No abstract

Sodium azide is an old poison with toxicity comparable to potassium cyanide. It would seem to be completely forgotten however, between 2000 and 2020, the number of intentional ingestions and murders committed with sodium azide significantly increased. Furthermore, due to its extreme instability, sodium azide is difficult to detect, which poses an additional risk when used to commit a crime. In this study, the epidemiology of sodium azide exposures between 1920 and 2020 was investigated. For the determination the azide concentration in biological samples, a simple, precise and selective headspace gas chromatography method (HS-GC-FID/FID) was developed and fully validated. The limit of quantification was 0.65 µg/mL; and the limit of detection was 0.35 µg/mL; precision and accuracy did not exceed 20%. The stability study was conducted for various biological fluids (urine, bile, blood, gastric content) for 91 days in the refrigerator (4 °C) and the method for stabilization of azide was presented. The addition of a mixture of borax and sodium fluoride (w/w 3:1) to the test tubes can stabilize this poison. The described unique technique of collecting the biological samples poses a great potential for azide detection in clinical and toxicology laboratories even long time after human exposure to this substance.

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Widespread access to the Internet has an increasing influence on how suicides are committed. On websites such as eBay® or Amazon.com® highly toxic substances including cyanides are available for purchase. In the last 5 years, a few fatal intoxications associated with Internet shopping and buying “suicide kits” have been reported. Epidemiology of intoxications reported by American Association of Poison Control Centers between 2000-2018 shows that about 10% of all exposures to cyanide were related to suicide attempts and intentional ingestion of this substance. In order to determine the cyanide concentration in four fatal intoxication cases associated with Internet shopping, a headspace gas chromatography with dual column/dual flame ionization detector (HS-GC-FID/FID) method was validated and applied to casework. The method was linear in range, from 1 to 50 µg/mL, with a coefficient of determination of 0.999 (R2). The limit of quantification was 1.0 µg/mL; the detection limit was 0.5 µg/mL. Intra- and inter-day validation precision and accuracy did not exceed 10% and 15%, respectively. Recovery and matrix effect values ranged from 94.8– 103.8% and -5.2─3.8%, respectively. The cyanide concentrations were determined in biological fluids (blood, urine, bile, vitreous humor, gastric content) and postmortem tissue samples (spleen, kidney, liver, brain). The headspace gas chromatographic method, which is routinely used in clinical and forensic toxicology to quantify ethanol with its congeners (methanol, acetone, isopropanol, n-propanol and n-butanol), can be also applied to determine cyanide in intoxication cases. The global problem of a high number of suicides each year, requires increasing and more restrictive control of highly toxic substances available online as well as caution monitoring of human exposure to cyanide. This old and well known poison is being increasingly used nowadays for suicidal purposes, therefore determination of cyanide in biological samples is still important in terms of clinical and forensic toxicology.

Purpose Development of ultra-high-performance liquid chromatography-triple quadrupole tandem mass spectrometry method for quantification of 4-fluoroisobutyryl fentanyl (4-FiBF) and its distribution in postmortem biological samples in four fatal intoxication cases, which occurred in September 2018, in Poland. Methods Biological fluids (blood, urine, vitreous humor, bile, gastric content) and tissues (brain, kidney, liver, stomach wall) were extracted with ethyl acetate from alkaline medium (pH 9). Fentanyl-d5 was used as internal standard. Results The validation parameters were as follows: lower limit of quantification: 0.1 ng/mL (biological fluids) and 0.1 ng/g (solid tissues), intra- and inter-day accuracies and precisions: not greater than 20%; recovery values: 86.9–110%; matrix effect: − 13.1–10.4%. Among all tested biological fluid, the highest concentration of 4-FiBF was found in bile (average concentration of 3390 ng/mL) while among the tissues, in liver (average concentration of 1650 ng/g). Furthermore, in collected specimens, there were also found other drugs and new psychoactive substances (NPS) e.g. N-ethylpentylon, 4-chloromethcathinone (4-CMC) and α-pyrrolidinoisohexanophenone (α-PiHP). Concentrations and distributions of these substances in postmortem samples have been also detailed. Examinations of seized drug (in case 4) revealed that it included the mix of 4-FiBF and α-PiHP. Conclusions The developed and fully validated method enabled for determination of 4-FiBF in postmortem biological fluids and tissues. To our knowledge, this is the first report of distribution study of 4-FiBF with other NPS (N-ethylpentylon, 4-CMC and α-PiHP) in authentic fatal intoxication cases.