Application of central composite design in the optimisation of thermal desorption parameters for the trace level determination of the chemical warfare agent chloropicrin

Abstract

A quantitative trace-level thermal desorption gas chromatography mass spectrometry method was developed for chloropicrin CCl₃NO₂ using central composite design. Factors influencing the thermal decomposition were elucidated and optimum conditions for maximum response deduced. Four factors were investigated: desorption time, desorption temperature, valve temperature and line temperature. Only valve and line temperature influenced the response. The storage stability of chloropicrin on Tenax TA™ was investigated. Only the storage conditions affected recovery: no significant loss of chloropicrin was observed for spiked tubes stored in a refrigerator for up to 30 days. The application of central composite design to study thermal degradation of chloropicrin has not been described in the literature. The benefits in adopting this approach are reflected in the limit of detection, 22 ng on the sorbent tube (equivalent to 3.2 ppbv), the lowest atmospheric detection limit reported to date.