High resolution mass spectrometry (HRMS) coupled to either
gas
chromatography or reversed-phase liquid chromatography is the generic
method to identify unknown disinfection byproducts (DBPs) but can
easily overlook their highly polar fractions. In this study, we applied
an alternative chromatographic separation method, supercritical fluid
chromatography-HRMS, to characterize DBPs in disinfected water. In
total, 15 DBPs were tentatively identified for the first time as haloacetonitrilesulfonic
acids, haloacetamidesulfonic acids, and haloacetaldehydesulfonic acids.
Cysteine, glutathione, and p-phenolsulfonic acid
were found as precursors during lab-scale chlorination, with cysteine
providing the highest yield. A mixture of the labeled analogues of
these DBPs was prepared by chlorination of 13C3-15N-cysteine and analyzed using nuclear magnetic resonance
spectroscopy for structural confirmation and quantification. A total
of 6 drinking water treatment plants utilizing various source waters
and treatment trains produced sulfonated DBPs upon disinfection. Those
were widespread in the tap water of 8 cities across Europe, with estimated
concentrations up to 50 and 800 ng/L for total haloacetonitrilesulfonic
acids and haloacetaldehydesulfonic acids, respectively. Up to 850
ng/L haloacetonitrilesulfonic acids were found in 3 public swimming
pools. Considering the stronger toxicity of haloacetonitriles, haloacetamides,
and haloacetaldehydes than the regulated DBPs, these newly found sulfonic
acid derivatives may also pose a health risk.