Curtin Water Quality Research Centre, Curtin University, Kent Street, Bentley 6102, Perth, Australia.
J Chromatogr A. 2012 Feb 17;1225:45-54. doi: 10.1016/j.chroma.2012.01.005. Epub 2012 Jan 11.
Halonitriles are a class of nitrogen-containing disinfection by-products (DBPs) that have been reported to be more toxic and carcinogenic than the regulated DBPs. While haloacetonitriles (HANs) are often measured in drinking waters, there is little information on the formation, characteristics, and occurrence of other, higher molecular weight halonitriles. Halopropionitriles and halobutyronitriles have been predicted to be highly toxic and carcinogenic, and may have sufficient potency and selectivity to account for epidemiological associations of chlorinated and chloraminated water with adverse health effects. This paper reports on the development, optimisation, and validation of a simple, robust, and sensitive analytical method for the determination of halonitriles in waters, as well as the application of the method to study the formation and characteristics of halonitriles. This is the first reported method development for analysis halopropionitriles and halobutyronitriles, and the first study on their formation and occurrence as DBPs in drinking waters. The new method uses headspace solid-phase microextraction to extract the halonitriles from water, which are then analysed using gas chromatography-mass spectrometry (HS SPME/GC-S). The method demonstrated good sensitivity (detection limits: 0.9-80 ng L⁻¹) and good precision (repeatability: 3.8-12%), and is linear over three orders of magnitude. Matrix effects from raw drinking water containing organic carbon (4.1 mg L⁻¹) were shown to be negligible in the analysis of halonitriles. The optimised method was used to study the stability and persistence of halonitriles in aqueous samples, and the formation and occurrence of halonitriles in waters. Results from laboratory-scale disinfection experiments showed that haloacetonitriles were formed in chlorinated and chloraminated samples, but 2,2-dichloropropionitrile was only measured in chloraminated samples. Results from surveys of several drinking water distribution systems confirmed the laboratory findings.
卤代腈是一类含氮的消毒副产物 (DBPs)，已被报道比受管制的 DBPs 更具毒性和致癌性。虽然卤乙腈 (HANs) 经常在饮用水中进行测量，但关于其他、更高分子量的卤代腈的形成、特性和出现的信息很少。卤代丙腈和卤代丁腈已被预测为具有高度毒性和致癌性，并且可能具有足够的效力和选择性，以解释氯化和氯胺化水与不良健康影响之间的流行病学关联。本文报告了一种简单、稳健和灵敏的分析方法的开发、优化和验证，用于测定水中的卤代腈，以及该方法在研究卤代腈的形成和特性中的应用。这是首次报道用于分析卤代丙腈和卤代丁腈的方法开发，也是首次研究它们作为饮用水中 DBPs 的形成和出现。新方法使用顶空固相微萃取 (HS SPME/GC-S) 从水中提取卤代腈。该方法表现出良好的灵敏度（检测限：0.9-80ng L⁻¹）和良好的精密度（重复性：3.8-12%），并且在三个数量级范围内呈线性。含有有机碳（4.1mg L⁻¹）的原水的基质效应在卤代腈的分析中可忽略不计。优化后的方法用于研究卤代腈在水溶液中的稳定性和持久性，以及卤代腈在水中的形成和出现。实验室规模的消毒实验结果表明，卤乙腈在氯化和氯胺化样品中形成，但 2,2-二氯丙腈仅在氯胺化样品中测量到。几个饮用水分配系统的调查结果证实了实验室的发现。
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