Qingfu Ye

Degradation Kinetics and Metabolites of Carbamazepine in Soil

The antiepileptic drug carbamazepine (CBZ) is one of the most frequently detected human pharmaceuticals in wastewater effluents and biosolids. Soil is a primary environmental compartment receiving CBZ through wastewater irrigation and biosolid application. In this study, we explored the transformation of CBZ to biologically active intermediates in soil. Both (14)C labeling and liquid chromatography-tandem mass spectrometry (LC-MS/MS) were used to track transformation kinetics and identify major degradation intermediates. Through 120 days of incubation under aerobic conditions, mineralization of CBZ did not exceed 2% of the spiked rate in different soils. Amendment of biosolids further suppressed mineralization. The fraction of non-extractable (i.e., bound) residue also remained negligible (<5%). On the other hand, CBZ was transformed to a range of degradation intermediates, including 10,11-dihydro-10-hydroxycarbamazepine, carbamazepine-10,11-epoxide, acridone-N-carbaldehyde, 4-aldehyde-9-acridone, and acridine, of which acridone-N-carbaldehyde was formed in a large fraction and appeared to be recalcitrant to further degradation. Electrocyclization, ring cleavage, hydrogen shift, carbonylation, and decarbonylation contributed to CBZ transformative reactions in soil, producing biologically active products. The persistence of the parent compound and formation of incomplete intermediates suggest that CBZ has a high risk for off-site transport from soil, such as accumulation into plants and contamination of groundwater.

Improved Measurements of Partition Coefficients for Polybrominated Diphenyl Ethers

Polybrominated diphenyl ethers (PBDEs) are a class of widely used brominated flame retardants with strong hydrophobicity. Due to their strong affinity for organic matter, accurate measurement of adsorption coefficients for PBDEs using conventional batch methods can be confounded by biases caused by their sorption to dissolved organic carbon (DOC). In this study, sorption isotherms were constructed for BDE-47 and BDE-99 in sediments by using different methods to measure the aqueous phase concentration Cw. Upon centrifugation, Cw measured by automated solid-phase microextraction (Cw-SPME) was consistently smaller than by liquid-liquid extraction (Cw-LLE), suggesting substantial association of PBDEs with DOC. Significant underestimations (1.2-106-fold) of sediment-water partition coefficient Kd occurred when Cw was measured by LLE. The log KDOC values derived from the SPME measurements ranged from 5.10 to 8.02 for eight congeners from BDE-28 to BDE-183, suggesting a strong tendency for PBDEs to complex with DOC. This study showed that PBDE congeners have larger sorption coefficients than would be measured by the conventional method. The high affinity to DOC also means a potential for DOC-facilitated transport, thus enhancing the environmental mobility of PBDEs.

Kinetics of extractable residue, bound residue and mineralization of a novel herbicide, ZJ0273, in aerobic soils

ZJ0273, propyl 4-(2-(4,6-dimethoxypyrimidin-2-yloxy)benzylamino)benzoate, is a broad-spectrum herbicide being marketed for use on rape crops. However, environmental behavior and fate of ZJ0273 remained poorly understood. In this study, we used ZJ0273 labelled with (14)C on the C ring to understand the transformation of ZJ0273 in aerobic soils. Results showed a first-order dissipation pattern for the parent compound, with half-lives ranging from 17.2 to 53.7 d, suggesting a short to moderate persistence. The dissipation of the parent molecule was accompanied by formation of bound residues and mineralization. The transformation of ZJ0273 appeared to decrease with decreasing soil pH and organic matter content. Differences were often observed in the formation of bound residues, and mineralization among different soils. After 100 d of incubation, the total bound residue accounted for 17.4-28.8% of the total applied amount in the three soils, while cumulative mineralization to CO(2) reached 1.2% for an acidic soil, 7.7% for neutral and 9.9% for alkaline soil, suggesting that the herbicide in the neutral and alkaline soils met the non-accumulative criteria as stated in the directives by the Commission of the European Communities.

Degradation of chiral neonicotinoid insecticide cycloxaprid in flooded and anoxic soil

Cycloxaprid (CYC), with two stereogenic centers from oxabridged ring, is a novel potent neonicotinoid insecticide. The investigation of relevant transformation products (TPs) is critical for the risk evaluation of CYC on environment impact and further regulatory decisions. In this study, stereoselective soil metabolism of CYC enantiomers was investigated using isotope labeling techniques. Liquid scintillation counting with LC-MS/MS was used to identify and quantify the major transformation products (TPs) of CYC enantiomers in four various soils under anoxic and flooded condition. Most of CYC had been transformed in four soils at 5d after treatment. Furthermore, CYC was found converted to a range of transformation products, which exhibited soil-specific dynamic changes. Cleavage of the oxabridged seven-member ring, reductive dechlorination in the chloropyridinyl and cleavage of C-N between the chloropyridinylmethyl and imidazalidine ring are the main transformation pathways of CYC. It is presumed that acidic condition may conduce to form the cleavage product of oxabridged seven-member ring. However, abiotic or biotic stereoselective persistence of TPs in all soils was not observed from the experimental data and may be attributed to the unstable oxabridged ring.

Stereoisomeric Isolation and Stereoselective Fate of Insecticide Paichongding in Flooded Paddy Soils

Chiral insecticide paichongding (IPP) is one of the prospective substitutes for imidacloprid used in China due to its higher activity against imidacloprid-resistant insects. However, little is known about the fate of IPP in soils, including especially the different behaviors among its stereoisomers. In this study, four stereoisomers of IPP were separated and applied in flooded soils. Kinetics of mineralization, extractable residues, and bound residues showed diastereoselectivity in IPP degradation, with enantiomers (5S,7R)-IPP (IPP-SR) and (5R,7S)-IPP (IPP-RS) being more readily mineralized and preferentially bound to soils than enantiomers (5R,7R)-IPP (IPP-RR) and (5S,7S)-IPP (IPP-SS). The overall mineralization was rather limited and did not exceed 4% of the spiked rate. Concurrent to the decreases of extractable residues, the fraction of bound residues increased with time and reached about 34% of the applied radioactivity for (14)C-IPP-SR and (14)C-IPP-RS as compared to about 23% for (14)C-IPP-RR or (14)C-IPP-SS. Soil properties such as organic matter content and pH likely contributed to the variability. Relatively rapid formation of bound residue suggests that IPP may be quickly detoxified in flooded paddy soil, decreasing the potential for off-site transport such as leaching or runoff, especially for enantiomers IPP-SR and IPP-RS.

Starch-based hydrogel loading with carbendazim for controlled-release and water absorption.

Starch, with properties of eco-friendliness and abundance, is one of the most important natural polymers. Starch-based hydrogels were investigated as carriers of carbendazim to combine controlled-release and water absorption (WA). Three carbendazim-loaded hydrogels (CLHs) with different WA capacities were prepared by solution polymerization. The CLHs were characterized by Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), and liquid-chromatography mass-spectrometry (LC-MS/MS). Release kinetics of CLHs was investigated using (14)C-labeling method. The diffusion parameters of CLHs were 0.47, 0.57 and 0.81 in deionized H2O (ddH2O). WA affected release profile significantly, the release longevity reaching 240 h when WA was 800 g/g in ddH2O. Solution pH influenced release profiles and the lowest release rate occurred in the lowest pH. Addition of CLH (1.3g/kg soil) markedly increased water-holding capacity (WHC) of soil by 8.2%. The study indicated that starch-based CLH was a good controlled-release agent for carbendazim and water absorbent for soil.

Diastereoselective Metabolism of a Novel Cis-Nitromethylene Neonicotinoid Paichongding in Aerobic Soils

Many pesticides are chiral but used as racemic mixtures, even though their stereoisomers are often degraded stereoselectively in soils. Evaluation of degradation of chiral compounds is mostly focused on the enantioselectivity rather than diastereoselectivity/epimer preferences. In this study, we explored the diastereoselective transformation of paichongding (IPP), a novel chiral neonicotinoid with broad-spectrum insecticidal activity, to several degradation intermediates in different soils. (14)C-Labeling coupled with LC-MS/MS and high resolution MS were used to track residues of IPP and identify major transformation metabolites. The stereoisomers of IPP known as 5R, 7R-IPP (RR-IPP), 5S, 7S-IPP (SS-IPP), 5S, 7R-IPP (SR-IPP), and 5R, 7S-IPP (RS-IPP) showed diastereoselective/epimer-selective persistence in all soils except an acidic clay soil. Moreover, IPP was transformed to a range of degradation intermediates (M1-M6), which also showed significant diastereoselective and soil preferential formation. Depropylation, nitrosylation, denitration, demethylation, dehydroxylation, and ketonization contributed to IPP transformation. The diastereoselective degradation of the parent compound and formation of incomplete intermediates implies that diastereomers/epimers should be regarded as different chemicals. The approach of coupling (14)C and MS may be used as an effective tool to understand the environmental processes and risks of other man-made chiral compounds.

Fate characterization of a novel herbicide ZJ0273 in aerobic soils using multi-position 14C labeling

ZJ0273, propyl 4-(2-(4,6-dimethoxypyrimidin-2-yloxy)benzylamino)benzoate, is a novel herbicide being developed for use on rape crops. The environmental behavior and fate of ZJ0273, however, are not well understood. In this study, multi-position (14)C-labeled compounds (B-ZJ0273 and C-ZJ0273) were used to investigate the fate of ZJ0273 in aerobic soils, and compare their differences in extractable residues (ER), bound residues (BR), and mineralization. ER for both (14)C labels followed a similar dissipation trend in the same soil, and results showed a strong effect of soil pH, with the ER level being significantly higher in acidic soils than neutral or alkaline soils. The disappearance of parent compound followed first-order dynamics for both labels in the same soils. No difference in BR was observed between the two (14)C-labels. BR increased with time and reached 17.5-35.3% of applied (14)C in the three soils after 100-d incubation, which is much smaller than the non-accumulative criteria (70%) as stated in the directives by the Commission of the European Communities. Mineralization to CO(2) also depended closely on the soil type, with the cumulative mineralized fraction being substantially greater in the neutral and alkaline soils than in the acidic soil. Results also showed that cumulative mineralization rates of the two labels in the acidic soil were much smaller than those in the neutral and alkaline soils. Mineralization of C-ZJ0273 (1.2-9.9%) was found to be more extensive than that of B-ZJ0273 (0.5-6.6%), suggesting that benzyl ring was more susceptible to cleavage than pyrimidine ring. The use of multi-position labeling proved to be valuable; it served the purpose of validating the rigorousness of experimental protocols, and provided insights into the behavior and fate of the different molecular fragments.

Plant availability and phytotoxicity of soil bound residues of herbicide ZJ0273, a novel acetolactate synthase potential inhibitor

The plant availability and phytotoxicity of soil bound residues (BR) of herbicide ZJ0273, a novel acetolactate synthase (ALS) potential inhibitor, to rice (Oryza sativa L.) and corn (Zea mays L.) was investigated in three different soils including a Fluvio-marine yellow loamy soil (S(1)), a Red clayey soil (S(2)), and a Coastal saline soil (S(3)), using (14)C-labeling tracer and bioassay techniques. When soils were amended with BR at 0.6, 1.2 and 1.8 nmol g(-1), dose-dependent and significant inhibition was observed for rice seedlings within 14d after treatment, but no significant inhibition occurred to corn seedlings in the same treatment. Radioactive analysis of soil extracts following sequential extractions showed that the (14)C labeled residues of ZJ0273 were released from the amended soil BR upon planting. For example, when amended with 1.8 nmol g(-1), about 68.3%, 57.0%, and 61.1%, respectively, of the added BR were released in S(1), S(2), and S(3) planted with rice seedlings, whereas 38.9%, 32.7% and 32.6% became available for uptake in the corresponding soils planted with corn seedlings. The released compounds were identified as ZJ0273 and its degradation products M1 and M2, with M2 as the primary component. Bioassay on rice showed that concentration for 50% inhibition (IC(50)) of ZJ0273, M1, and M2 were 33.16, 1.93 and 0.49 microM, respectively. Therefore, BR formed after application of ZJ0273 may become available for plant uptake during rice cultivation and lead to phytotoxic effects, and the phytotoxicity is mainly caused by the release of the biologically active metabolite M2. This knowledge is valuable for designing crop rotation practices so that crop injury and yield losses due to carry-over herbicide phytotoxicity may be avoided.

Stereoselective uptake and distribution of the chiral neonicotinoid insecticide, Paichongding, in Chinese pak choi (Brassica campestris ssp. chinenesis)

Neonicotinoid chiral insecticidal Paichongding is a promising substitute for the widely used imidacloprid. Four stereoisomers of Paichongding, 5R,7R, 5S,7S, 5S,7R and 5R,7S, were employed in both foliage and roots of Chinese pak choi to investigate their stereoselective uptake and distribution in pak choi. Results showed that after foliar application, no stereoselective absorption into pak-choi plants was observed among the enantiomers. Total absorptions were 35.40% of the applied amount for 5R,7R, 36.66% for 5S,7S, 36.80% for 5S,7R and 38.20% for 5R,7S at 96 HAT. The translocation of the four absorbed stereoisomers within pak choi occurred both acropetally and basipetally and the transport of (14)C from enantiomers 5R,7R and 5S,7S were significantly higher than for 5R,7S and 5S,7R. Significant stereoselective translocation inside plants was observed between Paichongding epimers. Total root uptake reached 16.49-19.85% for 5R,7R and 5S,7S, and 24.57-28.82% for 5S,7R and 5R,7S at 144 HAT. Both enantioselective and diastereoselective root uptake into pak-choi occurred between the four stereoisomers. The 5R,7S and 5S,7R enantiomers were more readily uptaken by the roots than 5R,7R and 5S,7S and accumulated in the edible leaves. These results will help to develop an understanding of Paichongding using only the target-active enantiomer of pesticides.