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The rate of degradation of the chemical warfare agent sulfur mustard, bis(2-chloroethyl) sulfide, was measured on ambient and moist concrete using (13)C Solid State Magic Angle Spinning Nuclear Magnetic Resonance (SSMAS NMR). Three samples of concrete made by the same formulation, but differing in age and alkalinity were used. The sulfur mustard eventually degraded to thiodiglycol and 1,4-oxathiane via the intermediate sulfonium ions CH-TG, H-TG, H-2TG and O(CH(2)CH(2))(2)S(+)CH(2)CH(2)OH on all of the concrete samples, and in addition formed 8-31% vinyl moieties on the newer, more alkaline concrete samples. This is the first observation of the formation of O(CH(2)CH(2))(2)S(+)CH(2)CH(2)OH on a solid substrate. The addition of 2-chloroethanol to concrete on which mustard had fully degraded to thiodiglycol and 1,4-oxathiane resulted in the formation of O(CH(2)CH(2))(2)S(+)CH(2)CH(2)OH, thus demonstrating the reversibility of sulfur mustard degradation pathways. The sulfur mustard degradation half-lives on ambient concrete at 22 degrees C ranged from 3.5 to 54 weeks. When the substrates were moistened, the degradation half-lives at 22 degrees C ranged from 75 to 350h. The degradation of sulfur mustard occurred more quickly at elevated temperatures and with added water. The non-volatile toxic sulfonium ions persisted for months to years on concrete at 22 degrees C and weeks to months on concrete at 35 degrees C, before decomposing to the relatively non-toxic compounds thiodiglycol and 1,4-oxathiane.

High surface area (887.3m(2)/g) silica nanoparticles were synthesized using aerogel route and thereafter, characterized by N(2)-Brunauer-Emmet-Teller (BET), SEM and TEM techniques. The data indicated the formation of nanoparticles of silica in the size range of 24-75 nm with mesoporous characteristics. Later, these were impregnated with reactive chemicals such as N-chloro compounds, oxaziridines, polyoxometalates, etc., which have already been proven to be effective against sulphur mustard (HD). Thus, developed novel mesoporous reactive sorbents were tested for their self-decontaminating feature by conducting studies on kinetics of adsorptive removal of HD from solution. Trichloroisocyanuric acid impregnated silica nanoparticles (10%, w/w)-based system was found to be the best with least half-life value (t(1/2)=2.8 min) among prepared systems to remove and detoxify HD into nontoxic degradation products. Hydrolysis, dehydrohalogenation and oxidation reactions were found to be the route of degradation of HD over prepared sorbents. The study also inferred that 10% loading of impregnants over high surface area and low density silica nanoparticles enhances the rate of reaction kinetics and seems to be useful in the field of heterogeneous reaction kinetics.

A facile solvent-free hydrolysis (chemical destruction) of the warfare agents VX (O-ethyl S-2-(diisopropylamino)ethyl methylphosphonothioate), GB (O-isopropyl methylphosphonofluoridate or sarin), and HD (2,2'-dichloroethyl sulfide or sulfur mustard) upon reaction with various solid-supported fluoride reagents is described. These solid reagents include different alumina-based powders such as KF/Al(2)O(3), AgF/KF/Al(2)O(3), and KF/Al(2)O(3) enriched by so-called coordinatively unsaturated fluoride ions (termed by us as ECUF-KF/Al(2)O(3)). When adsorbed on these sorbents, the nerve agent VX quickly hydrolyzed (t(1/2) range between 0.1-6.3 h) to the corresponding nontoxic phosphonic acid EMPA as a major product (>90%) and to the relatively toxic desethyl-VX (<10%). The latter byproduct was further hydrolyzed to the nontoxic MPA product (t(1/2) range between 2.2-161 h). The reaction rates and the product distribution were found to be strongly dependent on the nature of the fluoride ions in the KF/Al(2)O(3) matrix and on its water content. All variations of the alumina-supported fluoride reagents studied caused an immediate hydrolysis of the highly toxic GB (t(1/2) < 10 min) to form the corresponding nontoxic phosphonic acid IMPA. A preliminary study of the detoxification of HD on these catalyst supports showed the formation of the nontoxic 1,4-thioxane as a major product together with minor amounts of TDG and vinylic compounds within a few days. The mechanisms and the efficiency of these processes were successfully studied by solid-state (31)P, (13)C, and (19)F MAS NMR.

Efficient photocatalytic decomposition of chemical warfare agents is a process that may find application in emergency situations or for the controlled destruction of chemical warfare stockpiles. A series of heterogeneous photocatalysts comprising TiO2-activated carbon or N-TiO2-activated carbon composites exhibit excellent photocatalytic activity to effect the complete decomposition of yperite, soman, and VX in high concentrations. The remarkable photocatalytic activity arises from the synergism between adsorption on active carbon and photoactivity by titania. Nitridation makes the composite also active under visible-light irradiation.

Sulphur Mustard, or "Mustard Gas" is in fact an oily liquid which was used as a chemical weapon primarily for its vesicant action which necessitates whole body protection. It is also now recognised as a carcinogenic agent upon chronic exposure. Soil contaminated with Sulphur Mustard continues to present both acute and chronic human health risks and risks to groundwater, surface water and the wider ecology at a number of sites globally and, in some cases, has done for many decades. This is at odds with the simple aqueous chemistry of the compound which would suggest that it should be short lived in the environment, especially in the presence of water. A number of studies have examined the possible factors for this longevity and, though the causes are generally assumed to be understood, the precise reasons have not yet been definitively determined and the evidence in support of the existing theories is at best circumstantial. At present, the prevailing view is that Sulphur Mustard is somehow protected by oligomeric or polymeric sulphonium species produced during incomplete hydrolysis reactions. The following review discusses the pertinent degradation mechanisms in the environment; hydrolysis and thermal degradation and the reasons put forward for the longevity of Sulphur Mustard in the literature. Other factors, such as the role of polymeric species in Sulphur Mustard droplets in modifying the mobility of the agent are also examined. Ultimately, without a thorough understanding of the abiotic fate of the Sulphur Mustard, uncertainties will remain in the application of risk assessment and remediation strategies to such sites, potentially compromising the validity or effectiveness of such actions.

The rate constants and product ion branching ratios have been measured in a selected ion flow tube (SIFT) at 298 K for a variety of positive and negative ions reacting with 2-chloroethyl ethyl sulfide (2-CEES), a surrogate for mustard gas (HD). This series of experiments is designed to elucidate ion-molecule reactions that have large rate constants and produce unique product ions to guide the development of chemical ionization mass spectrometry (CIMS) detection methods for the chemical weapon agent using the surrogate instead. The negative ions typically used in CIMS instruments are essentially unreactive with 2-CEES, that is, SF 6 (-), SF 4 (-), CF 3O (-), and CO 3 (-). A few negative ions such as NO 2 (-) and NO 3 (-) undergo three-body association to give a unique product ion, but the bimolecular rate constants are small in the SIFT. Positive ions typically react at the collisional limit, primarily by charge and proton transfer, some of which is dissociative. For ions with high proton binding energies, association with 2-CEES has also been observed. Many of these reactions produced ions with the 2-CEES intact, including the parent cation, the protonated cation, and clusters. G3(MP2) calculations of the thermochemical properties for 2-CEES and mustard have been performed, along with calculations of the structures for the observed product cations. Reacting a series of protonated neutral molecules with 2-CEES brackets the proton affinity (PA) to between 812 ((CH 3) 2CO) and 854 (NH 3) kJ mol (-1). G3(MP2) calculations give a PA for 2-CEES of 823 kJ mol (-1) and a PA for mustard of 796 kJ mol (-1), indicating that the present results for 2-CEES should be directly transferable to mustard to design a CIMS detection scheme.

Rapid monitoring and retrospective verification are key issues in protection against and non-proliferation of chemical warfare agents (CWA). Such monitoring and verification are adequately accomplished by the analysis of persistent protein adducts of these agents. Liquid chromatography-mass spectrometry (LC-MS) is the tool of choice in the analysis of such protein adducts, but the overall experimental procedure is quite elaborate. Therefore, an automated on-line pepsin digestion-LC-MS configuration has been developed for the rapid determination of CWA protein adducts. The utility of this configuration is demonstrated by the analysis of specific adducts of sarin and sulfur mustard to human butyryl cholinesterase and human serum albumin, respectively.

Sulfur-containing compounds, such as mercaptans, alkali sulfides, alkali sulfites, and alkali thiosulfates, are byproducts of industrial processes and pollutants of waste and natural waters. Other sulfur-containing compounds such as yperite are dangerous chemical weapons. Efficient photocatalytic decomposition of these molecules is a process that can find applications in emergency situations or for the controlled destruction of chemical warfare stockpiles. A series of heterogeneous photocatalysts consisting of a metal phthalocyanine or 2,4,6-triphenylpyrylium as photoactive components encapsulated inside the cavities of zeolite Y or the mesoporous channels of MCM-41 or supported on silica or titania-silica was tested for the photocatalytic decomposition of yperite. Two types of photoreactors, either an open reactor naturally aerated or a closed quartz tube with a constant airflow using UV or visible ambient light were used. These tests demonstrated that iron and manganese phthalocyanine and 2,4,6-triphenylpyrylium embedded in NaY or titania-silica can be suitable solid photocatalysts for the degradation of yperite using UV and visible irradiation.

Numerous methods are used for destruction of sulfur mustard. Oxidation is one of those methods. There have been only limited data concerning application of the advanced oxidation technologies (AOTs) for mustard destruction available before. In this study sulfur mustard oxidation rate depending on kind of the oxidative system and process parameters used was assessed using selected AOT. The following were selected for mustard oxidation: ozone (O(3)), UV light (UV), hydrogen peroxide (H(2)O(2)); double systems: UV/O(3), UV/H(2)O(2), and O(3)/H(2)O(2); a triple system: O(3)/H(2)O(2)/UV and Fenton reaction. Effectiveness of the selected AOT methods has been evaluated and the most suitable one for mustard destruction was chosen. Using ozone in various combinations with hydrogen peroxide and UV radiation mustard can be destroyed much quicker comparing to the classical oxidizers. Fast mustard oxidation (a few minutes) occurred in those systems where ozone alone was used, or in the following combinations: O(3)/H(2)O(2), O(3)/UV and O(3)/H(2)O(2)/UV. When those advanced oxidation technologies are used, mustard becomes destroyed mainly in course of the direct oxidation with ozone, and reactions of mustard with radicals formed due to ozone action play a secondary role. Rate of sulfur mustard oxidation in the above mentioned ozone-containing oxidative systems decreases with pH value increasing from 2 to 12. Only when pH value of reaction solutions is close to pH 5, mustard oxidation rate is minimal, probably due to "disappearance" of radicals participating in oxidation in this pH. Sulfur mustard can be most effectively destroyed using just ozone in pH 7. In that case mustard destruction rate is only slightly lower than the rate achieved in optimal conditions, and the system is the simplest.

Objective: To increase awareness of the widespread environmental prevalence of the chemical warfare agent mustard gas, examine the acute and chronic toxic effects to exposed humans, and discuss medical treatment guidelines for mustard gas exposures., Data Sources: Literature retrieval of medical case reports and clinical studies was accomplished using PubMed and the Cochrane Database (1919-March 2007). Search terms included mustard, mustard gas, sulfur mustard, chemical warfare, blister agents, vesicants, and war gas. Historical information and current events were accessed through military field manuals and Internet searches., Study Selection and Data Extraction: All articles in English identified from the data sources were evaluated. Adult and pediatric populations were included in the review., Data Synthesis: Mustard gas and other chemical weapons are feared for their use as weapons of terror; however, the major threat of mustard gas lies elsewhere. Tons of this chemical agent were produced for war, then subsequently buried in landfills, disposed of at sea, or left to decay in storage facilities. There are documented and anecdotal reports of chemical weapon burial sites and ocean dumps across the globe spanning from the Arctic Circle to Australia. Numerous accidental exposures have occurred over the past decade. Mustard gas is corrosive to the skin, eyes, and respiratory tract. Extensive exposures can also affect other organ systems. Its ability to cause harm to multiple organ systems at extremely low doses in virtually any environmental condition makes it an extremely dangerous agent. Immediate decontamination of people exposed to mustard gas liquids and vapors is paramount. Supportive care and long-term followup is necessary for exposed persons. Research is under way to find antidotes or treatment methods for mustard gas exposure, but currently there are no definitive treatment guidelines., Conclusions: Mustard gas is a weapon, but also a prevalent environmental threat. Recognizing the immense environmental presence of mustard gas disposal sites and the signs and symptoms of exposure will help speed treatment to those accidentally or purposefully exposed.

Mechlorethamine (HN2) and 2-chloroethylethyl sulfide (CEES) are mustard vesicants. Butylated hydroxyanisole (BHA) is a phenolic antioxidant. In the present work, the ability of BHA to reduce the toxicity of HN2 and CEES was investigated using A-431 skin cells. HN2 toxicity was found to be dependent, at least in part, on the cellular glutathione (GSH) status. BHA also decreased HN2-induced DNA damage and lipid peroxidation. The cytoprotective activity of BHA was also compared with that of the structurally unrelated antioxidant ebselen. Whereas ebselen (30 microM) protected skin cells from the toxicity of both HN2 (10-80 microM) and CEES (10-40 microM), BHA (100 microM) reduced the toxicity of HN2 only. Taken together, these data suggest that antioxidants such as BHA or ebselen may serve as useful treatments for injury caused by blistering agents.

Detoxification reactions of sulphur mustard, a deadliest chemical warfare agent were studied on the surface of zinc oxide nanorods at room temperature (32+/-2 degrees C) and the data was compared with that of the bulk ZnO. Prior to the reaction, the nanorods of zinc oxide were synthesized by the hydrothermal method and subsequently characterized by XRD, SEM, TG, N(2) BET, FT-IR. The data revealed the formation of nanorods with diameter ranging from 100 nm to 500 nm with length in microns. Obtained nanomaterial along with bulk ZnO were tested as reactive sorbent for the detoxification of sulphur mustard. Reaction was monitored by GC-FID technique and the reaction products were characterized by GC-MS. Data explores the role of hydrolysis and elimination reactions in the detoxification of sulphur mustard and it also reveals that zinc oxide nanorods and bulk ZnO show the half lives of 8.48 h, 24.75 h in the first 12h and 122.47 h, 177.29 h from 12h to 48 h of the reaction.

A bacterial culture capable of utilizing products of mustard gas hydrolysis as a source of carbon was isolated from soil. This culture was tolerant to organochlorine substances in the hydrolysate. The bacterium was identified as Pseudomonas sp. The bacterium utilizes the major product of mustard gas hydrolysis, thiodiglycol, through two pathways. One involves the oxidation of the primary alcoholic groups in thiodiglycol, yielding thiodiglycolic and thioglycolic acids. The cleavage of the C-S bonds in these acids gives rise to acetate, which is then used further in the cell metabolism. The other pathway involves the cleavage of the C-S bond in the thiodiglycol molecule, yielding beta-mercaptoethanol, which is transformed by Pseudomonas sp. into thioglycolic acid. The results show the promise of this bacterium for the bioremediation of mustard gas-contaminated soils.

Bis(2-hydroxyethylthio)alkanes and bis(2-hydroxyethylthioalkyl)ethers are important biological and environmental degradation products of sulfur mustard analogs known as sesqui- and oxy-mustards. We used atmospheric pressure chemical ionization mass spectrometry (APCI MS) to acquire characteristic spectra of these compounds in positive and negative ionization modes. Positive APCI mass spectra exhibited [M + H](+); negative APCI MS generated [M + O(2)](-), [M - H](-), and [M - 3H](-); and both positive and negative APCI mass spectra contained fragment ions due to in-source collision-induced dissociation. Product ion scans confirmed the origin of fragment ions observed in single-stage MS. Although the spectra of these compounds were very similar, positive and negative APCI mass spectra of the oxy-mustard hydrolysis product, bis(2-hydroxyethylthiomethyl)ether, differed from the spectra of the other compounds in a manner that suggested a rearrangement to the sesqui-mustard hydrolysis product, bis(2-hydroxyethylthio)methane. We evaluated the [M + O(2)](-) adduct ion for quantification via liquid chromatography-MS/MS in the multiple-reaction monitoring (MRM) mode by constructing calibration curves from three precursor/product ion transitions for all the analytes. Analytical figures of merit generated from the calibration curves indicated the stability and suitability of these transitions for quantification at concentrations in the low ng/mL range. Thus, we are the first to propose a quantitative method predicated on the measurement of product ions generated from the superoxide adduct anion of the sesqui-and oxy-mustard hydrolysis products.

The kinetics of absorption, desorption, and degradation of sulfur mustard (HD) in alkyd coating was experimentally studied, and a one-dimension mass transfer model for the transportation of HD molecule in alkyd coating was established on the experimental data. The obtained results indicated that the persistence of HD molecule could be greatly increased due to the absorption of HD droplets by alkyd coating, and there still occurred the desorption of HD as vapor from coating for more than 3 days even after decontamination of HD droplets onto coating. It was also experimentally shown that the majority of HD both absorbed and desorbed was accomplished at an early stage, less than 10 h, and HD molecule was able to be degraded within the alkyd coating probably through the reactions of hydrolysis and elimination. The diffusion coefficient and degradation rate constant of HD in alkyd coating were determined to be practically around 10(-9) cm2/s and 2.4 x 10(-5) min(-1), respectively.

Breakthrough behaviour of sulphur mustard, the deadliest of persistent chemical warfare agents, on carbon systems such as NaOH/CrO(3)/C, NaOH/CrO(3)/EDA/C and RuCl(3)/C has been studied and the data were compared with that of active carbon. Effects of bed lengths of carbons on breakthrough time have also been correlated. Thereafter, the effects of flow rate of air-sulphur mustard mixture, concentration and temperature on the kinetic parameters such as rate constant (k(v)) and kinetic saturation capacity (W(e)) were analyzed and interpreted by means of modified Wheeler equation. Rate constant was found to be increasing while W(e) was found to be invariable with the increase in air flow rate. Both k(v) and W(e) decreased with the increase of temperature, however, no significant effect on W(e) and k(v) was observed due to concentration change (0.3-0.6 mg/l). The values of kinetic saturation capacity were used to predict the service lives/breakthrough times of carbon beds (when used in filtration systems).

A simple and economical chemical neutralization method is developed against highly toxic chemical warfare agent's viz. sulfur mustard (SM), sesquimustard, and their homologues/analogous. The method involves treatment of chemical warfare agents with sodium in inert solvents. This destruction method of sulfur mustards release innocuous products via desulfurization reactions. The products were characterized by GC-MS technique. The method is suitable in particular, for bulk destruction of heel of mustard stockpiles.

Sulphur mustard vapor breakthrough behavior on whetlerite carbon has been studied by using modified Wheeler equation. The values of pseudo-first-order rate constant (k(v)) and kinetic saturation capacity (W(e)) were calculated and the effects of various parameters such as bed height, air flow rate, concentration and temperature on the above parameters have also been studied. Rate constant is found to be increasing with air flow rate, while W(e) is found to be invariable. Both k(v) and W(e) decrease with the increase of temperature, however, no significant effect on W(e) and k(v) is observed due to concentration change. The values of kinetic saturation capacity are used to predict the service lives/breakthrough times of carbon beds (when used in filtration systems).

Molecularly imprinted polymers (MIPs) known as plastic antibodies (PAs) represent a new class of materials possessing high selectivity and affinity for the target molecule. Since their discovery, PAs have attracted considerable interest from bio- and chemical laboratories to pharmaceutical institutes. PAs are becoming an important class of synthetic materials mimicking molecular recognition by natural receptors. In addition, they have been utilized as catalysts, sorbents for solid-phase extraction, stationary phase for liquid chromatography and mimics of enzymes. In this paper, first time we report the preparation and characterization of a PA for the recognition of blistering chemical warfare agent sulphur mustard (SM). The SM imprinted PA exhibited more surface area when compared to the control non-imprinted polymer (NIP). In addition, SEM image showed an ordered nano-pattern for the PA of SM that is entirely different from the image of NIP. The imprinting also enhanced SM rebinding ability to the PA when compared to the NIP with an imprinting efficiency (alpha) of 1.3.

Bis-2-chloroethyl sulphide (sulphur mustard or HD) is an extremely toxic and persistent chemical warfare agent. For in situ degradation of HD and its analogues (simulants), i.e., dibutyl sulphide (DBS) and ethyl 2-hydroxyethyl sulphide (HEES), different carbon systems such as 11-molybdo-1-vanadophosphoric acid impregnated carbon (V(1)/C), ruthenium chloride impregnated carbon (Ru/C) and combination of these two (V(1)/Ru/C) were prepared. These carbons were characterized for cumulative micropore volume and surface area by N(2) BET. The kinetics of the in situ degradation of HD and its simulants were studied and found to be following the first order kinetics. Kinetic rate constants and t(1/2) values were determined. Products were characterized using NMR, IR and GC-MS. Reaction products were found to be sulphoxide and sulphone. The combined system, i.e., 11-molybdo-1-vanadophosphoric acid plus ruthenium chloride (V(1)/Ru/C) was found to be best for in-situ degradation of HD and its simulants. In-situ degradation by polyoxometalate based system was found to be stoichiometry based while Ru/C oxidized HD in presence of chemisorbed oxygen. In combined system of V(1)/Ru/C ruthenium worked as a catalyst and polyoxometalate acted as a source of oxygen. Effect of moisture was also studied in combined system. Rate of degradation of HD was found to be increasing with increased percentage of moisture content.

A preliminary study has been done to examine the sorption, diffusion and degradation of mustard (HD) in cement. The sample of dried cement paste is a meso-porous adsorbant with a BET surface area around 40.8 m2/g, which is able to adsorb vapor of HD at room temperature and to result in a multiple-layer isotherm of II type. The molecule of HD seemed to chemically adsorb onto cement surface. Droplet of HD contaminating cement was able to be degraded into less toxic products, but in a very low rate of k = 4.8 x 10(-5) min(-1) and t(1/2) = 16 x 10(4) min at room temperature. Droplet of HD is able to penetrate through the layer of cement, but a cement plate of 8mm can protect against HD droplets over 48 h. A decrease of thickness for cement layer or addition of sand in cement would lead to lower the protection time against HD droplets. The diffusion coefficient of HD molecule in cement was determined, about 1.3 x 10(-4) cm2/min and of a typical diffusion in solid.

HSA has been shown to react with many organic toxicants to form adducts that are useful biomarkers for exposure. Albumin isolation is an important first step for the analysis of these protein-toxicant adducts. We tested several approaches to isolate albumin from serum treated with an electrophilic organic toxicant known to form adducts with albumin, i.e., sulfur mustard agent (HD) (2,2'-dichloroethyl sulfide), in order to evaluate these techniques as purification methods. To select the most efficient isolation strategy, methods were evaluated using gel electrophoresis, total protein quantitation, and peptide-adduct identification by MS. Results suggest that the albumin-rich fractions obtained can be used to identify exposure by quantitating the albumin adducts to electrophilic organic toxicants such as HD. The HiTrap Blue HP albumin isolation system appears to display the most promising results for purifying albumin to detect HD-adducts, exhibiting high purification efficiency, satisfactory albumin recovery, promising specificity, and a higher loading capacity for serum.

Sulfur mustard (HD) undergoes hydrolysis to form various products such as thiodiglycol (TG) in biological and environmental systems. TG is a precursor in the production of HD and it is also considered as a "Schedule 2" compound (dual-use chemicals with low to moderate commercial use and high-risk precursors). Several toxicological studies on TG were conducted to assess environmental and health effects. The oral LD(50) values were >5000 mg/kg in rats. It was a mild skin and moderate ocular irritant and was not a skin sensitizer in animals. It was not mutagenic in Ames Salmonella, Escherichia coli, mouse lymphoma, and in vivo mouse micronucleus assays, but it induced chromosomal aberrations in Chinese hamster ovarian (CHO) cells. A 90-day oral subchronic toxicity study with neat TG at doses of 0, 50, 500, and 5000 mg/kg/day (5 days/week) in Sprague-Dawley rats results show that there are no treatment-related changes in food consumption, hematology, and clinical chemistry in rats of either sex. The body weights of both sexes were significantly lower than controls at 5000 mg/kg/day. Significant changes were also noted in both sexes in absolute weights of kidneys, kidney to body weight ratios, and kidney to brain weight ratios, in the high-dose group. The no-observed-adverse-effect level (NOAEL) for oral toxicity was 500 mg/kg/day. The developmental toxicity conducted at 0, 430, 1290, and 3870 mg/kg by oral gavage showed maternal toxicity in dams receiving 3870 mg/kg. TG was not a developmental toxicant. The NOAEL for the developmental toxicity in rats was 1290 mg/kg. The provisional oral reference dose (RfD) of 0.4 mg/kg/day was calculated for health risk assessments. The fate of TG in the environment and soil showed biological formation of thiodiglycalic acid with formation of an intermediate ((2-hydroxyethyl)thio)acetic acid. It was slowly biodegraded under anaerobic conditions. It was not toxic to bluegill sunfish at 1000 mg/L and its metabolism and environmental and biochemical effects are summarized.

Sulphur mustard is one of the major chemical warfare agents developed and used during World War I. Large stockpiles are still present in several countries. It is relatively easy to produce and might be used as a terroristic weapon. Sulphur mustard is a vesicant agent and causes cutaneous blisters, respiratory tract damage, eye lesions and bone marrow depression. The clinical picture of poisoning is well known from the thousands of victims during World War I and the Iran-Iraq war. In the latter conflict, sulphur mustard was heavily used and until now about 30,000 victims still suffer from late effects of the agent like chronic obstructive lung disease, lung fibrosis, recurrent corneal ulcer disease, chronic conjunctivitis, abnormal pigmentation of the skin, and several forms of cancer. Despite enormous research efforts during the last 90 years, no specific sulphur mustard antidote has been found. The prospering knowledge and developments of modern medicine created nowadays new chances to minimize sulphur mustard-induced organ damage and late effects.

A gas chromatograph coupled with an atomic emission detector was used to identify and to determine the products formed on oxidation of sulfur mustard. The oxidation rate and the resulting oxidates were studied in relation to oxidant type and reaction medium parameters. Hydrogen peroxide, sodium hypochlorite, sodium perborate, potassium monopercarbonate, ammonium peroxydisulfate, potassium peroxymonosulfate (oxone), and tert-butyl peroxide were used as oxidants. Oxidations were run in aqueous media or in solvents of varying polarities. The oxidation rate was found to be strongly related to oxidant type: potassium peroxymonosulfate (oxone) and sodium hypochlorite were fast-acting oxidants; sodium perborate, hydrogen peroxide, ammonium peroxydisulfate, and sodium monopercarbonate were moderate oxidants; tert-butyl peroxide was the slowest-acting oxidant. In non-aqueous solvents, the oxidation rate was strongly related to solvent polarity. The higher the solvent polarity, the faster the oxidation rate. In the acid and neutral media, the mustard oxidation rates were comparable. In the alkaline medium, oxidation was evidently slower. A suitable choice of the initial oxidant-to-mustard concentration ratio allowed to control the type of the resulting mustard oxidates. As the pH of the reaction medium was increased, the reaction of elimination of hydrogen chloride from mustard oxidates becomes more and more intensive.

Reactions of sulfur mustard with active components of decontaminants ORO and C9 (Polish abbreviations of organic decontaminating solutions) were studied and their products were identified by GC/AED. Quantitative determinations of individual products in the reaction mixtures allowed to evaluate the kinetic parameters of the mustard reactions. The major decontamination product was divinyl sulfide, the product of the elimination reaction. At certain proportions of mustard to the decontaminant's active component, substitution products were also formed.

An analytical method employing gas chromatography is presented for assessing the concentrations of the sulfur mustard hydrolysis product thiodiglycol (TDG) in cutaneous in vivo microdialysates. The use of a pulsed flame photometric detector allows for selective detection of the analyte following solvent exchange and derivatization with heptafluorobutyric anhydride. Quantitative assessment is performed using thiodipropanol (TDP) as a surrogate internal standard. A linear relationship and a very significant correlation (r2 = 0.9982) between the ratio of TDG and TDP concentrations and the ratio of the square root of peak heights is demonstrated. The suitability of the analytical method is verified by the evaluation of blank in vivo microdialysates spiked with known amounts of TDG. The limit of detection in microdialysates is 0.200 nmol/mL (24.4 ng/mL) and the limit of quantitation was 0.364 nmol/mL (44.4 ng/mL). The presented method provides selective, sensitive, rapid, and high-throughput analysis of microdialysates containing TDG, providing an efficient alternative for high-performance liquid chromatography and capillary electrophoresis techniques.

Kinetics of degradation of sulphur mustard (HD) on the surface of NaOH/CrO3/C, NaOH/CrO3/EDA/C and RuCl3/C systems has been examined by using gas chromatography technique by extracting and analyzing the residual HD periodically. The carbons were prepared by impregnating activated carbon with 4% sodium hydroxide plus 3% Cr(VI) as CrO3 with and without 5% ethylene diamine (EDA) and 5% ruthenium chloride by using their aqueous solutions. Obtained carbons were characterized for surface area analysis by BET conventional method. Kinetic plots reveal that the observed reactions are fast at the initial stages, slow at the later stages and progress to a steady state indicating the first order behavior. Effect of moisture on kinetic rate is also observed. In the case of NaOH/CrO3/C system the rate constant is decreased from 13.36 to 5.53 x 10(-2) h(-1) and half life is increased from 5.2 to 12.54 h while moisture content is increased from 1.9% to 11.2%. Whereas, the rate constant of HD degradation reaction is decreased from 10.4 to 4.14 x 10(-2) h(-1) and half life is increased from 6.7 to 16.72 h while moisture content is increased from 2.1% to 10.8% on NaOH/CrO3/EDA/C. Reaction on RuCl3/C system also behaves in the similar manner. Extracted reaction products were characterized by GC/MS and it is found that on NaOH/CrO3/C, HD degrades to hemisulphur mustard, thiodiglycol and 1,4-oxathiane. Whereas, on NaOH/CrO3/EDA/C, HD is degraded to 1,4-thiazane and it is degraded to divinyl sulphone on RuCl3/C. All these investigations reveal that above mentioned carbons can be used in nuclear, biological and chemical (NBC) filtration systems for protection against sulphur mustard.

Disinfection with photocatalysis, compared to with the conventional cleanout, is both high efficient and non contaminative, but the simple TiO2 photocatalyst is showing to be of low activity and low active stability so to be hardly practical application. In the paper, SO4(2-)/TiO2 were papered by surface modification of TiO2 with dilute H2SO4, and the photocatalytic degradation of 2-chloroethyl ethyl sulfide (2-CEES) on the samples was examined in a fixed-bed microreactor. The examination show that the acidic modification enhanced both the activity and the active stability of TiO2, and the sample ST200 prepared by calcination at 200 degrees C was better than ST400 by calcination at 400 degrees C. The effect of water vapor content and reaction temperature on the photocatalytic degradation of 2-CEES was also tested, showing that the sample ST200 had high activity and stability at 90 degrees C, and kept a constant activity when adding 30.5 mL/L water vapor into the reactive system in which 2-CEES initial concentration was low to < 61 microL x L(-1). In addition, it was found that supporting SO4(2-)/TiO2 on gamma-Al2O3, SiO2 and active carbon could improve on the activity and stability of SO4(2-)/TiO2, and on supports SiO2 is the best one.

Thermal desorption with gas chromatography-mass spectrometry (TD-GC-MS) remains the technique of choice for analysis of trace concentrations of analytes in air samples. This paper describes the development and application of a method for analysing the vesicant compounds sulfur mustard and Lewisites I-III. 3,4-Dimercaptotoluene and butanethiol were used to spike sorbent tubes and vesicant vapours sampled; Lewisite I and II reacted with the thiols while sulfur mustard and Lewisite III did not. Statistical experimental design was used to optimise thermal desorption parameters and the optimum method used to determine vesicant compounds in headspace samples taken from a decontamination trial. 3,4-Dimercaptotoluene reacted with Lewisites I and II to give a common derivative with a limit of detection (LOD) of 260 microg m(-3), while the butanethiol gave distinct derivatives with limits of detection around 30 microg m(-3).

Activated carbon of surface area 1100 m2/gm is impregnated with 4% sodium hydroxide plus 3% Cr(VI) as CrO3 with and without 5% ethylene diamine (EDA), 4% magnesium nitrate and 5% ruthenium chloride by using their aqueous solutions. These carbons are characterized for surface area analysis by BET conventional method and exposed to the vapours of sulphur mustard (HD) at room temperature (30 degrees C). After 24 h, the reaction products are extracted in dichloromethane and analyzed using gas chromatography and mass spectrometry (GC-MS). Hemisulphur mustard, thiodiglycol, 1,4-oxathiane are observed to be the products of reaction between sulphur mustard and NaOH/CrO3/C system, whereas on NaOH/CrO3/EDA/C system HD reacted to give 1,4-thiazane. On Mg(NO3)2/C system it gave hemisulphur mustard and thiodiglycol. On RuCl3/C system it degraded to divinyl sulphone. Residual sulphur mustard is observed along with reaction products in all systems studied. Reaction mechanisms are also proposed for these interesting surface reactions. Above-mentioned carbons can be used in filtration systems for protection against hazardous gases such as sulphur mustard.

A method for determining thiodiglycol (TDG), a mustard gas hydrolysis product in water, serum and urine samples using gas chromatography-mass spectrometry (GC-MS) after tert-butyldimethylsilylation (TBDMS) is described. Quantitation of TDG was performed by measuring the respective peak area on the extracted ion chromatogram of m/z 293, using an internal standard, the TDG homologue, thiodipropanol, peak area of which was measured as m/z 321. The presence of salts in the sample solution not only suppressed the loss of TDG by vaporization during the evaporation of water, but also facilitated the rate of production of di-silylated derivative, bis(tert-butyldimethylsilyoxylethyl)sulfide (TDG-(TBDMS)2). Under the pretreatment conditions used, in which 0.5 ml of water sample supplemented with 100 microM potassium chloride was evaporated to dryness under reduced pressure, followed by reaction with N-methyl-N-(tert-butyldimethylsilyl)trifluoroacetamide at 60 degrees C for 1 h, TDG-(TBDMS)2 was reproducibly detected with about a 55% recovery and a limit of detection (LOD, scan mode, S/N = 3) of 5.4 ng/ml. TDG was also determined by GC-MS from a 0.5 ml serum sample (after perchloric acid deproteinization) and from a 0.1 ml urine sample, after TBDMS derivatization. The LOD was determined to be 7.0 and 110 ng/ml for serum and urine, respectively.

Trifluoroacetylation reactions were optimized for gas chromatography-mass spectrometric (GC-MS) analysis of precursors of nitrogen and sulfur mustards using newly developed N-trifluoroacetylbenzimidazole (TFABI) and known N-trifluoroacetylimidazole (TFAI) and N-trifluoroacetylbenzotriazole (TFABT) reagents. TFAI and TFABI gave the best results in terms of yields and reaction time. Trifluoroacetyl derivatives showed clean total ion chromatograms in GC-MS analysis than trimethylsilyl (TMS) derivatives. The negative ion chemical ionization analysis of these derivatives gave pseudo molecular weight information, with low limit of detection.

We here report on the further development of the method comprising the pronase digestion of albumin alkylated by sulfur mustard and the subsequent mass spectrometric analysis of an adducted tripeptide. This includes significant improvements in both the albumin isolation procedure and the automation of the microliquid chromatography-electrospray-tandem mass spectrometric analysis. We also report on the results of a small reference range study, in which we have established that there are no detectable interferences in sera from unexposed individuals.

A standard operating procedure has been developed for an immunoslotblot assay of sulfur mustard adducts to DNA in human blood and skin for use in a field laboratory. A minimum detectable level of exposure of human blood in vitro (> or = 50 nM) sulfur mustard is feasible with the assay. In the case of human skin, a 1 s exposure to saturated sulfur mustard vapor (830 mg/m(-3)) could still be detected.

A procedure for the modified Edman degradation of globin for determination of sulfur mustard adducts to the N-terminal valine residue in human hemoglobin has been developed for use under field laboratory conditions. The minimum detectable exposure level of human blood (in vitro) to sulfur mustard using this procedure is 100 nM. The interindividual and intraindividual variabilities of the procedure were acceptable (standard deviation < 10% and < 20%, respectively). The procedure could be properly set up and carried out in another laboratory within one working day, demonstrating its robustness.

The photooxidation of 2-chloroethyl ethyl sulfide (2-CEES), a simulant for mustard gas, was studied using transmission IR spectroscopy on a mixed-oxide TiO2-SiO2 photocatalyst. Ultraviolet irradiation in the photon energy range from 2.1 to 5 eV was employed at a catalyst temperature of 200 K. Rapid photooxidation was observed by the loss of infrared intensity in the v(CHx) stretching region, and concomitant infrared features of adsorbed oxidation products were observed to develop. The oxidation products, captured on the photocatalyst at 200 K, were found to block 2-CEES readsorption. Upon heating the poisoned photocatalyst to about 300 K, infrared measurements indicate that the adsorbed CO2 oxidation product was desorbed. The capability for full readsorption of 2-CEES was achieved upon heating the poisoned photocatalyst to 397 K, and continued rapid photooxidation of the 2-CEES was then possible at about 1/3 the rate found for the fresh catalyst. Thus thermal treatment at 397 K of oxidation-product-poisoned TiO2-SiO2 material is able to partially restore the TiO2-SiO2 photooxidation activity.

Reaction with thiol converts the antitumor natural product leinamycin to an episulfonium ion that alkylates the N(7)-position of guanine residues in double-stranded DNA. The sequence specificity for DNA alkylation by this structurally novel compound has not previously been examined. It is reported here that leinamycin shows significant (>10-fold) preferences for alkylation at the 5'-G in 5'-GG and 5'-GT sequences. The sequence preferences for activated leinamycin are significantly different from that observed for the structurally simple episulfonium ion generated from 2-chloroethyl ethyl sulfide. DNA alkylation by activated leinamycin is inhibited by addition of salt (100 mM NaClO(4)), although the degree of inhibition is somewhat less than that seen for 2-chloroethyl ethyl sulfide. This result suggests that electrostatic interactions between the activated leinamycin and the N(7)-position of guanine residues facilitate efficient DNA alkylation. However, the observed sequence preferences for DNA alkylation by activated leinamycin do not correlate strongly with calculated sequence-dependent variations in the molecular electrostatic potential at the N(7)-atom of guanine residues in duplex DNA. Thus, electrostatic interactions between activated leinamycin and DNA do not appear to be the primary determinant for sequence specificity. Rather, the results suggest that sequence-specific noncovalent interactions of leinamycin with the DNA double helix on the 3'-side of the alkylated guanine residue play a major role in determining the preferred alkylation sites. Consistent with the notion that noncovalent binding plays an important role in DNA alkylation by leinamycin, experiments with 2'-deoxyoligonucleotide substrates confirm that the natural product does not alkylate single-stranded DNA under conditions where duplex DNA is efficiently alkylated.

Photocatalytic oxidation of gaseous 2-chloroethyl ethyl sulfide (2-CEES, ClCH2CH2SCH2CH3) over TiO2 illuminated with UV light and maintained at 25 or 80 degrees C in air has been investigated. 2-CEES was found to suffer progressive oxidation to yield ethylene (CH2CH2), chloroethylene (ClCHCH2), ethanol (CH3CH2OH), acetaldehyde (CH3C(O)H), chloroacetaldehyde (ClCH2C(O)H), diethyl disulfide (CH3CH2S2CH2CH3), 2-chloroethyl ethyl disulfide (ClCH2CH2S2CH2CH3), and bis(2-chloroethyl) disulfide (ClCH2CH2S2CH2CH2Cl) as the main primary intermediates, and water (H2O), carbon dioxide (CO2), sulfur dioxide (SO2), surface sulfate ions (SO4(2-)), and hydrogen chloride (HCl) as the final products. Trace concentrations of gaseous 2-chloroethanol (ClCH2CH2OH), ethanesulfonyl chloride (CH3CH2SO2Cl), ethyl thioacetate (CH3CH2SC(O)CH3), and considerable amounts of acetic acid (CH3C(O)OH), crotonaldehyde (CH3CHCHC(O)H), methyl acetate (CH3C(O)OCH3), and methyl formate (CH3OC(O)H) were also detected in the gas phase during the photooxidation conducted at 80 degrees C. Increase in temperature from 25 to 80 degrees C accelerates formation of gaseous ethanol, acetaldehyde, chloroacetaldehyde, diethyl disulfide, 2-chloroethyl ethyl disulfide, and bis(2-chloroethyl) disulfide but suppresses ethylene and chloroethylene production at initial stages of the process. Some aspects of the possible reaction mechanism leading to this wide array of intermediates and final products are discussed.

This work explores the ability of photocatalysis to decontaminate water and air from chemical warfare agent mustard using its simulant 2-phenethyl 2-chloroethyl sulfide (PECES). PECES like mustard slowly dissolves in water with hydrolysis, forming 2-phenethyl 2-hydroxyethyl sulfide (PEHES). Irradiation of TiO2 suspension containing PECES with the unfiltered light of a mercury lamp (lambda > or = 254 nm) decomposed all PECES mostly via photolysis. Reaction under filtered light (lambda > 300 nm) proceeds mainly photocatalytically and requires longer time. Sulfur from starting PECES is completely transformed into sulfuric acid at the end of the reaction. Detected volatile, nonvolatile, surface products, and the suggested scheme of degradation are reported. The main volatile products are styrene and benzaldehyde, nonvolatile--hydroxylated PEHES, surface--2-phenethyl disulfide. Photolysis of PECES produced the same set of volatile products as photocatalysis. Photocatalytic degradation of gaseous PECES in air results in its mineralization but is accompanied by TiO2 deactivation. The highest rate of mineralization with minimum deactivation was observed at about room temperature and a water concentration of 27,500 ppm. No gaseous products except CO2 were detected. The main extracted surface product was styrene. It was concluded that PECES photocatalytic degradation proceeds mainly via C-S bond cleavage and further oxidation of the products. Hydrolysis of the C-S bond was detected only in gas-phase photocatalytic degradation. The quantum efficiency of gas-phase degradation (0.28%) was much higher than that of liquid-phase degradation (0.008%). The results demonstrate the ability of photocatalysis to decontaminate an aqueous and especially an air environment

Although the interactions of sulfur mustard (HD) with nucleic acids and proteins have been well studied, the toxic interactions with the membrane matrix and specially the phospholipid bilayer have so far been poorly investigated. We have used several NMR techniques to study these interactions: 1H NMR to observe the localization of HD in membranes of small unilamellar vesicles (SUV) of lecithin; 31P NMR to verify the hypothesis of pore formation in membranes of large unilamellar vesicles (LUV); and pseudo solid state 31P and 2H NMR to analyze the dynamic consequences of the presence of HD in multilayer dispersions of dimyristoylphosphatidylcholine (DMPC). Immediate and late modifications of the DMPC-HD complexes have been observed at the macroscopic and microscopic levels. After intoxication, HD is spontaneously incorporated into the membrane and locates at the level of the chain methylene groups. This incorporation occurs without formation of pores in the membrane. The presence of HD in the phospholipid dispersion differentially increases the membrane fluidity depending upon the level involved. Weak at the superficial level (phosphate group), this increase is dose-dependent on progression into the membrane. This increase is related to a lowering of transition temperature when measured at the chain level. Macroscopically, HD induces dose- and time-dependent modifications of the DMPC-HD complexes, leading to the formation of an optically transparent gel. This gel formation is confirmed at a microscopic level, where all structures disappear after intoxication.

A block of yperite fished up from the Baltic Sea was analysed by gas chromatography coupled with atomic emission spectrometry and mass spectrometry. In the samples of the block about 50 compounds were detected, out of which 30 were identified. The identification of the compounds was performed by using the element chromatograms of the investigated compounds, and the data obtained by mass spectrometric detection. Thiodiglycol was not found among the compounds present in the investigated block. The calculations of the contents of sulphur mustard and some products in the block were performed by an external calibration method using bis(2-chloroethyl) sulphide as the standard. A satisfactory precision of elements determinations was obtained (RSD from 4.4 to 14.3%).

Thiodiglycol (TDG) is the predominant hydrolysis product of the chemical warfare agent sulfur mustard. The extraction of TDG was investigated using pressurised liquid extraction and the results compared for a variety of different solvents and soils. TDG was analysed underivatised by gas chromatography with flame photometric detection. A mixture of methanol-water (9:1), proved to be the most efficient extracting solvent for TDG at a temperature of 150 degrees C and 10 MPa.

This study reports the kinetic reaction of a chlorinated glycoluril, 1,3,4,6-tetrachloro-7, 8-diphenyl-2,5-diimino glycoluril, also known as S-330, with butyl 2-chloroethyl sulfide (half-sulfur mustard, H-MG) and bis-(2-chloroethyl) sulfide (sulfur mustard, HD) using electron paramagnetic resonance (EPR)/spin trapping and nuclear magnetic resonance (NMR) techniques. Both H-MG and HD are highly reactive in water and are capable of alkylating a variety of critical target molecules. It is well known that compounds containing reactive chlorine are useful neutralizers of HD and other vesicating agents. Organic compounds containing a chloroamide group are generally preferred. Currently, the reactive mechanism of this chlorinated glycoluril with these chloroethyl sulfides has not been documented. The kinetic experiments were performed by adding the monofunctional sulfur mustard (H-MG) directly to the spin trap agent alpha-phenyl-N-tert-butylnitrone (PBN, pH 7.1). The intensity of the EPR spectra obtained from the resulting spin adduct (hyperfine coupling constants aN = 1.45 mT and abetaH = 0.225 mT) was sensitive to the rate at which the spin adduct was formed. Different concentrations of the chloroamide were added to the reaction mixtures of PBN and H-MG. The EPR spectra of separate identical reaction mixtures were recorded with the spectrometer set for kinetic experiments. The rate constant determined by EPR was 1.78 +/- 0.14 x 10(7) M(-1)s(-1). It was found that S-330 reacts 55 times faster than PBN. The results obtained for S-330 by EPR indicate that S-330 is an efficient scavenger of H-MG. Furthermore, a 13C-NMR chemical shift of 0.903 +/- 0.002 ppm was observed for the Cl-N-C-N-Cl carbon in S-330 after exposure to HD (1 mM). In addition, the decay of 13C-NMR resonance at 91.7 ppm chemical shift was observed in the presence of HD. The 13C-NMR data showed that the formation of the ethylene sulfonium ion usually found in the case of HD was not observed in the presence of S-330.

Chemical warfare threats require the development of diverse models for the assessment of countermeasures. Human skin products, Skin2 (differentiating keratinocytes on a fibroblast-collagen matrix) and EpiDerm (differentiating keratinocytes) were exposed (2 h) to the sulfur mustard 2-chloroethyl ethyl sulfide (CEES, 1-2 mg l(-1) min(-1)) in humidified air or to humidified air alone. Tissues were evaluated histologically, ultrastructurally and for viability 22 h later; media and tissues were also analyzed for inflammatory mediators. Histology showed that CEES induced the separation of dermal and epidermal regions in Skin2 with severe damage to basal keratinocytes. Histology and electron microscopy of both products revealed condensation of nuclear chromatin, retraction of spinous processes, collapse of the tonofibrillar network and cytoplasmic vacuolization and blebbing in those cells with loss of pseudobasement membrane integrity. Exposure of Skin2 to CEES increased extracellular interleukin-1alpha (IL-1alpha), prostaglandin-E2 (PGE2) and especially IL-1 receptor antagonist (IL-1Ra) release (56,334 vs 84,614 pg ml(-1)), but decreased interleukin-6 (IL-6, 4,755 vs 351 pg ml(-1)). Exposure of EpiDerm to CEES led to unaffected extracellular and reduced intracelluar IL-1alpha (371 vs 92 pg ml(-1)). Extracellular IL-1Ra greatly increased (2,375 vs 24,875 pg ml(-1)), whereas cellular levels decreased (16,5425 vs 96,625 pg ml(-1)). Extracellular (224 vs 68 pg ml(-1)) and intracellular (485 vs 233 pg ml(-1)) soluble interleukin-1 receptor H (sIL-1RII) decreased. Prostanglandin E2 increased (1,835 vs 2,582 pg ml(-1)), whereas heat shock protein 70A (Hsp70A) remained statistically unchanged (57,000 vs 96,000 pg ml(-1)). Failure to obtain a heat shock response to CEES may contribute to the susceptibility of tissue to the alkylating agent. Consistent and marked responses of cellular and extracellular IL-1Ra to CEES suggest a potential for use as a tissue status marker and primary antiinflammatory regulator in skin.

The complexation of mustard gas Cl(CH(2))(2)S(CH(2))(2) Cl, HD, yperite) and of ethers and thioethers derivatives by cyclodextrins: natural alpha-cyclodextrin (ACD) and substituted B-cyclodextrins was studied by NMR. A 1/1 stoechiometry was found in all cases, while affinity constants were found relatively weak (from 5 M(-1) to 100 M(-1)). However, these results show that chelation of HD by cyclodextrins can be reasonably expected, especially if chemical modifications provide stronger affinity constants.

An approach to developing an ecologically safe technology for disposal of yperite-lewisite mixtures has been developed. The technology includes three sequential stages: (1) detoxification by alkaline hydrolysis (resulting in the loss of toxic properties); (2) electrochemical treatment of detoxification products (electrocoagulation, to eliminate arsenic salts, and electrochemical oxidation, to convert all organic components into bioutilizable matter); and (3) degradation of the compounds obtained at the two preceding stages by a bred microbial association.

To develop a mass spectrometric assay for the detection of sulfur mustard adducts with human serum albumin, the following steps were performed: quantitation of the binding of the agent to the protein by using [(14)C]sulfur mustard and analysis of acidic and tryptic digests of albumin from blood after exposure to sulfur mustard for identification of alkylation sites in the protein. The T5 fragment containing an alkylated cysteine could be detected in the tryptic digest with micro-LC/tandem MS analysis. Attempts to decrease the detection limit for in vitro exposure of human blood by analysis of the alkylated T5 fragment were not successful. After Pronase treatment of albumin, S-[2-[(hydroxyethyl)thio]ethyl]Cys-Pro-Phe was analyzed by means of micro-LC/tandem MS, allowing a detection limit for in vitro exposure of human blood of 10 nM, which is 1 order of magnitude lower than that obtained by means of modified Edman degradation. The analytical procedure could be successfully applied to the analysis of albumin samples from Iranian victims of the Iran-Iraq war.

The degradation of thiodiglycol (I) and benzyl sulfide (II) was attempted using Coriolus versicolor and Tyromyces palustris to investigate the potential ability of basidiomycetes to degrade Yperite (bis(2-chloroethyl) sulfide), a mass-produced and stored chemical warfare agent. I was very rapidly degraded by both fungi. The metabolic pathway of II was elucidated, showing that the initial step was the hydrolytic cleavage of the thioether bond to yield benzyl alcohol and benzyl mercaptan. Benzyl alcohol was further oxidized and finally mineralized. Benzyl mercaptan is reversibly converted to benzyl disulfide and also converted to benzyl alcohol. Finally, the effective degradation of bis(2-bromoethyl) sulfide strongly suggests that basidiomycete would be a potential tool for Yperite degradation.