Formation mechanism of chloropicrin from amines and free amino acids during chlorination: A combined computational and experimental study.

Chloropicrin as one of the most frequently detected N-DBPs has drawn great attention due to its high toxicity. However, our understanding of its formation mechanism is still very limited. A combined computational and experimental approach was used in this study to reveal chloropicrin formation mechanism during chlorination. Ethylamine, n-propylamine, alanine and tryptophan along with the above two amines and their four derivatives substituted by -OH or/and -NO2 groups were chosen as computational and experimental model precursors, respectively. The results indicate that primary amines and free amino acids are more likely to share the same chloropicrin formation pathway including N-chlorination, imidization, ß-C-alcoholization, N-nitration, α-C-chlorination and dealdehydation processes. Moreover, elimination of hydrochloric acid from N,N-dichloro-amine and electrophilic addition of N-chloroalkylimide with hypochlorous acid were found to be the rate-limiting steps among all the elementary reactions. By skipping over both of the above rate-limiting steps, RCH(OH)CH2NO2 and RCH(OH)CH2NH(OH) compounds were proposed to be potent chloropicrin precursors, and experiments confirmed that 2-nitroethanol and N-methylhydroxylamine have the highest chloropicrin yields in the chlorination among all the precursors reported to date. The findings of this work are helpful for expanding the knowledge of chloropicrin formation mechanisms and predicting the potential chloropicrin precursors.

Tetracycline antibiotics as precursors of dichloroacetamide and other disinfection byproducts during chlorination and chloramination.

Pollution of natural water and even source water with pharmaceuticals is problematic worldwide and raises concern about the possibility of disinfection byproduct (DBP) formation during subsequent water treatment. In this study, the formation of DBPs, especially dichloroacetamide (DCAcAm), was investigated during chlorination and chloramination of tetracyclines, which are a class of broad-spectrum antibiotics. DBPs including DCAcAm were formed during chlorination and chloramination of tetracycline (TC). Although the concentrations and theoretical cytotoxicity of the DBPs formed from TC were affected by the contact time, disinfectant dose, and pH, DCAcAm was the main contributor determining the yields and cytotoxicity of the measured DBPs. The DCAcAm yields from four tetracycline antibiotics ranged from 0.43% to 54.26% for chlorination. For chloramination, the DCAcAm yields reached 44.57%, and the nitrogen in DCAcAm mainly came from tetracycline antibiotics rather than chloramines. ClO2 pre-oxidation and UV photolysis decreased DCAcAm formation during chlorination and chloramination of TC. The high yields observed in this study suggest that tetracycline antibiotics are possible precursors of DCAcAm.

ClO2 pre-oxidation impacts the formation and nitrogen origins of dichloroacetonitrile and dichloroacetamide during subsequent chloramination.

Chlorine dioxide (ClO2) can be used as a pre-oxidant when chloramination is performed in water treatment plants. However, the effects of ClO2 pre-oxidation on the formation of nitrogenous disinfection by-products, such as dichloroacetonitrile (DCAN) and dichloroacetamide (DCAcAm), during chloramination are not well understood. In this study, the effects of ClO2 pre-oxidation on the formation of DCAN and DCAcAm during chloramination of 28 model compounds and seven real water samples were investigated. The sources of nitrogen for DCAN and DCAcAm formation were investigated using 15N-labeled monochloramine. ClO2 pre-oxidation affected DCAN and DCAcAm formation during chloramination of model compounds in different ways. ClO2 pre-oxidation increased unlabeled and 15N-labeled DCAN and DCAcAm formation during chloramination of six amino acids and peptides and five indoles and tertiary amines. ClO2 pre-oxidation decreased DCAN formation but increased DCAcAm formation during chloramination of three hydroxybenzamide compounds, but had the opposite effects for four tetracyclines. ClO2 pre-oxidation generally decreased DCAN and DCAcAm formation during chloramination of the phenolic compounds that are precursors not containing nitrogen. 2-Aminoacetophenone, formamid-trans-muconic acid, and unsaturated ketones were found to be transformation products of ClO2 oxidation of 3-methylindole, salicylamide, and resorcinol, respectively. Possible DCAN and DCAcAm formation pathways during chloramination after ClO2 oxidation were identified. For most of the water samples, ClO2 pre-oxidation decreased the amounts of DCAN and DCAcAm formed during chloramination by 36%-70% and 11%-59%, respectively. This may have been caused by ClO2 oxidation destroying phenolic precursors and macromolecular proteins rather than amino acids in the water samples.