We examined the usefulness of thiosulfate as an indicator of hydrogen sulfide poisoning by analysing sulfide and thiosulfate in three cases. In the first (non-fatal) case sulfide and thiosulfate were not detected in the blood samples from any of the four workers involved in the accident. In the urine samples, only thiosulfate was detected in three out of the four workers at a concentration of 0.12-0.43 micromol/ml, which was 4-14 times higher than the level in a healthy person. In the second (fatal) case sulfide and thiosulfate were detected in the blood sample at concentrations of 0.007 micromol/ml for sulfide, and 0.025 micromol/ml for thiosulfate. The thiosulfate concentration was at least 8 times higher than the level in a healthy person. In the third (fatal) case sulfide and thiosulfate were detected in the blood sample at concentrations of 0.95 micromol/ml for sulfide, and 0.12 micromol/ml for thiosulfate. Based on the above results, we concluded that thiosulfate in urine is the only indicator to prove hydrogen sulfide poisoning in non-fatal cases, while the analysis of sulfide in fatal cases should be accompanied by the measurement of thiosulfate in blood.

SummaryCyanide can be extracted from whole blood samples by headspace solid-phase microextraction (SPME) with a Carbowax/divinylbenzene-coated fiber. Dm'ing heating a vial of a whole blood sample containing cyanide and acetonitrile as internal standard (IS) at 50 ~ in the presence of Na2SO4, a Carbowax/divinylbenzene-coated SPME fiber was exposed in the headspace of the vial for 45 rain to allow adsorption of cyanide and IS. The fiber needle was then injected into a capillary gas chromatography (GC) instrument equipped with nitrogen-phosphorus detection. The headspace SPME-GC with a Supel-Q PLOT fused silica capillary column gave large peaks for cyanide and IS; almost no interfering peaks appeared. Recoveries of cyanide and IS flom human whole blood were 3.02-4.06 % and 0.21%, respectively. The calibration curve for cyanide added to human blood showed excellent linearity in the range of 0.04-4.0 pg mL-1; the detection limit was about 0.02 pg mL -1. The coefficients of intra-day and inter-day variation were not greater than 7.1 and 9.2 %. Good correlation (r 2 = 0.999) was found between the present SPME-GC method and the conventional microdiffusion colorimetric method. Data on determination of cyanide in rat blood after intraperitoneal administration are also presented.

The development of a new configuration of chemical ionization (CI)-based ion source is presented. The ambient air containing the gaseous sample is sniffed into an enclosed ionization chamber which is of sub-ambient pressure, and is subsequently mixed with metastable species in front of the ion inlet of the mass spectrometer. Metastable helium atoms (He*) are used in this study as the primary ionizing agents and are generated from a dielectric barrier discharge (DBD) source. The DBD is powered by an AC high-voltage supply and the configuration of the electrodes is in such a way that the generated plasma is confined within the discharge tube and is not extended into the ionization chamber. The construction of the ion source is simple, and volatile compounds released from the bulky sample can also be analyzed directly by approaching the sample to the sampling nozzle. When combined with heated nitrogen or other desorption methods, its application can also be extended to non-volatile compounds, and the consumption for helium can be kept minimum solely for maintaining the stable discharge and gas phase ionization. Applications to non-proximate sample analysis, direct determination of active ingredients in drug tablets and the detection of trace explosive such as hexamethylene triperoxide diamine are demonstrated.

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We have demonstrated that, with simple pH adjustment, volatile drugs such as methamphetamine, amphetamine, 3,4-methylenedioxymethamphetamine (MDMA), ketamine, and valproic acid could be analyzed rapidly from raw biofluid samples (e.g. urine and serum) without dilution, or extraction, using atmospheric pressure ionization. The ion source was a variant type of atmospheric pressure chemical ionization (APCI) that used a dielectric barrier discharge (DBD) to generate the metastable helium gas and reagent ions. The sample solution was loaded in a disposable glass pipette, and the volatile compounds were purged by nitrogen gas to be reacted with the metastable helium gas. The electrodes of the DBD were arranged in such a way that the generated glow discharge was confined within the discharge tube and was not exposed to the analytes. A needle held at 100-500 V was placed between the ion-sampling orifice and the discharge tube to guide the analyte ions into the mass spectrometer. After pH adjustment of the biofluid sample, the amphiphilic drugs were in the form of a water-insoluble oil, which could be concentrated on the liquid surface. By gentle heating of the sample to increase the evaporation rate, rapid and sensitive detection of these drugs in raw urine and serum samples could be achieved in less than 2 min for each sample.