An improved method for cyanide determination in blood using solid‐phase microextraction and gas chromatography/mass spectrometry

Abstract

A new method is described for the qualitative and quantitative analysis of cyanide, a very short-acting and powerful toxic agent, in human whole blood. It involves the conversion of cyanide into hydrogen cyanide and its subsequent headspace solid-phase microextraction (HS-SPME) and detection by gas chromatography/mass spectrometry (GC/MS) in selected ion monitoring (SIM) mode. Optimizing the conditions for the GC/MS (type of column, injection conditions, temperature program) and SPME (choice of SPME fiber, effect of salts, adsorption and desorption times, adsorption temperature) led to the choice of a 75-microm carboxen/polydimethylsiloxane SPME fiber, with D3-acetonitrile as internal standard, and a capillary GC column with a polar stationary phase. Method validation was carried out in terms of linearity, precision and accuracy in both aqueous solutions and blood. The limit of detection (LOD) and limit of quantitation (LOQ) were determined only in aqueous solutions. The assay is linear over three orders of magnitude (water 0.01-10, blood 0.05-10 microg/mL); and the LOD and LOQ in water were 0.006 and 0.01 microg/mL, respectively. Good intra- and inter-assay precision was obtained, always <8%. The method is simple, fast and sensitive enough for the rapid diagnosis of cyanide intoxication in clinical and forensic toxicology.

Determination of cyanide and volatile alkylnitriles in whole blood by headspace solid-phase microextraction and gas chromatography with nitrogen phosphorus detection

“…Different fibers were tested working on the headspace mode and better results were obtained with the carboxenpolydimethylsiloxane fiber (Fig. 3), confirming the results already reported for hydrogen cyanide [21]. Sample pH is an important parameter as cyanide could occur both in its ionic form, nonvolatile, or protonated, a gas at room temperature (bp = 26 • C).…”

“…More recently, it has been carried out including a separation step coupled to a detection technique such as high performance liquid chromatography coupled to a fluorimetric detection [12] or capillary electrophoresis coupled to an ultraviolet detector [13]. Moreover, gas chromatography (GC) coupled to electron capture detector has been increasingly used following a derivatization step [14,15], headspace GC coupled to electron capture detector [16,17] or nitrogen-phosphorus detector (NPD) [18,19] and solid-phase microextraction (SPME) GC combined with NPD [19,20] or mass spectrometry [21]. Nevertheless, only a limited number of studies have been carried out for alkylnitriles determination in whole blood and to the best of our knowledge only one work deals with the simultaneous determination of cyanide and volatile alkylnitriles using headspace-GC-NPD [22].…”

Simultaneous derivatization and extraction of free cyanide in biological samples with home-made hollow fiber-protected headspace liquid-phase microextraction followed by capillary electrophoresis with UV detection

“…The performance of the developed procedure is summarized in Table 1, and compared with the HS-SDME [25], HS-SPME [14]. The calibration curve was linear for concentrations of CN − in the range from 0.1 to 20 mol L −1 (R 2 = 0.9987).…”

“…Several analytical methods, including optical [8,9], electrochemical [10,11] and chromatographic [12][13][14], have been published for the determination of cyanide in various sample matrices. The cyanide determination in body fluids requires the separation of cyanide from sample matrix, which is usually achieved through acidification.…”

Ninhydrin-based spectrophotometric assays of trace cyanide

“…2 New cyanide detection systems and sample pretreatment procedures for environmental, biological and plant samples have been so far reviewed. [6][7] Numerous reports have been published last years concerning the determination of trace levels of cyanide by spectrophotometry, [8][9][10] voltammetry, [11][12][13] combined colorimetric/fluorimetric [14][15][16] or enzymatic 11,13 sensors, different chromatographic 17,18 and electrophoretic 19,20 techniques.…”