Derivatization-free multi-step extraction for trace haloacetic acids analysis with ion chromatography: Performance and mechanisms

Haloacetic acids (HAAs) are a type of disinfection byproducts commonly found in drinking water with carcinogenic, mutagenic, or teratogenic risks to humans. Currently, the analytical methods of trace HAAs are either labor-intensive or very expensive. We herein propose a facile multiple-step extraction strategy for HAAs analysis with common ion chromatography (IC). This study is based on a fundamental water chemistry principle that HAAs become protonated featuring positive logK(ow) values (> 0.34) under pH < pKa but deprotonated featuring negative logK(ow) values (<-2.37) under pH > pKa. By taking advantage of the species and property switches, HAAs can be extracted and enriched into methyl tert-butyl ether first at pH < 0.5 and then back-extracted into neutral water and enriched again. Equally important, interfering anions in IC chromatogram are eliminated because they have negative logK(ow) values. Verification results show that HAAs were enriched by 11.4 times in average while interfering anions were almost eliminated (> 99%). Although similar to USEPA Method 552.3 in method detection limits (0.033-0.246 mu g/L), recoveries (70%~110%), and relative standard deviations (< 9.91%), this method took <= 70 min to run a batch of samples without derivatization, which takes over 2 h. The methodology may be applicable to other pollutants that also have contrasting K-ow values at different pH.