Comparing toxicity and biodegradation of racemic glufosinate and L-glufosinate in green algae Scenedesmus obliquus.

Glufosinate-ammonium, a widely used chiral herbicide, has become the focus of attention because of its toxicity toward non-target organisms and its degradation behavior in the environment. With the introduction of L-glufosinate-ammonium products, the toxicity and environmental behavior of rac-glufosinate-ammonium and L-glufosinate-ammonium have become the subject of increasing interest. The overall goal of this study was to investigate the differences in toxicity and biodegradation of rac-glufosinate-ammonium and L-glufosinate-ammonium in an aquatic organism, Scenedesmus obliquus. The toxicity of rac-glufosinate-ammonium and L-glufosinate-ammonium to S. obliquus was compared by measuring EC50, malondialdehyde (MDA) content, protein content and antioxidant enzyme activity. The 96-h EC50 values of rac-glufosinate-ammonium and L-glufosinate-ammonium were 57.22 µg/mL and 25.55 µg/mL, respectively, which indicated that L-glufosinate-ammonium was more toxic to S. obliquus than rac-glufosinate-ammonium. Based on the MDA content, protein content, and antioxidant enzyme (SOD and CAT) activity, we found that L-glufosinate-ammonium could cause more serious oxidative damage than rac-glufosinate-ammonium. The residual amount of glufosinate-ammonium and its metabolites in the culture medium and S. obliquus were determined by HPLC-HRMS. Comparison of glufosinate-ammonium concentrations in algae-free and algae-containing media, showed that glufosinate-ammonium degradation in the S. obliquus system was significantly increased, and the degradation rate of L-glufosinate-ammonium was faster than that of D-glufosinate-ammonium. No enantiomerization was observed for pure L-glufosinate-ammonium treatment. N-acetyl-glufosinate was identified as the main metabolite of glufosinate-ammonium.

Four Propiconazole Stereoisomers: Stereoselective Bioactivity, Separation via Liquid Chromatography-Tandem Mass Spectrometry, and Dissipation in Banana Leaves.

In this study, we evaluated the stereoselective bioactivity of four propiconazole stereoisomers against the causal agents of the banana leaf spot disease (Curvularia lunata and Colletotrichum musae). We also evaluated the stereoselective degradation of the stereoisomers in banana leaves under field test conditions. The Superchiral S-OX column successfully separated the four propiconazole stereoisomers. X-ray single-crystal diffraction confirmed that the absolute configuration of the cis-stereoisomer-(+)-A of propiconazole was (2R,4S)-propiconazole and that of the cis-stereoisomer-(-)-A of propiconazole was (2S,4R)-propiconazole. In vitro antibacterial results revealed that (2R,4S)-(+)-propiconazole had the highest activity against the two target plant fungi. In this study, a new and efficient high-performance liquid chromatography tandem mass spectrometry method was developed for the determination of the four stereoisomeric residues of propiconazole in banana leaves. The mean recoveries of the method for the stereoisomers were 76.3-103% with relative standard deviations of 1.25-11.4%. The four propiconazole stereoisomers had a detection limit of 0.002-0.006 mg/kg and a limit of quantification of 0.02-0.03 mg/kg in banana leaves. Propiconazole-(-)-B and propiconazole-(-)-A degraded slightly faster than their corresponding enantiomers propiconazole-(+)-B and propiconazole-(+)-A in banana leaves collected from three typical banana production areas.

Dissipation Dynamics, Terminal Residues and Dietary Risk Assessment of Two Isomers of Dimethacarb in Rice by HPLC-MS/MS.

Dimethacarb is a carbamate insecticide developed in China that contains 3,5-dimethylphenyl methylcarbamate (XMC) and 3,4-dimethylphenyl methylcarbamate (MPMC) isomers. Dimethacarb has been registered for use in rice in China, but no residue or degradation of dimethacarb in rice has been reported and the maximum residue limits (MRLs) for rice have not been established. A versatile high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) method was developed with modified QuEChERS sample preparation to determine two isomers of dimethacarb in rice. The average recovery of XMC and MPMC in brown rice, rice husk, and rice straw ranged from 71.69 to 100.60%, with spike levels of 0.01 to 1 mg/kg and relative standard deviations (RSDs) of 0.21 to 8.41%. Field experiments showed that the half-lives of XMC and MPMC in rice straw were 4.08 to 4.23 days and 3.48 to 3.69 days, respectively. Final residues of XMC and MPMC in rice husk after 21 days of spraying at six sites ranged from 0.23-2.65 mg/kg and 0.06-1.10 mg/kg, and <0.01-0.16 mg/kg and <0.01-0.04 mg/kg in brown rice. The ratio of XMC to MPMC content in the rice husk differed from the original 50% dimethacarb EC, indicating the difference in the degradation rate of XMC and MPMC. The estimated risk quotient (RQ) for both XMC and MPMC was less than 30%. These data for residues from six representative locations could provide a reference for establishing the MRL of dimethacarb in rice.

Enantioselective Analysis and Degradation Studies of Four Stereoisomers of Difenoconazole in Citrus by Chiral Liquid Chromatography-Tandem Mass Spectrometry.

Four difenoconazole stereoisomers were well separated on a Superchiral S-OX column. The absolute configurations of the four stereoisomers of difenoconazole eluted in an orderly fashion with the chiral column were confirmed as (2S,4S), (2S,4R), (2R,4R), and (2R,4S)-difenoconazole, respectively, by single-crystal X-ray diffraction. For the first time, a simple and efficient trace detection method for the determination of residues of the four stereoisomers of difenoconazole in a plant sample by HPLC-MS/MS was developed. The mean recoveries were 78.23-104.38% with RSDs of 0.33-9.95%. The limits of detection for the four difenoconazole enantiomers were 0.0002-0.0004 mg/kg, and the limits of quantitation were 0.0044-0.011 mg/kg in citrus leaves and whole fruits. There was no obvious enantioselectivity upon degradation of the four stereoisomers in citrus leaves and whole fruits in Hunan and Guizhou. In Guangzhou, the rate of degradation of (2R,4R)-difenoconazole was the slowest among the four stereoisomers of difenoconazole.