National Research Council of Canada. Measurement Science and Standards
Cyanide; Pentafluorobenzyl bromide; Soil; Isotope dilution; Gas chromatography-mass Spectrometry
The high toxicity of cyanide, along with its widespread industrial use, has fuelled interest in the development of analytical methods for its determination in complex matrices. In this study, we propose a novel approach for the measurement of total cyanide in soil samples based on single-step derivatization with pentafluorobenzyl bromide (F₅Bn−Br) followed by quantitation with gas chromatography mass spectrometry in negative chemical ionization mode.
The reaction between CN⁻ and F₅Bn−Br resulted in the identification of several derivatives such as F₅Bn−CN, (F₅Bn)(F₅Ph)CH−CN, and (F₅Bn)₂(F₅Ph)C−CN. The relative proportion between such compounds was dependent on experimental conditions. When a 100 μL aliquot of an alkaline-aqueous extract was reacted with 700 μL of 1.3% F₅Bn−Br in acetone, the tri-alkylated derivative was the most abundant. In such conditions a detection limit of 0.5 ng/g of CN⁻ was attained.
Soil samples were initially spiked with an alkaline solution of K¹³C¹⁵N internal standard and suspended in 7.5% aqueous NaOH. Determination of total cyanide was achieved by digestion of the alkaline extract with H₃PO₄ to produce HCN which was then trapped in 0.1% NaOH in a sealed double vial system, followed by reaction with F₅Bn−Br. Isotope dilution calibration was chosen for quantitation, and the validity of the novel method was demonstrated by analysis of soil Certified Reference Materials (CRMs) and by spike recovery tests.