Determination of pesticides and their degradation products in sediment samples by accelerated solvent extraction and solid-phase extraction with high-performance liquid chromatography-high-resolution mass spectrometry.

A new sensitive and selective methods was developed to quantify different types of pesticides and their degradation products in sediment. The method developed was optimized and modified based on the accelerated solvent extraction, followed by the solid-phase extraction clean-up technique. High-performance liquid chromatography coupled with mass spectrometry was used for analysis. The influence of various parameters on the extraction process was investigated, including the extraction temperature, extraction solvent, purification column and purification solvent, etc. Under the optimal conditions, the relative recoveries of the pesticides and their degradation products ranged from 80 to 106% for spiked blank sediment and environmental sediment samples with relative standard deviations of 1-9%. The method displayed low method detection limits for both sediment matrices and achieved good linearity over the tested range of concentrations. The physical and chemical properties of sediment showed that high content of sediment water content and humic acid would affect the extraction efficiency of sample pretreatment. The method was applied to environmental sediment to quantify pesticide residues in the samples. Based on the instrument and method performance validation results, the developed methods can be applied in environmental pesticide residue analysis, thus providing a scientific method for the detection of sediment samples.

Degradation of 2,6-dichloro-1,4-benzoquinone by UV/H2O2/O3 treatment: Effectiveness, water matrix effects, and degradation mechanism.

2,6-dichloro-1,4-benzoquinone (DCBQ), a typical representative of Halobenzoquinones, is an emerging aromatic disinfection by-product (DBP) with high toxicity and carcinogenicity, generated commonly through the chlorination in the drinking water disinfection process while there is still a lack of research on its removal. In this study, the effects of ultraviolet-based advanced oxidation processes (UV-AOPs) on the degradation of DCBQ were evaluated. The results showed that UV-AOPs are effective in degrading DCBQ. The removal of DCBQ by UV/H2O2/O3 was more significant than by UV/H2O2 or UV/O3, achieving a 96.7% removal rate at both the O3 and H2O2 doses of 1 mg/L. The results also indicated the alkaline and weakly acidic environments could facilitate the degradation of DCBQ, inorganic anions could inhibit DCBQ degradation and the degree of inhibition increased as the matrix concentration increased. The degradation of DCBQ was inhibited more by the CO32- than the other matrix components, such as Cl- and NO3-. It was shown by the density functional theory simulations and the ultrahigh-performance liquid chromatography (UPLC) - Orbitrap mass spectra that the electrons in DCBQ are mainly on the chlorine atom connected to the carboatomic ring and that OH• can attack the chlorine atom to cause de-chlorination. The DCBQ degradation pathway may involve the oxidation of DCBQ to 3-hydroxy-2,6-DCBQ (HO-DCBQ) and 3,5-dichloro-1,2,4-pyrogallol, the further degradation of intermediate products by OH• to dechlorinated forms of HO-DCBQ and DCBQ.

The characteristic of N-nitrosodimethylamine precursor release from algal organic matter and degradation performance of UV/H2O2/O3 technology.

Seasonal cyanobacterial blooms in eutrophic water releases algal organic matter (AOM), which contains large amount of dissolved organic nitrogen (DON) and is difficult to be removed effectively by conventional treatment processes (e.g., coagulation and sand filtration) because of its high hydrophilicity. Moreover, N-nitrosodimethylamine (NDMA) can be generated by the reaction of AOM with disinfectants in the subsequent disinfection process. In this study, the formation of NDMA from different AOM components was explored and the control of algal-derived NDMA precursors by UV/H2O2/O3 was evaluated. The results showed that the hydrophilic and polar components of AOM with the low molecular weight had higher NDMA yields. UV-based advanced oxidation process (AOPs) is effective in degrading NDMA precursors, while the removal rate can be affected greatly by UV doses. The removal rate of NDMA precursors by UV/H2O2/O3 is higher than by UV/H2O2 or UV/O3 which can reach 95% at the UV dose of 400 mJ/cm2. An alkaline environment reduces the oxidation efficiency of UV/H2O2/O3 technology, while an acidic environment is conducive to its function. Inorganic anions such as HCO3-, SO42-, Cl- and NO3- are potential to compete with target algal-derived NDMA precursors for the oxidants reaction and inhibit the degradation/removal of these precursors. The degradation of algal-derived NDMA precursors by UV/H2O2/O3 is mainly accomplished by the oxidation of DON with secondary amide groups, and the main degradation mechanism by UV/H2O2/O3 was through the initial decomposition of macromolecular organic compounds such as biopolymers and humic substances and the further degradation of resulting small molecular components.