A ng/L Level LC-MS Method Using Membrane SPE as Sampling Technology: Determination of Nine Halobenzoquinones in Potable Water.

A promising method was established for the determination of nine halobenzoquinones (HBQs) in potable water by membrane solid-phase extraction (MSPE) pretreatment and the liquid chromatography-mass spectrometry (LC-MS) method. A 500 mL water sample was taken for enrichment by the SDB-RPS membrane, which was previously activated by methanol and ultrapure water. The sample was eluted with methanol and re-dissolved with the initial mobile phase after nitrogen blowing. Then, it was detected in negative ion mode using the working curve, and HBQs were quantified by the external standard method. The linearity was satisfactory in the concentration range of 4-1000 ng/L, with correlation coefficients of 0.9963~0.9994. The recoveries were 73.5~126.6% at three spiked levels, with relative standard deviations (RSDs) of 6.8~15.5%. The limits of detection (LOD, S/N = 3) values were 0.1~0.7 ng/L. The results demonstrate that the MSPE-LC-MS method is reliable, rapid, and sensitive for the simultaneous analysis of nine HBPs in potable water.

Comprehensive Toxicological Assessment of Halobenzoquinones in Drinking Water at Environmentally Relevant Concentration.

Halobenzoquinones (HBQs), an emerging unregulated category of disinfection byproduct (DBP) in drinking water, have aroused an increasing concern over their potential health risks. However, the chronic toxicity of HBQs at environmentally relevant concentrations remains largely unknown. Here, the occurrence and concentrations of 13 HBQs in drinking water from a northern megacity in China were examined using ultrahigh performance liquid chromatography coupled with triple-quadrupole tandem mass spectrometry (UHPLC-MS/MS). Four HBQs, including 2,6-dichloro-1,4-benzoquinone (2,6-DCBQ), 2,6-dibromo-1,4-benzoquinone (2,6-DBBQ), 2,3,6-trichloro-1,4-benzoquinone (TriCBQ), and 2,5-dibromo-1,4-benzoquinone (2,5-DBBQ), were detected beyond 50% occurrence frequency and at median concentrations from 4 to 50 ng/L. The chronic toxicity of these four HBQs to normal human colon and liver cells (FHC and THLE-2) was investigated at these concentrations. After 90 days of exposure, 2,5-DBBQ and 2,6-DCBQ induced the highest levels of oxidative stress and deoxyribonucleic acid (DNA) damage in colon and liver cells, respectively. Moreover, 2,5-DBBQ and 2,6-DCBQ were also found to induce epithelial-mesenchymal transition (EMT) in normal human liver cells via the extracellular signal regulated kinase (ERK) signaling pathway. Importantly, heating to 100 °C (boiling) was found to efficiently reduce the levels of these four HBQs in drinking water. These results suggested that environmentally relevant concentrations of HBQs could induce cytotoxicity and genotoxicity in normal human cells, and boiling is a highly efficient way of detoxification for HBQs.

[Determination of twelve halobenzoquinones in drinking water by solid phase extraction-ultra-performance liquid chromatography-tandem mass spectrometry].

OBJECTIVE: To establish a method for twelve halobenzoquinones(HBQs) in drinking water by solid phase extraction-ultra-performance liquid chromatography coupled with electrospray-tandem mass spectrometry(SPE-UPLC-MS/MS). METHODS: The drinking water was acidified with formic acid and concentrated by Bond Elut Plexa solid phase extraction column. The sample solution was separated using Waters ACQUITY HSS T3 column(100 mm×2.1 mm, 1.8 µm) with gradient elution using methanol-water containing 0.1% formic acid as mobile phase. The target compouds were detected in negtive electrospray ionization(ESI~-) and multiple reaction monitoring. RESULTS: The concentration of twelve HBQs showed good linearity in the range 5.0-150.0 ng/mL, respectively, with the correlation coefficients greater than 0.999. The limits of detection(LOD) of twelve HBQs were lower than 2.0 ng/mL, and the limits of quantification(LOQ) for twelve HBQs were lower than 5.0 ng/mL, respectively. The recoveries of three levels in the matrix were 70.0%-84.0%. The matrix effffect was 0.08-0.64. CONCLUSION: The SPE-UPLC-MS/MS method has high sensitivity, good accuracy and fast analysis speed for the detection of halobenzoquinones in drinking water.

Phototransformation of halobenzoquinones in aqueous solution under the simulate sunlight: Kinetics, mechanism and products.

Halobenzoquinones (HBQs) are a novel family of unregulated disinfection byproducts (DBPs). Little is known about their phototransformation activities in natural water. Here, five HBQs with various halogenated substituent types, numbers, and structures positions were selected to investigate the kinetics of degradation in aqueous solutions at various concentrations and in the presence of common environmental variables (Cl-, NO2-, and humic acid). The results indicated that dichloride and dibromo-substituted HBQs were photolyzed, whereas tetrachloro-substituted HBQs showed little degradation. The photolysis rate constant (k) of HBQs decreased with increasing initial concentration. The presence of NO2- and Cl- promoted the degradation of HBQs mainly through the formation of hydroxyl radical (•OH), which were confirmed by electron paramagnetic resonance (EPR). In contrast, humic acid played a negative role on HBQs transformation due to the adsorption and quenching reactions. Possible conversion pathways for HBQs were proposed based on the identification of two major photodegradation products, hydroxylated HBQs and halogenated-benzenetriol, as well as reactive free radicals. This study provided meaningful insights into the environmental fates and risk assessments of HBQs in natural aquatic system.

Formation and toxicity contribution of chlorinated and dechlorinated halobenzoquinones from dichlorophenols after ozonation.

Halobenzoquinones (HBQs) are a class of disinfection byproducts with high cytotoxicity and potential carcinogenicity, which have been widely detected in chlorination of drinking water and swimming pool water. However, to date, the formation of HBQs upon ozonation and the HBQ precursors have been overlooked. This study investigated the formation of chlorinated and dechlorinated HBQs from six dichlorophenol (DCP) isomers. The monomeric and dimeric HBQs were identified in all the ozonation effluents, exhibiting 1-100 times higher toxicity levels than their precursors. The sum of detected HBQs intensity had a satisfactory linear relation with the maximum toxic unit (R2 = 0.9657), indicating the primary toxicity contribution to the increased overall toxicity of effluents. Based on density functional theory calculations, when ozone attacks the para carbon to the hydroxyl group of 2,3-DCP, the probability of producing chlorinated HBQs is 80.41 %, indicating that the para carbon attack mainly resulted in the formation of monomeric HBQs. 2,3-dichlorophenoxy radicals were successfully detected in ozonated 2,3-DCP effluent through electron paramagnetic resonance and further validated using theoretical calculation, revealing the formation pathway of dimeric HBQs. The results indicate that chlorinated phenols, regardless of the positions of chlorine substitution, can potentially serve as precursors for both chlorinated and dechlorinated HBQs formation during ozonation.

The alternation of halobenzoquinone disinfection byproduct on toxicogenomics of DNA damage and repair in uroepithelial cells.

Halobenzoquinones (HBQs) were recently discovered as an emerging class of drinking water disinfection byproducts with carcinogenic concern. However, the molecular mechanism underlying HBQs-induced DNA damage is not clear. In this study, we integrated in vitro genotoxicity, computational toxicology, and the quantitative toxicogenomic analysis of HBQs on DNA damage/repair pathways in human bladder epithelial cells SV-HUC-1. The results showed that HBQs could induce cytotoxicity with the descending order as 2,6-DIBQ > 2,6-DCBQ ≈ 2,6-DBBQ. Also, HBQs can increase DNA damage in SV-HUC-1 cells and thus generate genotoxicity. However, there is no significant difference in genotoxicity among the three HBQs. The results of molecular docking and molecular dynamics simulation further confirmed that HBQs had high binding fractions and stability to DNA. Toxicogenomic analysis indicated that HBQs interfered with DNA repair pathways, mainly affecting base excision repair, nucleotide excision repair and homologous recombination repair. These results have provided new insights into the underlying molecular mechanisms of HBQs-induced DNA damage, and contributed to the understanding of the relationship between exposure to DBPs and risks of developing bladder cancer.