Volatile chlorinated substances produced by chlorination of humic acid were identified, and possible formation mechanism of one of these substances, chloropicrin, was investigated.
The results obtained were as follows.
(1) Volatile chlorinated substances were identified chloropicrin and carbon tetrachloride besides chloroform by GC-MS with a computarized data system.
(2) Precursors for the chloropicrin formation were amino acids such as alanine, threonine, ornithine, gultamic acid and glycine; nitro- or nitrosophenols; nitro- or nitrosoresorcinols; nitromethane and nitro- ethane.
(3) Chloropicrin was produced by chlorination of humic acid and resorcinol in the presence of nitrite.
(4) Mechanism of chloropicrin formation by chlorination of alanine was proposed as follows : Alanine was decarboxylated (-COOH→CO
2↑), oxidized (-NH
2→-NO2) and consequently chlorinated to chloropicrin.
(5) As for mechanism of chloropicrin formation by chlorination of resorcinol in the presence of nitrite, it was recognized that nitrososubstitution of resorcinol occurred in the presence of nitrite and produces nitrosoresorcinol, which was oxidized to nitroresorcinol with hypochlorite, and finally nitroresorcinol formed chloropicrin by the way of the ROOK's reaction of chloroform formation from resorcinol.
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