Guoyu Ding

A Picture of Polar Iodinated Disinfection Byproducts in Drinking Water by (UPLC/)ESI-tqMS

Iodinated disinfection byproducts (DBPs) are generally more toxic than their chlorinated and brominated analogues. Up to date, only a few iodinated DBPs in drinking water have been identified by gas chromatography/mass spectrometry. In this work, a method for fast selective detection of polar iodinated DBPs was developed using an electrospray ionization-triple quadrupole mass spectrometer (ESI-tqMS) by conducting precursor ion scan of iodide at m/z 126.9. With such a method, pictures of polar iodinated DBPs in chlorinated, chloraminated, and chlorine-ammonia treated water samples were achieved. By coupling state-of-the-art ultra performance liquid chromatography (UPLC) to the ESI-tqMS, structures of 17 iodinated DBPs were tentatively proposed. The results fully demonstrate that, with respect to the DBP number/levels among the three disinfection processes, chloramination generally generated the most/highest iodinated DBPs, chlorination generally produced the fewest/lowest iodinated DBPs, and chlorine-ammonia sequential treatment formed iodinated DBPs lying in between; the numbers of iodinated DBPs in chloraminated Suwannee River Fulvic Acid (SRFA) and Humic Acid (SRHA) were nearly the same, but the levels of aliphatic iodinated DBPs were higher in the chloraminated SRFA while the levels of aromatic iodinated DBPs were higher in the chloraminated SRHA; a couple of nitrogenous iodinated DBPs were found in chloramination and chlorine-ammonia treatment. The ratio of total organic iodine levels in chlorine-ammonia sequential treatment and chloramination could be expressed as a function of the lag time of ammonia addition.

Formation of New Brominated Disinfection Byproducts During Chlorination of Saline Sewage Effluents

Chlorination could be the most cost-effective method for disinfecting saline sewage effluents resulting from toilet flushing with seawater. Upon chlorination, the high levels of bromide ions in saline sewage effluents (up to 32 mg/L) can be oxidized to hypobromous acid/hypobromite, which could then react with organic matter in the sewage effluents to form brominated disinfection byproducts (Br-DBPs). In this study, primary and secondary saline sewage effluents were collected and chlorinated at different chlorine doses, and a powerful precursor ion scan method using ultra performance liquid chromatography/electrospray ionization-triple quadrupole mass spectrometry was adopted for detection and identification of polar Br-DBPs in these samples. With the new method, 54 major polar Br-DBPs were detected in the chlorinated saline effluents and six of them were newly identified as wastewater DBPs, including bromomaleic acid, 5-bromosalicylic acid, 3,5-dibromo-4-hydroxybenzaldehyde, 3,5-dibromo-4-hydroxybenzoic acid, 2,6-dibromo-4-nitrophenol, and 2,4,6-tribromophenol. The formation of polar Br-DBPs, especially those newly detected ones, during chlorination of the saline effluents was studied. For the secondary saline effluent, various polar Br-DBPs formed and reached their maximum levels at different chlorine doses, whereas for the primary saline effluent, the formation of polar Br-DBPs basically kept increasing with increasing chlorine dose. Compared with the secondary saline effluent, the primary saline effluent generated fewer and less Br-DBPs and rarely generated nitrogenous Br-DBPs.

Formation of halogenated organic byproducts during medium-pressure UV and chlorine coexposure of model compounds, NOM and bromide.

When chlorine is applied before or during UV disinfection of bromide-containing water, interactions between chlorine, bromide and UV light are inevitable. Formation of halogenated organic byproducts was studied during medium-pressure UV (MPUV) and chlorine coexposure of phenol, nitrobenzene and benzoic acid and maleic acid, chosen to represent electron-donating aromatics, electron-withdrawing aromatics, and aliphatic structures in natural organic matter (NOM), respectively. All were evaluated in the presence and absence of bromide. MPUV and chlorine coexposure of phenol produced less total organic halogen (TOX, a collective parameter for halogenated organic byproducts) than chlorination in the dark, and more haloacetic acids instead of halophenols. Increases in TOX were found in the coexposure of nitrobenzene and benzoic acid, but maleic acid was rather inert during coexposure. The presence of bromide increased the formation of brominated TOX but did not significantly affect total TOX formation, in spite of the fact that it reduced hydroxyl radical levels. MPUV and chlorine coexposure of NOM gave a higher differential UV absorbance of NOM and a larger shift to lower molecular weight compounds than chlorination in the dark. However, TOX formation with NOM remained similar to that observed from dark chlorination.