Tingting Gong

Determination of iodide, iodate and organo-iodine in waters with a new total organic iodine measurement approach

The dissolved iodine species that dominate aquatic systems are iodide, iodate and organo-iodine. These species may undergo transformation to one another and thus affect the formation of iodinated disinfection byproducts during disinfection of drinking waters or wastewater effluents. In this study, a fast, sensitive and accurate method for determining these iodine species in waters was developed by derivatizing iodide and iodate to organic iodine and measuring organic iodine with a total organic iodine (TOI) measurement approach. Within this method, organo-iodine was determined directly by TOI measurement; iodide was oxidized by monochloramine to hypoiodous acid and then hypoiodous acid reacted with phenol to form organic iodine, which was determined by TOI measurement; iodate was reduced by ascorbic acid to iodide and then determined as iodide. The quantitation limit of organo-iodine or sum of organo-iodine and iodide or sum of organo-iodine, iodide and iodate was 5 μg/L as I for a 40 mL water sample (or 2.5 μg/L as I for an 80 mL water sample, or 1.25 μg/L as I for a 160 mL water sample). This method was successfully applied to the determination of iodide, iodate and organo-iodine in a variety of water samples, including tap water, seawater, urine and wastewater. The recoveries of iodide, iodate and organo-iodine were 91-109%, 90-108% and 91-108%, respectively. The concentrations and distributions of iodine species in different water samples were obtained and compared.

Formation and toxicity of halogenated disinfection byproducts resulting from linear alkylbenzene sulfonates.

Linear alkylbenzene sulfonates (LAS) are an important group of organic pollutants in urban wastewater effluents. The practice of using seawater for toilet flushing results in saline wastewater effluents, which contain high levels of bromide ions. Chlorine is most commonly used in wastewater disinfection. During chlorination of freshwater or saline wastewater effluents, some halogenated disinfection byproducts (DBPs) resulting from LAS could be formed. In this study, the overall formation of halogenated DBPs resulting from LAS was quantified by total organic halogen (TOX) measurement. Polar halogenated DBPs resulting from LAS were detected with a novel precursor ion scan method. The structures and formation pathways of the major ones were tentatively proposed. The overall toxicity of different scenarios of LAS samples was evaluated with embryos of a marine polychaete Platynereis dumerilii. The results demonstrate that chlorinated DBPs were generated during chlorination of LAS without bromide, while brominated DBPs were generated during chlorination of LAS with bromide. The TOX concentrations were relatively low, indicating that LAS were not quite reactive with halogen. The major polar chlorinated and brominated DBPs resulting from LAS were proposed to be 2,6-dichloro-3,5-dihydroxy-4-dodecylbenzenesulfonic acid and 2,6-dibromo-3,5-dihydroxy-4-dodecylbenzenesulfonic acid, which belong to a group of DBPs with similar structures but different halogen atoms, and their formation pathways were tentatively proposed. The results also reveal that the undisinfected LAS sample was the least toxic, followed by the chlorinated LAS sample without bromide, and the chlorinated LAS sample with bromide was the most toxic.

Facile synthesis of graphene nano zero-valent iron composites and their efficient removal of trichloronitromethane from drinking water.

Halonitromethanes (HNMs), as an emerging class of disinfection by-products containing nitrogen (N-DBPs) in drinking water, have possessed public health concerns. Two most studied materials, graphene and nanometer-sized zero-valent iron, have been successfully combined into binary nanocomposites (G-nZVI) via facile carbonization and calcinations of glucose and ferric chloride, which was used in the removal of HNMs from drinking water in this study. When the Fe/C mass ratio was 1:5, the as-prepared G-nZVI hybrids comprised numerous dispersed Fe(0) nanoparticles with a range of 5-10 nm in diameter. Batch experimental results indicated that the as-prepared G-nZVI could effectively remove trichloronitromethane (TCNM), a dominant in the group of HNMs from drinking water. About 99% of initial TCNM could be adsorbed and degraded under 60 mg/L G-nZVI dosage within 120 min. Kinetic studies indicated that the removal of TCNM by G-nZVI followed a pseudo first order rate (R(2) > 0.9). The degradation pathways of TCNM by G-nZVI nanocomposites might include dechlorination and denitration of TCNM. The Fe was in the form of iron oxides in the graphene material shape which was then restored to Fe(0) again via calcinations. These results indicated that the synthesized G-nZVI nanocomposites could be a powerful material to remove HNMs from drinking water.

Characterization of halogenated DBPs and identification of new DBPs trihalomethanols in chlorine dioxide treated drinking water with multiple extractions

Chlorine dioxide (ClO2) is a widely used alternative disinfectant due to its high biocidal efficiency and low-level formation of trihalomethanes and haloacetic acids. A major portion of total organic halogen (TOX), a collective parameter for all halogenated DBPs, formed in ClO2-treated drinking water is still unknown. A commonly used pretreatment method for analyzing halogenated DBPs in drinking water is one-time liquid-liquid extraction (LLE), which may lead to a substantial loss of DBPs prior to analysis. In this study, characterization and identification of polar halogenated DBPs in a ClO2-treated drinking water sample were conducted by pretreating the sample with multiple extractions. Compared to one-time LLE, the combined four-time LLEs improved the recovery of TOX by 2.3 times. The developmental toxicity of the drinking water sample pretreated with the combined four-time LLEs was 1.67 times higher than that pretreated with one-time LLE. With the aid of ultra-performance liquid chromatography/electrospray ionization-triple quadrupole mass spectrometry, a new group of polar halogenated DBPs, trihalomethanols, were detected in the drinking water sample pretreated with multiple extractions; two of them, trichloromethanol and bromodichloromethanol, were identified with synthesized standard compounds. Moreover, these trihalomethanols were found to be the transformation products of trihalomethanes formed during ClO2 disinfection. The results indicate that multiple LLEs can significantly improve extraction efficiencies of polar halogenated DBPs and is a better pretreatment method for characterizing and identifying new polar halogenated DBPs in drinking water.

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.

Tracing the sources of iodine species in a non-saline wastewater

There are two types of wastewater in Hong Kong, non-saline and saline wastewaters. When it comes to disinfection, iodide is an important inorganic ion in concern because it may involve in the formation of iodinated disinfection byproducts, which show significantly higher toxicity than their brominated and chlorinated analogues. In this study, it was found that a non-saline wastewater in Hong Kong contained an unexpected high level of iodine. To trace the iodine sources of this non-saline wastewater, the information of the corresponding area was collected to find the possible iodine sources; then, the water samples from the possible iodine sources were collected; the concentrations of iodine species (iodide, iodate and organic iodine) in these collected water samples were determined; finally, the contribution percentages of iodine species from different sources were calculated. The results revealed that a specific domestic wastewater was the major iodine source, contributing to 68.6% of total iodine, 66.3% of iodide, 57.0% of iodate, and 112% of organic iodine in the non-saline wastewater, while landfill leachate, industrial and hospital wastewaters were the minor iodine sources, contributing to 6.6%, 3.1%, and 3.0% of total iodine in the non-saline wastewater, respectively. Furthermore, it was found that the extensive use of salt might result in high levels of iodine in the domestic wastewater and thus lead to the high level of iodine in the non-saline wastewater.

Formation of iodinated trihalomethanes and haloacetic acids from aromatic iodinated disinfection byproducts during chloramination

Iodinated disinfection byproducts (DBPs) are widely present in disinfected drinking waters and wastewater effluents, and they have drawn increasing concern owing to their high toxicity. To date, the reported iodinated DBPs mainly include aliphatic and aromatic ones, and iodinated trihalomethanes (THMs) and haloacetic acids (HAAs) are the most commonly detected aliphatic iodinated DBPs in disinfected waters. In this study, the formation of iodinated THMs and HAAs from aromatic iodinated DBPs during chloramination was investigated. The decomposition kinetics of the aromatic iodinated DBPs and the formation of iodinated THMs and HAAs were studied, the formation pathways of iodinated THMs and HAAs from the aromatic iodinated DBPs were explored, the factors affecting the formation were examined, and the toxicity change was evaluated. The results revealed that four aromatic iodinated DBPs (2,4,6-triiodophenol, 3,5-diiodo-4-hydroxybenzaldehyde, 3,5-diiodosalicylic acid, and 2,6-diiodo-4-nitrophenol) all underwent transformation to form triiodomethane (TIM), monoiodoacetic acid (MIAA), and diiodoacetic acid (DIAA) during chloramination. The decomposition of the aromatic iodinated DBPs all followed a pseudo-first-order decay during chloramination, and the rank order of the decomposition rate constants was as follows: 2,4,6-triiodophenol > 3,5-diiodo-4-hydroxybenzaldehyde ≥ 3,5-diiodosalicylic acid > 2,6-diiodo-4-nitrophenol. Several polar iodinated intermediates were detected and identified (e.g., 2,6-diiodo-1,4-benzoquinone and iodobutenedioic acid) during chloramination of 2,4,6-triiodophenol, based on which the formation pathways of TIM, MIAA, and DIAA from 2,4,6-triiodophenol during chloramination were proposed and further validated. The results also revealed that monochloramine dose, pH, temperature, and short free chlorine contact time all affected the formation of TIM, MIAA, and DIAA from 2,4,6-triiodophenol during chloramination. The cytotoxicity order of the eight iodinated DBPs was MIAA > 2,6-diiodo-4-nitrophenol > 2,4,6-triiodophenol > 2,6-diiodo-1,4-benzoquinone > DIAA ≥ 3,5-diiodosalicylic acid >3,5-diiodo-4-hydroxybenzaldehyde > TIM. The toxicity of the chloraminated 2,4,6-triiiodophenol sample first decreased and then increased over time due to the transformation.

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.

Molecularly imprinted solid phase extraction coupled with gas chromatography-mass spectrometry for determination of N-Nitrosodiphenylamine in water samples

In this study, the molecularly imprinted polymers (MIPs) with high specific surface area and extraction efficiency of N-Nitrosodiphenylamine (NDPhA) were successfully prepared and a highly sensitive and selective method was developed for determination of NDPhA in water samples using MIPs solid-phase extraction (SPE) coupled with gas chromatography mass spectrometry (GC-MS) detection. The MIPs were successfully prepared using the method of precipitation polymerization and using methacrylic acid as the functional monomer, ethylene glycol dimethacrylate as the cross-linker, and N, N-Diphenylformamide as the template molecule. The newly synthesized MIPs were characterized and used as SPE sorbents. Under the optimized conditions, the average recoveries of NDPhA spiked in ultrapure water were higher than 94% ± 2.9% at three different concentrations and the limit of detection and limit of quantitation were 0.8 ng L-1 and 2.4 ng L-1, respectively. Moreover, the high selectivity of MIPs was attained and the satisfactory recoveries of NDPhA which were spiked in to real samples were achieved in the range of 92-107% with relative standard deviations (RSDs) within 0.3-7.9%. The low levels of NDPhA were detected in the two of twelve wastewater samples with concentrations of 5.6 ng L-1 and 3.6 ng L-1 with RSDs of 5.6% and 2.8%, respectively. The developed MIP-SPE method was proved to be practically feasible for selective extraction and enrichment of NDPhA in real water samples.

Rapid and complete dehalogenation of halonitromethanes in simulated gastrointestinal tract and its influence on toxicity

Halonitromethanes (HNMs) as one typical class of nitrogenous disinfection byproducts in drinking water and wastewater are receiving attentions due to their high toxicity. This study applied a simulator of the human gastrointestinal tract to determine the dehalogenation processes of trichloronitromethane, bromonitromethane and bromochloronitromethane for the first time. Influence of digestion process of HNMs on gut microbiota and hepatotoxicity was further analyzed. Results showed that the three HNMs were rapidly and completely dehalogenated in the gastrointestinal tract, especially in the stomach (2 h retention Time) and small intestine (4 h retention Time). Mucin, cysteine, pancreatin and bile salts in the digestive juice played major roles in the dehalogenation process. HNMs and their dehalogenation products in the resulting fluids of stomach induced the highest toxicity followed by those in intestine and colon, exhibiting dose-dependent effects. Although most HNMs were degraded in the stomach and small intestine, residual HNMs entered into colon changed the microbial community. Abundance of several genera, such as Bacteroides, Lachnospiraceae_unassigned and Lactobacillus had high correlation with exposure concentration of HNMs. This study sheds new light on dehalogenation and toxic processes of HNMs by oral exposure, which provides basic data for their human health risk assessment.