Разработана методика определения тиодигликоля, 1,1-сульфонил-бис[2-(метилсульфонил)-этна], 1-метилсульфонил-2-[2-(метилтио)этилсульфонил]этана (биомаркеры иприта), метилфосфоновой кислоты, О-этилметилфосфоновой кислоты, О-изопропилметилфосфоновой кислоты, О-пинаколилметилфосфоновой кислоты (биомаркеры фосфорорганических отравляющих веществ) в моче. Методика включает извлечение компонентов жидкостной экстракцией, получение производных, разделение газожидкостной хроматографией и детектирование пламенно-фотометрическим и масс-спектрометрическим детекторами. Методика применена для анализа образцов искусственной мочи методом “введено-найдено”.

A procedure has been developed for the determination of thioglycol, 1,1′-sulfonyl-bis[2-(methylsulfonyl)-ethane], 1-methylsulfonyl-2-[2-(methylthio)ethylsulfonyl]ethane (biomarkers of mustard agent) and methylphosphonic acid, O-ethylmethylphosphonic acid, O-isopropylmethylphosphonic acid, and O-pinacolyl methylphosphonic acid (biomarkers of organophosphoric toxic agents) in urine. The procedure includes the recovery of components by liquid extraction, derivatization, separation by gas-liquid chromatography, and detection by flame-photometric and mass spectral detectors. The procedure has been applied to the analysis of samples of artificial urine by the standard addition method.

Разработана методика газохроматографического определения S-[2-(N,N-диэтиламино)этил]метилтиофосфоновой кислоты (монотиола) в воде на уровне 5 ? 10-5. Методика основана на извлечении монотиола из воды жидкостно-жидостной экстракцией, обработкой экстракта изопропанолом в присутствии AgNO3 и диазометаном для получения О-изопропил-О-метилметилфосфоната и хроматографировании полученного производного с использованием пламенно-фотометрического детектора. Относительная погрешность определения монотиола в воде не превышает 35%, продолжительность анализа составляет 60 мин.

A procedure is proposed for the gas-chromatographic determination of S-[2-(N,N)-diethylamino) ethyl]methylphosphonothioic acid (monothiol) in water at a level of 5 × 10−5%. The procedure is based on the extraction of monothiol from water by liquid-liquid extraction, treatment of the extract with isopropanol in the presence of AgNO3 and with diazomethane to obtain O-isopropyl-O-methyl methylphosphonate, and the chromatographic detection of the derivative obtained with a flame-photometric detector. The relative error of determining monothiol in water does not exceed 35%; the time of analysis is 60 min.

A procedure was proposed for the gas-chromatographic determination of trace O-isobutyl-S-2-(N,N-diethylamino)ethyl ester of methylthiophosphonic acid (mixed ester, ME) in burning products formed after the detoxication of elements in building constructions, personal protection equipment, waste degassing solutions, and other production wastes (slime) at a level of (1.0–10.0) × 10−8 mg/g. The procedure is based on the extraction of ME from an analyzed material with a mixture of aqueous solutions of monoethanolamine and NaOH, its back extraction to hexane, the evaporation of the hexane layer (with the addition of HCl) to dryness, the transformation of ME into methyl ester of O-isobutylmethylphosphonic acid with the use of methanol in the presence of AgNO3, and the chromatography of the derivative on an open tubular column with the chemically modified HP-INN OWax stationary phase with the use of a flame-photometric detector.

A procedure was developed for the gas-chromatographic determination of sarin and soman in the atmospheric air of work zones and inhabited areas at a level of the maximum permissible concentration 2 × 10−5 and 1 × 10−5 mg/m3 and the tentative safe exposure level 2 × 10−7 and 1 × 10−7 mg/m3, respectively. The procedure is based on the recovery of sarin and soman from analyzed air using an absorbing solution, the extraction of sarin and soman from this solution with ethyl acetate and hexane, respectively, the evaporation of the corresponding extracts to a residual volume of 0.1 cm3, and their subsequent chromatography with flame-photometric and thermoionic detectors. The relative error in the determination of sarin and soman is 20 and 18 rel %, respectively, in the air of work zones and 27 and 23 rel %, respectively, in the air of inhabited areas.

A technique for determining the enantiomeric composition of 2-octanol and α-phenylethylamine with the use of gas chromatography on optically inactive stationary phases is proposed. The technique is based on the formation of symmetrical diastereomeric derivatives upon the interaction of enantiomers with bifunctional achiral reagents: dimethyldichlorosilane, bromochloromethane, and dibromoethane. The reagents were chosen from the viewpoint of the synthesis of diastereomers with a minimum distance between the chiral centers. This minimum distance is responsible for a difference in the energies of interaction of the derivatives with the stationary liquid phase, which is sufficient for the separation of these derivatives.

A method was proposed for the separate gas-chromatographic determination of β-chlorovinylarsonous dichloroanhydride (lewisite) and anhydride (lewisite oxide) in samples of soil and construction materials. Because of the absence of regulations for the maximum permissible concentration (MPC) of lewisite and lewisite oxide in construction materials (concrete, bricks, facing tile, etc.), the MPC level of lewisite in soil (0.1 mg/kg) was taken as the maximum permissible concentration in the development of the method for their determination in the above samples. The method is based on the solid-liquid extraction converting lewisite and lewisite oxide into components that can be separated at the stage of blowing-out the extractant in an inert gas flow and their subsequent conversion into acetylene with a 30% aqueous solution of sodium hydroxide and the chromatography of the vapor phase with flame-ionization detection. The error in the determination is no larger than ±20 rel %. The time of analysis is within 1.5 h.

A gas-chromatographic procedure is proposed for the determination of O-isobutyl S-2-(N,N-diethylamino)ethyl methyl phosphonothioate (mixed ester) at the maximum permissible level for the working area air (5 × 10–6 mg/m3) and at the safe reference level of impact for the community air (5 × 10–8 mg/m3). The procedure is based on trapping the mixed ester from air by a chemisorbent. Next, the analyte is extracted by hexane; transformed to O-methyl-O-isobutyl methyl phosphonate by silver nitrate in methanol; and, in the case of the working area air, the methanol solution of the derivative is chromatographed. In the determination of the mixed ester in the community air, a solution of O-methyl-O-isobutyl methyl phosphonate (dialkyl methyl phosphonate) in methanol is passed through a column with an adsorbent and transferred to the chromatographic system with a thermal desorption system. The relative error of the determination of the mixed ester in the working area and community air is no more than 28 and 40 rel. %, respectively.

A gas chromatographic procedure is developed for the determination of β,β-dichlorodiethylsulfide (yperite, sulfur mustard) and β-chlorovinyldichloroarsine (lewisite) in the working area and community air at a level defined by the hygienic regulations for community air (2 × 10–6 and 4 × 10–6 mg/m3 for sulfur mustard and lewisite, respectively) and at the maximum permissible level for a working area (2 × 10–4 mg/m3). The procedure for the determination of sulfur mustard is based on the trapping of the analyte from air with Silochrom S-120 impregnated with Apiezon L with further extraction by a 1 : 1 acetone–hexane mixture, the evaporation of the extract to a small residual volume, and chromatography with an electron capture detector. The procedure for the determination of β-chlorovinyldichloroarsine (lewisite) involves the absorption of the analyte with a 2.2% solution of triethanolamine in 0.1 M hydrochloric acid, the conversion of lewisite to acetylene by treating the trap contents with 30% alkali solution, and the chromatography of the vapor phase using a flame ionization detector. The error of the determination is no more than ±23 rel %. The analysis takes 1.5 h.