Quantification of aqueous cyanogen chloride and cyanogen bromide in environmental samples by MIMS

Membrane introduction mass spectrometry (MIMS) was developed and verified for the direct quantification of cyanogen chloride (CNCl) and cyanogen bromide (CNBr) in environmental samples without any sample workup. Factors including the membrane temperature and the liquid flow rates were examined for system optimization. The MIMS method provided linear responses for three orders of magnitude of concentrations. The instrument detection limits of CNCl and CNBr were 1.2 and 3.8 μg/L, respectively, and the method detection limits of CNCl and CNBr were both 1.7 μg/L. Effects of pH and the water matrix including synthetic water, saline water, natural surface water, and wastewater, on the responses were also examined. A pH ranging from 3 to 10 did not affect the quantification. The average recoveries of CNCl and CNBr in the water matrixes tested were 98.5% and 92.7%, respectively. The use of the MIMS method in on-line monitoring of the formation of cyanogen halide was demonstrated in chlorination of aqueous solutions containing glycine and bromide ions. The results indicated the important role of bromide ions in cyanogen halide speciation.