified by ESI-MS. Molecular ion peaks were detected for every compound with little or no fragmentation. The distinctive MS signatures for the [Salen((t)Bu)Al(NA)](+) compounds provide a new technique for identifying nerve agents from aqueous solution. The energetics of the displacement of Ac(-) by the nerve agents to form [Salen((t)Bu)Al(NA)](+)[Ac](-) were determined computationally.

Among the chemical warfare agents, the extremely toxic nerve agent VX (O-ethyl S-2-(diisopropylamino)ethyl methylphosphonothioate) is a target of high importance in the development of decontamination methods, due to its indefinite persistence on common environmental surfaces. Liquid decontaminants are mostly characterized by high corrosivity, usually offer poor coverage, and tend to flow and accumulate in low areas. Therefore, the development of a noncorrosive decontaminant, sufficiently viscous to resist dripping from the contaminated surface, is necessary. In the present paper we studied different polysaccharides-thickened fluoride aqueous solutions as noncorrosive decontaminants for rapid and efficient VX degradation to the nontoxic product EMPA (ethyl methylphosphonic acid). Polysaccharides are environmentally benign, natural, and inexpensive. Other known decontaminants cannot be thickened by polysaccharides, due to the sensitivity of the latter toward basic or oxidizing agents. We found that the efficiency of VX degradation in these viscous solutions in terms of kinetics and product identity is similar to that of KF aqueous solutions. Guar gum (1.5 wt %) with 4 wt % KF was chosen for further evaluation. The benign nature, rheological properties, adhering capabilities to different surfaces, and decontamination from a porous matrix were examined. This formulation showed promising properties for implementation as a spray decontaminant for common and sensitive environmental surfaces.

This study examined the ability of activated sludge (AS) to sorb and biodegrade ethylmethylphosphonic acid (EMPA) and malathion, a degradation product and surrogate, respectively, for an organophosphate chemical warfare agent. Sorption equilibrium isotherm experiments indicate that sorption of EMPA and malathion to AS is negligible. EMPA at a concentration of 1 mg L(-1) degraded by approximately 30% with apparent first-order kinetics, possibly via co-metabolism from nitrification. Heterotrophic bacteria and abiotic mechanisms, however, are largely responsible for malathion degradation also with apparent first-order kinetics. EMPA did not inhibit chemical oxygen demand (COD) oxidation or nitrification activity, although malathion did appear to induce a stress response resulting in inhibition of COD oxidation. The study also included a 30-day experiment in which malathion, at a concentration of 5 mg L(-1), was repeatedly fed to AS in bench-scale sequencing batch reactors (SBRs) operating at different solids retention times (SRTs). Peak malathion concentrations occurred at day 4.5, with the longer SRTs yielding greater peak malathion concentrations. The AS reduced the malathion concentrations to nearly zero by day 10 for all SRTs, even when the malathion concentration in the influent increased to 20.8 mg L(-1). The data suggest a biodegradation pathway for malathion involving an oxygenase. Phylogenetic analyses revealed that all samples had an abundance of Zoogloea, though there was greater bacterial diversity in the SBR with the SRT of 50 days. The SBR with an SRT of 9.5 days had an apparent reduction in the diversity of the bacterial community.

The catalytic degradation of the nerve agent VX (O-ethyl S-2-(diisopropylamino)ethyl methylphosphonothioate) by water-swelled polymer-supported ammonium fluorides is described. VX (0.06-0.53 mol/mol F(-)) is rapidly degraded (t(1/2) approximately 10-30 min) to form the "G-analogue" (O-ethyl methylphosphonofluoridate), which hydrolyzes (t(1/2) approximately 1-1.5 h) to the nontoxic EMPA (ethyl methylphosphonic acid). The toxic desethyl-VX is not formed. The catalytic effect of fluoride is maintained even when 6 equiv of VX are loaded. GB (O-isopropyl methylphosphonofluoridate) and desethyl-VX agents are also degraded under these conditions.

The fate of the persistent OP nerve agent O-ethyl S-[2-(diisopropylamino)ethyl] methylphosphonothioate (VX) on granular activated carbons that are used for gas filtration was studied by means of 31P magic angle spinning (MAS) NMR spectroscopy. VX as vapor or liquid was adsorbed on carbon granules, and MAS NMR spectra were recorded periodically. The results show that at least 90% of the adsorbed VX decomposes within 20 days or less to the nontoxic ethyl methylphosphonic acid (EMPA) and bis(S-2-diisopropylaminoethane) {(DES)2}. Decomposition occurred irrespective of the phase from which VX was loaded, the presence of metal impregnation on the carbon surface, and the water content of the carbon. Theoretical and practical aspects of the degradation are discussed.

The nerve agent VX (O-ethyl S-2-diisopropylaminoethyl methyl phosphonothiolate) was analyzed on the surface of concrete samples using an ion trap secondary ion mass spectrometer (IT-SIMS). It was found that VX could be detected down to an absolute quantity of 5 ng on a concrete chip, or to a surface coverage of 0.0004 monolayers on crushed concrete. To achieve these levels of detection, the m/z 268-->128 ion fragmentation was measured using MS2, where m/z 268 corresponds to [VX + H]+, and 128 corresponds to a diisopropylvinylammonium isomer, that is formed by the elimination of the phosphonothiolate moiety. Detection at these levels was accomplished by analyzing samples that had been recently exposed to VX, i.e., within an hour. When the VX-exposed concrete samples were aged, the SIMS signature for intact VX had disappeared, which signaled the degradation of the compound on the concrete surface. The VX signature was replaced by ions which are interpreted in terms of VX degradation products, which appear to be somewhat long lived on the concrete surface. These compounds include ethylmethylphosphonic acid (EMPA), diisopropyl taurine (DIPT), diisopropylaminoethanethiol (DESH), bis(diisopropylaminoethane) disulfide [(DES)2], and a particularly tenacious compound that may correspond to diisopropylvinylamine (DIVA), or an isomer thereof. It was found that the thiolamine-derived degradation products DIPT, DESH, and (DES)2 were removed with isopropyl alcohol extraction. However, the DIVA-related degradation product was observed to strongly adhere to the concrete surface for longer than one week. Although quantitation was not possible in this set of experiments, the results clearly show the rapid degradation of VX on concrete, as well as the surface sensitivity of the IT-SIMS for intact VX and its adsorptive degradation products.

A method of detecting signature methylphosphonic acid (MPA) breakdown products of V and G nerve agents in environmental samples was developed using capillary ion electrophoresis with conductivity detection. The electrolyte (30 mM L-histidine, 30 mM 2-(N-morpholino)ethanesulfonic acid, 0.7 mM tetradecyltrimethylammonium hydroxide, and 0.03 weight% Triton X-100) allowed baseline separation of MPA, ethyl methylphosphonic acid (EMPA), isopropyl methylphosphonic acid (IMPA), and pinacolyl methylphosphonic acid (PMPA) in less than 10 min. Detector response was linear in the 6-60 micrograms/ml concentration range (correlation coefficient = 0.99) with a detection limit around 6 micrograms/ml. The application of this method for screening MPA, EMPA, IMPA, and PMPA in surface water, groundwater, and soil extracts is demonstrated.

For the unequivocal proof of the use of a nerve agent O-ethyl S-2-diisopropylaminoethyl methylphosphonothiolate (VX), a rapid, accurate and sensitive method which allows us to identify its main hydrolysis product ethyl methylphosphonic acid (EMPA) in human serum was explored by GC-MS. GC-MS analysis was performed after solvent extraction with acetonitrile in acidic conditions from the serum sample, which was previously deproteinized by micro-ultrafiltration, and subsequent tert.-butyldimethylsilyl derivatization with N-methyl-N-(tert.-butyldimethylsilyl)trifluoroacetamide (MTBSTFA) with 1% tert.-butyldimethylsilyl chloride (t-BDMSC). Linear calibration curves were obtained in the concentration range from 50 to 500 ng/ml for EMPA in the full-scan EI mode and from 5 to 50 ng/ml for EMPA in the SIM EI mode. The relative standard deviation obtained at a sample concentration of 50 ng/ml was 8.4% in the full-scan mode and 7.3% in the SIM mode. Upon applying the full-scan EI and CI mode, 40 ng/ml and 80 ng/ml were the detection limits. Using the SIM-EI mode, in which the ion at m/z 153 was chosen, the limit was 3 ng/ml.