Coumarin was detected as one of the most abundant compounds
by
nontargeted analysis of natural product components in actual water
samples prior to disinfection. More importantly, prechlorination of
humic acid generated 3-hydroxycoumarin and monohydroxy-monomethyl-substituted
coumarin with a total yield of ≤10.1%, which suggested the
humic substance in raw water is an important source of coumarins.
7-Hydroxycoumarin, 6-hydroxy-4-methylcoumarin, 6,7-dihydroxycoumarin,
and 7-methoxy-4-methylcoumarin were identified in raw water by high-performance
liquid chromatography–tandem high-resolution mass spectrometry
because only some coumarin standards were commercially available.
Their chlorination generated monochlorinated and polychlorinated coumarins,
and their structures were confirmed by the synthesized standards.
These products could form at various dosages of chlorine and pH levels,
and some with a concentration of 600 ng/L can be stable in tap water
for days. 3,6,8-Trichloro-7-hydroxycoumarin, 3-chloro-7-methoxy-4-methylcoumarin,
and 3,6-dichloro-7-methoxy-4-methylcoumarin were first identified
in finished water with concentrations of 0.0670, 78.1, and 14.7 ng/L,
respectively, but not in source water, suggesting that they are new
DBPs formed during disinfection. The cytotoxicity of 3-chloro-7-methoxy-4-methylcoumarin
in CHO-K1 cells was comparable to those of 2,6-dibromo-1,4-benzoquinone
and 2,6-dichloro-1,4-benzoquinone in TIC-Tox analyses, suggesting
that further investigation of their occurrence and control in drinking
water systems is warranted.