Simultaneous determination of iodinated haloacetic acids and aromatic iodinated disinfection byproducts in waters with a new SPE-HPLC-MS/MS method.

Iodinated disinfection byproducts (DBPs) are an emerging category of halogenated DBPs in concern due to their high toxicity. Among them, polar iodinated DBPs, mainly including iodinated haloacetic acids (HAAs) and aromatic iodinated DBPs, were reported to be especially toxic. Thus, simultaneous determination of these polar iodinated DBPs in disinfected waters is of great significance for DBP studies. In this study, it was found that traditional liquid-liquid extraction, which was adopted for the determination of polar iodinated DBPs, was actually not suitable for the determination of monoiodoacetic acid (MIAA) and diiodoacetic acid (DIAA) due to the low recoveries, and thus a new SPE-HPLC-MS/MS method was developed for the simultaneous determination of iodinated HAAs and aromatic iodinated DBPs. The parameters for SPE pretreatment were optimized, including SPE cartridge, eluent volume, formic acid content in eluent, and sample pH before SPE. The new method was demonstrated to be sensitive and accurate with detection limits of 0.15, 0.04, 0.03, 0.02, 0.06, and 0.06 ng/L, quantitation limits of 0.48, 0.13, 0.10, 0.06, 0.19, and 0.19 ng/L, and precision of 8.3%, 6.0%, 12.3%, 8.8%, 11.4%, and 15.6% for MIAA, DIAA, 3,5-diiodo-4-hydroxybenzaldehyde, 3,5-diiodosalicylic acid, 2,6-diiodo-4-nitrophenol and 2,4,6-triiodophenol, respectively. The recoveries of these six polar iodinated DBPs were all in the range of 70-110%. The new method was applied to the determination of iodinated HAAs and aromatic iodinated DBPs in nine tap water samples, and they were detected with concentrations ranging from 0.03 to 3.97 ng/L, among which MIAA was detected in all the samples with the highest concentrations.

Transformation among Aromatic Iodinated Disinfection Byproducts in the Presence of Monochloramine: From Monoiodophenol to Triiodophenol and Diiodonitrophenol.

Aromatic iodinated disinfection byproducts (DBPs) are a newly identified category of highly toxic DBPs. Among the identified aromatic iodinated DBPs, 2,4,6-triiodophenol and 2,6-diiodo-4-nitrophenol have shown relatively widespread occurrence and high toxicity. In this study, we found that 4-iodophenol underwent transformation to form 2,4,6-triiodophenol and 2,6-diiodo-4-nitrophenol in the presence of monochloramine. The transformation pathways were investigated, the decomposition kinetics of 4-iodophenol and the formation of 2,4,6-triiodophenol and 2,6-diiodo-4-nitrophenol were studied, the factors affecting the transformation were examined, the toxicity change during the transformation was evaluated, and the occurrence of the proposed transformation pathways during chloramination of source water was verified. The results revealed that 2,4,6-triiodophenol and 2,6-diiodo-4-nitrophenol, which could account for 71.0% of iodine in the transformed 4-iodophenol, were important iodinated transformation products of 4-iodophenol in the presence of monochloramine. The transformation pathways of 4-iodophenol in the presence of monochloramine were proposed and verified. The decomposition of 4-iodophenol in the presence of monochloramine followed a pseudo-second-order decay. Various factors including monochloramine dose, pH, temperature, nitrite concentration, and free chlorine contact time (before chloramination) affected the transformation. The cytotoxicity of the chloraminated 4-iodophenol samples increased continuously with contact time. The proposed transformation pathways occurred during chloramination of source water.

Selection and applicability of quenching agents for the analysis of polar iodinated disinfection byproducts.

Iodide is widely present in drinking water sources as well as wastewater effluents. Chlorination and chloramination are the most commonly used disinfection methods. During chlorination or chloramination of drinking water/wastewater effluents, iodide may be oxidized to hypoiodous acid, which may further react with organic matter to form iodinated disinfection byproducts (DBPs). Recently, several new polar iodinated DBPs have been identified in drinking water as well as chlorinated wastewater effluents, and they have drawn increasing concerns due to their high toxicity. In DBPs studies, the selection of an appropriate quenching agent is critical to prevent further formation or any decomposition of DBPs during the holding time between sample collection and analysis. A previous study reported the applicability of different quenching agents for the analysis of various categories of chlorinated and brominated DBPs. But the applicability of quenching agents for the analysis of polar iodinated DBPs has not been reported. In this study, four different quenching agents (sodium sulfite, sodium thiosulfate, ascorbic acid and sodium borohydride) were tested for their suitability for the analysis of polar iodinated DBPs, and ascorbic acid was selected as the suitable quenching agent. Furthermore, it was found that ascorbic acid was applicable for the analysis of polar iodinated DBPs under the quenching agent doses of 0-0.42 mmol/L (stoichiometric amounts equivalent to 0-30 mg/L Cl2), contact times within 24 h, and pHs in the range of 6-8. Therefore, ascorbic acid was a widely applicable quenching agent for the analysis of polar iodinated DBPs under various conditions.