Cyanide quantification in post-mortem biological matrices by headspace GC–MS

Abstract

Cyanide is a powerful chemical asphyxiant found in some forensic cases following voluntary (suicide) or involuntary ingestion (fire, accidental exposure). A quantification method for cyanide that is specifically suited to post-mortem forensic purposes was developed. Determination was performed by headspace gas chromatography coupled to mass spectrometry using a GS-GASPRO column on an HP-6890 gas chromatograph with an HP-5973N mass detector. The biological sample was treated with an internal standard, frozen, glacial acetic acid was added and the sample was then incubated at 60°C for 15 min. The headspace was sampled with a disposable syringe, and analyzed to quantify hydrogen cyanide. Isotopically labeled cyanide ((13)C(15)N) was used as the internal standard to minimize matrix effect and sampling error. The method produced an extended linear dynamic range (0.07-50 μg/mL), and a method detection limit of 0.02 μg/mL. Identical calibration curves were obtained when blood, gastric contents and aqueous solutions were used as the calibration standard matrix. This method was also successful in quantitating cyanide in gastric contents, one of the most variable biological fluids. The method has been validated and is being used for current forensic cases such as fire victims and suicides.

Headspace gas chromatography-mass spectrometry method for the determination of total cyanide concentration in water and postmortem blood samples

“…Many methods have been developed for the determination of the cyanide species in different types of samples including ion chromatography 6,7 , capillary electrophoresis (CE) 12,13 , headspace gas chromatography (HS-GC) 14 , GC-Mass Spectrometry (MS) [15][16][17][18] , electrochemicalsensors8 , [19][20][21] , Headspace(HS)-single-drop microextraction (SDME)-NanoDrop® microspectrophotometry (ND) 11 , HS-GC-ato-O n L i n e F i r s t mic emission detector (AED) 22 , HS-GC-electron capture detector(ECD) 23 , HS-GC-ECD/photoionization detection (PID) 24 , HS-GC-Nitrogen-phosphorus detector (HS-GC-NPD) [25][26][27][28][29][30] , HS-solid-phase microextraction (HS-SPME)-NPD 31 , HS-SPME-CE 32 , HS-GC-MS 9,15,33,34 , HS-SPME-GC-MS 35 .…”

Determination of cyanide, thiocyanate, cyanate, hexavalent chromium, and metal cyanide complexes in various mixtures by ion chromatography with conductivity detection

“…The methods have been used for determination of free cyanide and cyanide species includes spectrophotometry, [13][14][15][16][17][18] electroanalysis, [19][20][21] indirect determination of free cyanide with flow injection-AAS, [22] capillary electrophoresis, [23, 24] capillary gas chromatography, [25] gas chromatography-mass spectrometry (GC-MS), [26][27][28][29] headspace gas chromatography (HS-GC), [30] high performance liquid chromatography (HPLC) with fluorometric detection, [31,32] electrospray ionization tandem mass spectrometry (ESI-MS-MS), [33] ion chromatography (IC) with pulsed amperometric detection, [34, 35] and ion chromatography with either electrochemical detection [36][37][38] or fluorescence detection. [39] Most procedures require the extraction or derivatization of cyanides, and yet suffer from related with interference and from a lack of specificity.…”

Headspace sorptive solid phase microextraction (HS-SPME) combined with a spectrophotometry system: A simple glass devise for extraction and simultaneous determination of cyanide and thiocyanate in environmental and biological samples

“…It is simple, eco-friendly and rapid compared with traditional analytical techniques in addition to its suitability to for volatile and semi-volatile compounds [13][14][15]. A headspace single drop microextraction (HS-SDME) coupled fiber optic based cuvetteless micro spectrophotometry has been developed by Jain et al 2016 [1] for total cyanide determination.…”

“…However, problems such as limited contact between the headspace inside the syringe channel and the organic solvent film at the interface are associated with HS-SDME. Headspace coupled gas chromatogr-aphy has been developed for cyanide determination in various biological samples [14][15][16]. HS-SPME uses a stir bar coated by a thick film of polydimethyl-siloxane (PDMS) suspended in the vial headspace where the analyte is evaporated from sample and then adsorbed on the film [17].…”