A fatal disaster case based on exposure to hydrogen sulfide — an estimation of the hydrogen sulfide concentration at the scene

doi:10.1016/0379-0738(94)90335-2

Forensic Science International

Volume 66, Issue 2, 3 June 1994, Pages 111-116

https://doi.org/10.1016/0379-0738(94)90335-2 Get rights and content

Abstract

Four adult men fell into an artificial lake which was being used to raise flatfish, after a water pipe had been connected to a tube allowing seawater to flow into the lake. Forensic autopsies were carried out on three of the four men, who died soon after the incident. From autopsy findings, the cause of death was diagnosed to be suffocation after aspirating seawater in the three victims. To clarify why the men fell into the lake, a chemical analysis for hydrogen sulfide was carried out using the extractive alkylation technique combined with gas chromatography/mass spectrometry. The sulfide was detected as its derivative, bis(pentafluorobenzyl)sulfide, in body tissues taken from all the victims, and the concentration of hydrogen sulfide gas at the scene was estimated as having been nearly fatal.

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Gas chromatographic analysis of sulfides was initially carried out via its pentafluorobenzyl derivative detection using mass spectrometry [150]. This technique was applied to post mortem analysis in forensic studies for sulfide fatal toxicity [151] and to investigate blood sulfide as a marker of bowel fermentation processes [93]. Later on, sulfide analysis was achieved in the headspace for tissue homogenates [38] or post silylation in human sera [152].
Hydrogen sulfide (H₂S) is currently considered among the endogenously produced gaseous molecules that exert various signaling effects in mammalian species. It is the third physiological gasotransmitter discovered so far after NO and CO. H₂S was originally ranked among the toxic gases at elevated levels to humans. Currently, it is well-known that, in the cardiovascular system, H₂S exerts several cardioprotective effects including vasodilation, antioxidant regulation, inhibition of inflammation, and activation of anti-apoptosis. With an increasing interest in monitoring H₂S, the development of analysis methods should now follow.
This review stages special emphasis on the several analytical technologies used for its determination including spectroscopic, chromatographic, and electrochemical methods. Advantages and limitations with regards to the application of each technique are highlighted with special emphasis on its employment for H₂S in vivo measurement i.e., biofluids, tissues.
Fluorescence methods applied for H₂S measurement offer an attractive non-invasive and promising approach in addition to its selectivity, however they cannot be considered as H2S-specific probes. On the other hand, colorimetric assays are among the most common methods used for in vitro H₂S detection, albeit their employment in vivo H₂S measurement has not yet been possible . Separation techniques such as gas or liquid chromatography offer higher selectivity compared to direct spectrophotometric or fluorescence methods especially for suitable for endpoint H₂S measurements i.e. plasma or tissue samples. Despite all the developed analytical procedures used for H₂S determination, the need for highly selective, much work should be devoted to resolve all the pitfalls of the current methods.
Chemical aspects of hydrogen sulfide measurements in physiological samples
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The product was extracted into organic solvents, followed by GC analysis of the organic phase. This technology was used to study blood sulfide concentrations after alkalization [102] and in forensic studies for sulfide poisoning post mortem [102,103]. Further development of the method allowed detection of protein bound persulfide moieties or polysulfides after reduction at pH 5, alkylation and extraction into hexane [104].
Owing to recent discoveries of many hydrogen sulfide-mediated physiological processes, sulfide biology is in the focus of scientific research. However, the promiscuous chemical properties of sulfide pose complications for biological studies, which led to accumulation of controversial observations in the literature.
We intend to provide an overview of fundamental thermodynamic and kinetic features of sulfide redox- and coordination-chemical reactions and protonation equilibria in relation to its biological functions. In light of these chemical properties we review the strengths and limitations of the most commonly used sulfide detection methods and recently developed fluorescent probes. We also give a personal perspective on blood and tissue sulfide measurements based on proposed biomolecule–sulfide interactions and point out important chemical aspects of handling sulfide reagent solutions.
The diverse chemistries of sulfide detection methods resulted in orders of magnitude differences in measured physiological sulfide levels. Investigations that were aimed to dissect the underlying molecular reasons responsible for these controversies made the important recognition that there are large sulfide reserves in biological systems. These sulfide pools are tightly regulated in a dynamic manner and they are likely to play a major role in regulation of endogenous-sulfide-mediated biological functions and avoiding toxic side effects.
Working with sulfide is challenging, because it requires considerable amounts of chemical knowledge to adequately handle reagent sulfide solutions and interpret biological observations. Therefore, we propose that a rigorous chemical approach could aid the reconciliation of the increasing number of controversies in sulfide biology. This article is part of a Special Issue entitled Current methods to study reactive oxygen species - pros and cons and biophysics of membrane proteins. Guest Editor: Christine Winterbourn.
Fatal and non-fatal cases of lime sulfide exposure and pathogenetic mechanisms underlying pancreatic injury: Case reports with an animal experiment
2012, Journal of Forensic and Legal Medicine
Citation Excerpt :
Sulfide poisoning has hitherto been considered to occur mostly in industrial and various other situations associated with inhalation of hydrogen sulfide,1–6 but recently a marked increase has also been noted in the number of suicide cases associated with oral ingestion of sulfide-containing household products, notably detergents and bathing items, which are widely available in Japan.7
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Toxicological analysis of 17 autopsy cases of hydrogen sulfide poisoning resulting from the inhalation of intentionally generated hydrogen sulfide gas
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Citation Excerpt :
Aside from being a by-product of many industrial processes, this gas is naturally produced during the putrefaction of sulfur-containing organic substances. Although many cases of fatal hydrogen sulfide poisoning have been reported [1–21], in most of these cases, it resulted from accidents in sewer systems, excrement disposal institutions, chemical factories, volcanoes and hot-spring areas [1–11,15–21]. To our knowledge, there are few reports of fatal poisoning due to the inhalation of hydrogen sulfide gas that was intentionally generated [13,14].
Although many cases of fatal hydrogen sulfide poisoning have been reported, in most of these cases, it resulted from the accidental inhalation of hydrogen sulfide gas. In recent years, we experienced 17 autopsy cases of fatal hydrogen sulfide poisoning due to the inhalation of intentionally generated hydrogen sulfide gas. In this study, the concentrations of sulfide and thiosulfate in blood, urine, cerebrospinal fluid and pleural effusion were examined using GC/MS. The sulfide concentrations were blood: 0.11–31.84, urine: 0.01–1.28, cerebrospinal fluid: 0.02–1.59 and pleural effusion: 2.00–8.59 (μg/ml), while the thiosulfate concentrations were blood: 0–0.648, urine: 0–2.669, cerebrospinal fluid: 0.004–0.314 and pleural effusion: 0.019–0.140 (μmol/ml). In previous reports, the blood concentration of thiosulfate was said to be higher than that of sulfide in hydrogen sulfide poisoning cases, although the latter was higher than the former in 8 of the 14 cases examined in this study. These results are believed to be strongly influenced by the atmospheric concentration of hydrogen sulfide the victims were exposed to and the time interval between exposure and death.
Fatal hydrogen sulfide poisoning at a dye works
2004, Legal Medicine
An adult Japanese man (A) entered a pit to remove sludge in a drainage pipe at a dye works in Japan. When he took off a joint of the pipe, the sludge in the pipe flowed into the pit. As he suddenly lost consciousness, three colleagues (B, C, D) entered the pit to rescue him. All of these (A, B, C and D) lost consciousness in the pit, and died soon after the accident. Since hydrogen sulfide gas was detected in the sludge of the pit, gas poisoning was suspected. Toxicological analyses of sulfide and thiosulfate, a metabolite of sulfide, in blood and urine of the victims were made, using the extractive alkylation technique combined with gas chromatography/mass spectrometry.
Sulfide and thiosulfate were detected in whole blood of the four workers at levels of 0.32–9.36 mg/l and 0.11–0.23 mmol/l, respectively. These concentrations were at least 6–187 times higher in sulfide and 37–77 times higher in thiosulfate than those in healthy persons, and were similar to values found in fatal cases of hydrogen sulfide poisoning. Thiosulfate was not detected in the urine of four workers, which indicated acute death.
Based on these results, all four patients were victims of hydrogen sulfide poisoning, who died soon after the exposure.
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2002, Journal of Chromatography B: Analytical Technologies in the Biomedical and Life Sciences
Sulfur is a chemically and biologically active element. Sulfur compounds in animal tissues can be present in two forms, namely stable and labile forms. Compounds such as methionine, cysteine, taurine and sulfuric acid are stable sulfur compounds. On the other hand, acid-labile sulfur and sulfane sulfur compounds are labile sulfur compounds. The sulfur atoms of labile sulfur compounds are liberated as inorganic sulfide by acid treatment or reduction. Therefore, the determination of sulfide is the basis for the determination of labile sulfur. Determination of sulfide has been performed by various methods, including spectrophotometry after derivatization, ion chromatography, high-performance liquid chromatography after derivatization, gas chromatography, and potentiometry with a sulfide ion-specific electrode. These methods were originally developed for the determination of sulfide in air and water samples and were then applied to biological samples. The metabolic origin of labile sulfur in animal tissues is cysteine. The pathways of cysteine metabolism leading to the formation of sulfane sulfur are discussed. Finally, reports on the physiological roles and pathological considerations of labile sulfur are reviewed.

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A fatal disaster case based on exposure to hydrogen sulfide — an estimation of the hydrogen sulfide concentration at the scene

Abstract

J. Chromatogr.

J. Chromatogr.

J. Chromatogr.

J. Chromatogr.

Biochem. Biophys. Acta