Tribromopyrrole, Brominated Acids, and Other Disinfection Byproducts Produced by Disinfection of Drinking Water Rich in Bromide

Abstract

Using gas chromatography/mass spectrometry (GC/MS), we investigated the formation of disinfection byproducts (DBPs) from high bromide waters (2 mg/L) treated with chlorine or chlorine dioxide used in combination with chlorine and chloramines. This study represents the first comprehensive investigation of DBPs formed by chlorine dioxide under high bromide conditions. Drinking water from full-scale treatment plants in Israel was studied, along with source water (Sea of Galilee) treated under carefully controlled laboratory conditions. Select DBPs (trihalomethanes, haloacetic acids, aldehydes, chlorite, chlorate, and bromate) were quantified. Many of the DBPs identified have not been previously reported, and several of the identifications were confirmed through the analysis of authentic standards. Elevated bromide levels in the source water caused a significant shift in speciation to bromine-containing DBPs; bromoform and dibromoacetic acid were the dominant DBPs observed, with very few chlorine-containing compounds found. Iodo-trihalomethanes were also identified, as well as a number of new brominated carboxylic acids and 2,3,5-tribromopyrrole, which represents the first time a halogenated pyrrole has been reported as a DBP. Most of the bromine-containing DBPs were formed during pre-chlorination at the initial reservoir, and were not formed by chlorine dioxide itself. An exception wasthe iodo-THMs, which appeared to be formed by a combination of chlorine dioxide with chloramines or chlorine (either added deliberately or as an impurity in the chlorine dioxide). A separate laboratory study was also conducted to quantitatively determine the contribution of fulvic acids and humic acids (from isolated natural organic matter in the Sea of Galilee) as precursor material to several of the DBPs identified. Results showed that fulvic acid plays a greater role in the formation of THMs, haloacetic acids, and aldehydes, but 2,3,5-tribromopyrrole was produced primarily from humic acid. Because this was the first time a halopyrrole has been identified as a DBP, 2,3,5-tribromopyrrole was tested for mammalian cell cytotoxicity and genotoxicity. In comparison to other DBPs, 2,3,5-tribromopyrrole was 8x, 4.5x, and 16x more cytotoxic than dibromoacetic acid, 3-chloro-4-(dichloromethyl)-5-hydroxy-2-[5H]-furanone [MX], and potassium bromate, respectively. 2,3,5-Tribromopyrrole also induced acute genomic damage, with a genotoxic potency (299 microM) similar to that of MX.

Formation of Haloacetonitriles, Haloacetamides, and Nitrogenous Heterocyclic Byproducts by Chloramination of Phenolic Compounds

“…Moreover, the presence of brominated pyrroles was reported from chlorinated 307 saline wastewater effluents (M. Yang et al, 2014). Tribromopyrrole is a major chlorination by-308 product of bromide-containing waters and has been demonstrated to be strongly cytotoxic and 309 genotoxic to mammalian cells (Richardson et al, 2003). 310…”

Optimization of methods for the determination of DBPs

“…Thus, the first report of a DBP having an aminoxy structure was reported by Taguchi who identified 1-aminoxy-1-chlorobutan-2-ol and 1-aminoxy-1-bromobutan-2-ol in drinking water treated with chlorine using GC/MS with low and high resolution and EI and CI modes and GC/MS/MS (Taguchi, 2001). On the other hand, the presence of an halogenated pyrrole as a DBP has been recently reported (Richardson et al, 2003). This compound, 2,3,5-tribromopyrrole and other new brominated carboxylic acids were identified by GC/LRMS and GC/HRMS and EI and CI modes and 2,3,5-tribromopyrrole proved to be more cytotoxic than bromate, bromoacetic acid and MX.…”

“…Their determination is important toxicologically because iodoacetic acid has been shown to induce neural tube closure defects and other developmental abnormalities in mouse embryos (Hunter and Tugman, 1995;Hunter et al, 1996). Methylation derivatization with BF 3 -methanol were used to enable the identification of iodinated carboxylic acid DBPs such as iodoacetic, bromoiodoacetic, (Z) and (E)-3-bromo3-iodopropenoic and (E)-2-iodo-3-methylbutenedioic acid with GC/MS in drinking water samples from source water with high concentrations of bromide and iodide that was treated with chloramines (Richardson et al, 2003). Haloacetic acids have been also analyzed by LC/MS with negative ion electrospray (ESI) (Hashimoto et al, 1998;Takino et al, 2000;Loos and Barceló, 2001) or ESI of stable association complexes to reduce problems with brominated trihaloacetic acids (Magnuson and Kelty, 2000a).…”

“…However, several authors (Chen et al, 2002;Richardson et al, 2003) when analyzed trihalonitromethanes (i.e. bromopicrin) modified the commonly used injection port temperatures and transfer line in GC/MS analysis to ≤170ºC and ≤225ºC, respectively, to avoid decomposition (i.e.…”

Qualitative and Quantitative Analysis of the Inorganic Materials Changes with Time in the Stages of the Wastewater Treatment Plant

“…Under certain circumstances, these oxidants could induce the formation of the harmful by-products due to their highly reactivity with water matrix components and micro pollutants [18][19][20][21][22][23][24]. These oxidants were generally low cost; one was chlorine, the one used in water disinfection in pre and post treatments.…”