Enantiomeric Fractions Research Articles

Enantioselective toxicity, degradation and transformation of the chiral insecticide fipronil in two algae culture

The occurrence of pesticides and their metabolites in the environment can alter the ecological relationships between aquatic food chains. Fipronil is a broad-spectrum insecticide which release in the environment may harm the non-target organisms. However, the toxicity and biotransformation of its two enantiomers are far from fully understood. The present study aimed to investigate the aquatic toxicity and environmental behavior of fipronil at enantiomeric level using two freshwater algae, Scenedesmus quaclricauda (S. quaclricauda), and Chlorella vulgaris (C. vulgaris) through an integrative approach the transformation process of the individual enantiomer isolated and in racemic form. The 72 h-EC50 values of rac-, R-, S-fipronil varied from 3.27 to 7.24 mg L−1 with R-fipronil posing a more significant effect on algal growth inhibition. Chlorophyll a was more susceptible to fipronil exposure than chlorophyll b and carotenoids. Enantioselective alterations on physiological and biochemical parameters (chlorophyll a, chlorophyll b, carotenoids, and the activities of antioxidant enzyme catalase (CAT) and superoxide dismutase (SOD)) were also observed. The half-lives (T1/2) of R-fipronil and S-fipronil in algae culture were 3.4–3.5 d and 4.0–4.9 d, respectively. By the end of the 17-d exposure, the enantiomer fractions (EFs) increased to 0.59, indicating a preferential depuration of R-fipronil. The metabolites monitoring showed the fipronil sulfide was the main metabolite followed by fipronil sulfone. The results revealed that the enantiomers of fipronil pose enantiospecific behaviors induced by these two algae, with the R-enantiomer more toxic to algal growth and favorable in degradation. These analyses are beneficial for understanding the ecological effect of chiral pesticide in aquatic environment, and the enantiomeric differences of the toxicity, degradation and the formation of toxic metabolites could be helpful for the eco-environmental risk evaluation.

Stereoselective degradation pathway of amide chiral herbicides and its impacts on plant and bacterial communities in integrated vertical flow constructed wetlands

This study demonstrates the stereoselective degradation patterns and biodegradation mechanisms of metolachlor (MET) and napropamide (NAP) in integrated vertical flow constructed wetlands (IVCW). The higher interphase transferability of NAP resulted in higher degradation rates of 90.60 ± 4.09%. The enantiomeric fraction (EF) values of 0.38 ± 0.02 and 0.54 ± 0.03, respectively, recorded for the enantiomers S-MET and R-NAP, with higher herbicidal activities, demonstrated their highly selective biodegradation patterns. The antioxidant enzyme activities and fluorescence parameters of plants showed positive correlations with the degradation efficiency and enantioselectivity of MET and NAP. Adaptive regulations by plants promoted the proliferation of microbial genera like Enterobacter and unclassified_Burkholderiales, which could facilitate plant growth. Moreover, enrichment of the herbicide-degrading functional bacteria Terrimonas (5.10%), Comamonas (4.05%) Pseudoxanthomonas (4.49%) and Mycobacterium (1.42%) demonstrably promoted the preferential degradation of S-MET and R-NAP. Furthermore, the abundance of Ferruginibacter favored the use of R-NAP as carbon source to achieve co-removal of R-NAP and NO3–-N.

Toxification metabolism and treatment strategy of the chiral triazole fungicide prothioconazole in water

Toxification metabolism of the chiral triazole fungicide prothioconazole in the environment has attracted an increasing amount of attention. To better understand the fate of prothioconazole in aquatic ecosystems and develop a treatment strategy, the stereoselective toxicity, degradation and bioconcentration of prothioconazole were investigated in water with algae at the enantiomer level. There was remarkable enantioselectivity against Chlorella pyrenoidosa, and the highly toxic S-prothioconazole was preferentially degraded with enantiomer fraction values ranging from 0.5 to 0.74. Metabolism experiment results showed that the parent compound was quickly eliminated driven by biodegradation and abiotic degradation (hydrolysis, photolysis). Fourteen phase I and two phase II metabolites involved in the reactions of hydroxylation, methylation, dechlorinating, desulfuration, dehydration and conjugation were identified, where prothioconazole-desthio was the major metabolite. The highly toxic metabolite prothioconazole-desthio persisted in water and hardly degraded with or without C. pyrenoidosa. Furthermore, the reaction system including 1 mg of cobalt coated in nitrogen doped carbon nanotubes and 0.156 g of peroxymonosulfate was used to eliminate prothioconazole-desthio. Approximately 96% prothioconazole-desthio was eliminated and transformed to low toxicity metabolites. This work provides a strategy for the risk evaluation of prothioconazole in aquatic ecosystems and proposes a workable plan for the elimination of pesticide residues in water.

Diastereomer- and enantiomer-selective accumulation and depuration of 1,2-dibromo-4-(1,2-dibromoethyl) cyclohexanes (DBE-DBCHs) and 1,2,5,6-tetrabromocyclooctanes (TBCOs) in earthworms (Eisenia fetida)

Due to the regulation of hexabromocyclododecane (HBCD), much attention has been paid to its potential substitutes, 1,2-dibromo-4-(1,2-dibromoethyl) cyclohexane (DBE-DBCH) and 1,2,5,6-tetrabromocyclooctane (TBCO). DBE-DBCH and TBCO contain several diastereomers and enantiomers, which may exhibit different environmental behaviors and biological effects. In this study, the accumulation and depuration of individual DBE-DBCH and TBCO diastereomers by earthworms (Eisenia fetida) from diastereomer-contaminated soils were evaluated. The accumulation and depuration kinetics of DBE-DBCH and TBCO diastereomers followed one-compartment first-order kinetics. The biota soil accumulation factor (BSAF) of β-DBE-DBCH (2.74 goc glip−1) was 1.26 times that of α-DBE-DBCH (2.18 goc glip−1), while the BSAF of β-TBCO (2.15 goc glip−1) was 1.62 times that of α-TBCO (1.3 goc glip−1), showing the diastereomer-specific accumulation of DBE-DBCH and TBCO. DBE-DBCH and TBCO diastereomers appeared to be transformed in earthworm-soil systems; however, no evidence of bioisomerization of the four diastereomers in earthworms was found, and no potential metabolites of debromination and hydroxylation were detected. Furthermore, the selective enrichment of E1-α-DBE-DBCH and E1-β-DBE-DBCH (E1 represents the first enantiomer eluted) occurred in earthworms as the enantiomer fractions (EFs) for α-DBE-DBCH (0.562–0.763) and β-DBE-DBCH (0.516–0.647) were significantly greater than those in the technical products (0.501 for α-DBE-DBCH and 0.497 for β-DBE-DBCH, p < 0.05), especially in the depuration stage. The results demonstrated the diastereomer- and enantiomer-selective accumulation of DBE-DBCH and the diastereomer-selective accumulation of TBCO in the earthworm.

Simultaneous determination of fourteen β2-agonist enantiomers in food animal muscles by liquid chromatography coupled with tandem mass spectrometry

Illegal drug residues in animal derived foods are closely related to human's life and health. Studies on illegal drug residues and the metabolism, such as β2-agonists in animals have attracted more and more attention. In most cases, β2-agonists are suppliedand used astheracemate. The metabolic process and distribution of the two enantiomers in animal tissues are different. Therefore, it is very necessary to develop a simple and fast method for chiral resolution of these drugs in animal tissues. In this paper, a reliable resolution and determination method was presented using liquid chromatography-tandem mass spectrometry (LC-MS/MS) for fourteen enantiomers of seven β2-agonist racemates, clenbuterol (CLE), salbutamol (SAL), cimaterol (CIM), terbutaline (TER), clorprenaline (CLO), tulobuterol (TUL), penbuterol (PEN) in pork, beef, and lamb muscle samples. The samples were added the internal standard solution (IS) and extracted in the alkaline medium with acetonitrile. The further sample purification was accomplished through MCX solid phase extraction cartridge. Chromatographic chiral separation was carried out on a VancoShell chiral column (100 mm × 4.6 mm, 2.7 μm) with an isocratic mobile phase consisting of methanol and 10 mmol mL−1 ammonium formate aqueous solution (85:15, v/v). Under the optimized conditions, the resolution (R) of CIM was 2.0, CLE and PEN were 1.5, the others were all greater than 1.0. Enantiomeric determination was performed in the positive electrospray ionization mode using multiple reaction monitoring (MRM). The correlation coefficient (r) in the range of 0.2–25.0 μg L−1 was above 0.993. The average recoveries at the three spiking levels ranged from 95.3% to 117.7% with the relative standard deviation (RSD) lower than 15%. The limit of detection (LOD) and the limit of quantification (LOQ) of β2-agonist enantiomers was 0.2 μg kg−1 and 0.5 μg kg−1 respectively. The method was successfully applied in the analysis and evaluation of β2-agonist enantiomers in positive food animal muscle samples, CLE, SAL, TEB and CIM enantiomers were detected. The concentrations of the corresponding enantiomers were in the range of 1.06–17.3 μg kg−1, the lowest enantiomer fraction (EF) value was 0.42, and the highest value was 0.69. The work is expected to provide a method for chiral separation and enantiomeric determination of the further study of pharmacology, toxicity and residue elimination of β2-agonist enantiomers.

Enantioselective evaluation of the chiral fungicide mandipropamid: Dissipation, distribution and potential dietary intake risk in tomato, cucumber, Chinese cabbage and cowpea

A chiral analytical method was developed and validated for the determination of mandipropamid enantiomers in tomato, cucumber, Chinese cabbage and cowpea. The linearity (R2 > 0.99), accuracy (recovery: 73.8–106%) and precision (relative standard deviation: < 11%) were adequate for the detection of mandipropamid enantiomers in four vegetables. Field trials were further conducted to investigate the dissipation and residue distribution of mandipropamid and the possible enantioselectivity in different vegetables. Due to the shorter half-lives, mandipropamid dissipated more rapidly in Chinese cabbage (1.8–2.0 d) and cowpea (1.6–2.4 d) than in tomato (5.0–8.4 d) and cucumber (2.4–5.5 d). The residues of mandipropamid were 45–179 µg/kg in tomato 14 d at low dose, 48–98 µg/kg in cucumber 7 d after spraying twice at low dose, and < 2.5–1942 µg/kg in Chinese cabbage and cowpea in all treatments, which were below the maximum residue limits of mandipropamid set by the European Union and Codex Alimentarius Commission. Enantioselectivity was observed during the mandipropamid dissipation process in four vegetables. The S-(+)-enantiomer dissipated more rapidly than the R-(−)-enantiomer in tomato and Chinese cabbage (enantiomeric fractions > 0.5). For cucumber and cowpea, the dissipation of the R-enantiomer was preferential (enantiomeric fractions < 0.5). According to the risk quotient data (<< 100%), the residues of mandipropamid in four vegetables were safe for Chinese consumers. This study could provide useful information for the dissipation fate and residue distribution of mandipropamid in vegetables at the enantiomer level and offer some guidance for the dietary intake risk evaluation of mandipropamid in vegetables.

Chiral inversion of 2-arylpropionoic acid (2-APA) enantiomers during simulated biological wastewater treatment

This study examined the removal and enantio‑specific fate of a suite of eleven chiral 2-arylpropionic acids (2-APAs) during biological wastewater treatment simulated in a laboratory-scale membrane bioreactor (MBR). Using pure (R)- and (S)- enantiomers in the MBR influent, chiral inversion was determined through the increase in the concentration of the non-dominant enantiomer and changes in the enantiomeric fraction (EF) between the two enantiomers during the treatment process. Effective (>90%) and similar removal rates between (R)- and (S)- enantiomers were confirmed for eight 2-APAs. In this study, 2-APAs exhibited diverse and distinctive chiral inversion behaviours: two 2-APAs showed (R→S) unidirectional inversion, three 2-APAs showed (S→R) unidirectional inversion, and six 2-APAs showed bidirectional inversion. This is the first study to report chiral inversion behaviours of a comprehensive suite of 2-APAs with a variety of functional groups substituted onto the aryl ring. A decrease in effluent EF over time was observed for two 2-APAs. This study shows that chiral inversion of 2-APAs varies significantly from compound to compound, despite the high similarity in their chemical structures.

Organochlorine pesticides and polychlorinated biphenyls from a greenhouse area on the Mediterranean coast of Turkey: Distribution, air-soil exchange, enantiomeric signature, and source implications

Levels, seasonal variation, and air-soil exchange of 22 organochlorine pesticides (OCPs) and 15 polychlorinated biphenyls (PCBs) were determined in addition to the first insight into the enantiomeric signatures of chiral OCPs in an agricultural region of Turkey. A total of 47 polyurethane foam disk passive air samples and 34 surface/in-depth soil samples were analyzed. ∑OCP and ∑PCB levels in air samples were 32.6–741 pg/m3 and nd-2764 pg/m3, while they were nd-28.1 ng/g dw and nd-0.302 ng/g dw in soil samples, respectively. Dichlorodiphenyltrichloroethane (DDT) and its metabolites and endosulfan isomers were the most prevalent chemicals along with the light-weighted PCB congeners. During this study, lower or similar contamination levels were observed compared to global studies conducted in agricultural regions. The enantiomer fractions of o,p’-DDT in air samples might be due to re-volatilization of equally depleted enantiomers or fresh input of racemic o,p'-DDT to the air. The fugacity fractions showed that net deposition is the dominant mechanism.

Environmentally friendly analytical method to assess enantioselective behaviour of pharmaceuticals and pesticides in river waters

Reported herein is the first enantioselective method for simultaneous separation of chiral pharmaceuticals and pesticides using ultra-high-performance liquid chromatography-tandem mass spectrometry. Separation was achieved using a ChiralPak IG-U® column (amylose tris(3-chloro-5-methylphenylcarbamate) stationary phase) and ethanol as a ‘green’ mobile phase organic modifier. Minimum enantiomer resolutions ranged from 0.5 to 6.9 for 28 pharmaceuticals, herbicides, fungicides and insecticides. The total run time was 26 min and is considerably shorter than other multi-residue enantioselective methods for similar numbers of pesticides, and is the first to facilitate simultaneous pharmaceutical separation. Direct injection of river water samples enabled omission of acetonitrile and methanol from the sample treatment step (and the whole methodology). This approach was considerably faster than enantioselective methodologies that rely on solid phase extraction and avoids the need for large sample volumes for analysis. The suitability of this approach was demonstrated by the method's sensitivity with enantiomer method quantitation limits in the range 0.005–0.6 μg L-1. The new method was applied to river water microcosms to investigate enantiospecific transformation of racemic pharmaceuticals and pesticides. The pharmaceutical omeprazole, fungicide prothioconazole and insecticide profenofos were all subject to enantioselective transformation under biotic conditions, represented by a change in enantiomeric fraction of ≥0.1 units. Individual enantiomer microcosms revealed chiral inversion of R-omeprazole to S-omeprazole in the environment for the first time. In conclusion, this method offers comparatively fast enantioselective analysis for a high number of pharmaceuticals and pesticides in river water, and is achieved in an environmentally friendlier way than previously reported liquid chromatography methods.

Polychlorinated biphenyl (PCB) concentrations and profiles in marine mammals from the North Atlantic Ocean

Polychlorinated biphenyls (PCBs) can provide crucial information into the bioaccumulation and biomagnification of POPs in marine mammals. Muscle tissue samples were obtained for detailed PCB congener specific analysis of all 209 PCBs in 11 species of marine mammals stranded across the coast of the UK between 2010 and 2013. At least 145 PCB congeners were found in each individual. The highest concentrations of PCBs were recorded in a killer whale (318 mg/kg lipid) and the highest toxic equivalent in a Risso's dolphin (1687 pg/g TEQ2005 wet). Concentrations of PCBs in the majority of samples exceeded toxic thresholds (9 mg/kg lipid) for marine mammals, highlighting the health risk they face from PCB exposure. Many PCB profiles did not fit typical ‘Aroclor’ signatures, but instead indicated patterns of congeners that are resistant to biotransformation and elimination. However, this study identified a novel PCB signature in a sei whale that has not yet been previously observed in marine mammals. The whale had a PCB profile that included lighter and inadvertent PCB congeners such as PCB 11, suggesting that the main source of exposure was through atmospheric deposition, rather than terrestrial discharges. Seven subsamples were chosen for chiral analysis of PCB 95, 136 and 149. The enantiomer fractions (EFs) of C-PCBs 95 and 149 were non racemic suggesting there may be enantiomer selective metabolism in marine mammals. Although there has been a shift in the literature towards emerging pollutants, this study acts as a stark reminder that PCBs continue to pose a significant risk to wildlife.

Occurrence, spatial distribution, and fate of polycyclic musks in sediments from the catchment of Chaohu Lake, China.

Twenty-nine surface sediments from Chaohu Lake in China and from its six main tributaries were sampled to investigate the concentrations of two important polycyclic musks (PCMs), 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta(g)-2-benzopyran (galaxolide, HHCB) and 7-acetyl-1,1,3,4,4,6-hexamethyl-1,2,3,4-tetrahydronaphthalene (tonalide, AHTN), as well as the concentration of 4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta(g)-2-benzopyran-1-one (galaxolidon, HHCB-lactone), which is the main degradation product of HHCB. Except for the high concentrations of AHTN and HHCB measured in the Nanfei River (879ng/g dw and 5,513ng/g dw, respectively), the levels of AHTN and HHCB in the river sediments were 7.08-44.9ng/g dw and 20.6-268ng/g dw, respectively, which are slightly lower than those documented in various areas worldwide. The concentrations of AHTN and HHCB in the sediments of Chaohu Lake were one or two orders of magnitude lower than those in the tributary rivers and showed a clear regional distribution. The concentrations of HHCB-lactone were comparable to those of HHCB and presented a significant positive correlation with the concentrations of HHCB, suggesting that the HHCB-lactone originated directly from the degradation of HHCB in wastewater treatment plants (WWTPs) or in the natural environment. The diagnostic ratios of HHCB/AHTN and HHCB-lactone/HHCB and the enantiomeric fractions (EFs) of these PCMs showed that the direct origins of the target PCMs in the study area were municipal and industrial wastewaters discharged from adjacent cities or point sources and that the HHCB-lactone in sediment originated from the natural degradation of HHCB in the rivers and the lake. The results of the risk assessment showed that the PCMs in the watershed sediments were unlikely to pose a threat to aquatic species. However, the effluents of industrial and municipal wastewaters that are discharged into the Nanfei River should be investigated in future research.

Gas Chromatography Multiresidue Method for Enantiomeric Fraction Determination of Psychoactive Substances in Effluents and River Surface Waters

Determination of psychoactive substances (PAS) and/or their metabolites in surface waters is crucial for environmental risk assessment, and disclosure of their enantiomeric fractions (EF) allows discrimination between consumption, direct disposal, and synthesis pathways. The aim of this study was to develop and validate an indirect method by gas chromatography coupled to mass spectrometry (GC–MS) based on derivatization using (R)-(−)-α-methoxy-α-(trifluoromethyl) phenylacetyl chloride as chiral derivatization reagent, for enantiomeric quantification of amphetamine (AMP), methamphetamine (MAMP), 3,4-methylenedioxymethamphetamine (MDMA), norketamine, buphedrone (BPD), butylone, 3,4-dimethylmethcathinone (3,4-DMMC), 3-methylmethcathinone, and quantification of 1-benzylpiperazine and 1-(4-metoxyphenyl)-piperazine. The method allowed to evaluate the occurrence, spatial distribution, and the EF of the target chiral PAS in Portuguese surface waters and in effluents from 2 wastewater treatment plants (WWTP). For that, water samples were pre-concentrated by solid phase extraction using OASIS® MCX cartridges, derivatized and further analyzed by GC–MS. Both enantiomers of AMP, (R)-MDMA, (S)-MAMP, and the first eluted enantiomer of BPD (configuration not assigned) were found in surface waters, while effluent samples showed both enantiomers of MDMA, (S)-MAMP, (R)-AMP, and the first eluted enantiomer of BPD and 3,4-DMMC. According to our knowledge, this is the first multiresidue analytical method by CG–MS enrolling cathinones, amphetamines, and piperazines. The presence of illicit synthetic cathinones in Douro River estuary is here reported for the first time, along with other amphetamine derivatives. The potential of the method to monitor consumption of the target PAS was demonstrated.

Significance of biotransformation and excretion on the enantioselective bioaccumulation of hexabromocyclododecane (HBCDD) in laying hens and developing chicken embryos

Although (–)-α-hexabromocyclododecane (HBCDD) and (+)-γ-HBCDD are preferentially enriched in chickens, the key factors contributing to their selective bioaccumulation in hens and their potential biotransformation in developing chicken embryos remain unclear. Herein, in vivo and in ovo exposure experiments using hens and fertilized eggs were conducted to investigate the absorption, excretion, and biotransformation of HBCDDs in chickens. γ-HBCDD (76%) exhibited a higher absorption efficiency than α- (22%) and β- (69%) HBCDDs. However, α-HBCDD was dominant in hen tissues, although γ-HBCDD accounted for >75% in the spiked feed. Moreover, chicken embryos biotransformed approximately 9.5% and 11.7% of absorbed α- and γ-HBCDDs, respectively, implying that diastereomer-selective elimination causes the predominance of α-HBCDD in hens. The concentration and enantiomer fraction (EF) of α-HBCDD in laid eggs were significantly positively correlated, suggesting enantioselective elimination. The EFs of α- and γ-HBCDDs varied between feces from the exposure and depuration periods, indicating the preferred excretion of (+)-α- and (–)-γ-HBCDDs. Furthermore, the enantioselective biotransformation of (–)-γ-HBCDD was confirmed in developing chicken embryos. These results show that excretion and biotransformation contribute to the diastereomer- and enantiomer-selective bioaccumulation of HBCDDs in chickens; The results may improve our understanding of the environmental fate and ecological risks of HBCDDs in biota.

Chiral Fungicide Famoxadone: Stereoselective Bioactivity, Aquatic Toxicity, and Environmental Behavior in Soils.

In this study, the stereoselective bioactivity, acute toxicity, and environmental fate for famoxadone enantiomers were reported for the first time. Five representative pathogens (e.g., Alternaria solani) were used to investigate enantioselective activity, and three non-target organisms (e.g., Selenastrum bibraianum) were used to evaluate acute toxicity. S-Famoxadone was 3.00-6.59 times more effective than R-famoxadone. R-Famoxadone also showed 1.80-6.40 times more toxicity than S-famoxadone toward S. bibraianum and Daphnia magna. The toxicity of R-famoxadone was 100 times more toxic than S-famoxadone toward Danio rerio. Under aerobic conditions, the half-life (t1/2) for famoxadone enantiomer degradation was 46.2-126 days in different soils and the enantiomeric fraction (EF) ranged from 0.435 to 0.470 after 120 days. R-Famoxadone preferentially degraded in three soils, resulting in an enrichment of S-famoxadone. Under anaerobic conditions, t1/2 of famoxadone enantiomers was 62.4-147 days in different soils and the EF ranged from 0.489 to 0.495, indicating that famoxadone enantiomers were not enantioselective. This study will be useful for the environmental and health risk assessments for famoxadone enantiomers.

Polychlorinated biphenyls (PCBs) in the colostrum samples from the Yangtze River Region: Exposure profile and risk assessment

Polychlorinated biphenyls (PCBs) may transfer into the neonates through the placental transfer and via breastfeeding after the delivery, thus might be harmful to the infant. Sixty colostrum samples in the Yangtze River Region were collected to investigate the concentration, distribution pattern, and enantiomer characteristic of the PCB exposure. Among all samples, over 90% of pollutants were tetra-to hepta-chlorinated PCBs. The sum concentration of the PCB was 512 (IQR: 322–856) ng g−1 lipid weight. Enantiomer fraction (EF) of PCB 95 and PCB 149 was found lower than the racemic value, while EFs of PCB 45 and PCB 136 were found higher and near-racemic state, respectively. The concentration pattern and enantiomeric properties of the PCBs indicated that the mothers from Mianyang had a recent exposure to PCBs. Among all samples, similar exposure and metabolic pathways of the PCB congeners were observed. PCB exposure showed no significant correlation with the birth outcome of the infants, but 43.3% of the infants have potential health risks via breastfeeding.

Effects of Cd2+ and Pb2+ on enantioselective degradation behavior of α-cypermethrin in soils and their combined effect on activities of soil enzymes

Heavy metals may coexist with pesticides in farmland through wastewater irrigation, application of pesticides and chemical fertilizers, or unappropriated waste disposal. Heavy metals are toxic to soil microorganism, which may influence the environmental behavior of pesticides subsequently. In this study, the influence of Cd2+ and Pb2+ on the degradation of α-cypermethrin and its metabolites, 3-phenoxphenoxybenzoic acid (3-PBA) and 3-(2',2'-dichlorovinyl)-2,2-dimethylcyclopropane carboxylic acid (DCCA), were investigated through soil incubation experiment. It was found heavy metals like Cd2+ and Pb2+ will inhibit the degradation of α-cypermethrin, especially at high concentrations. Pb2+ has a stronger inhibitory effect on the degradation of α-cypermethrin than Cd2+ in the same concentration. With the presence of 10 mg/kg Pb2+, the half-life of α-cypermethrin increased from 41.1 to 99.9 days, even the half-life was 129.3 days with 50 mg/kg of Pb2+. Besides, heavy metals influenced the chiral selective degradation of α-cypermethrin. The enantiomer fraction was near 0.5 when 10 mg/kg of heavy metals existed. Furthermore, the adverse effects of heavy metals on soil urease, catalase, and sucrase activity were assayed. In tested concentrations (10 and 50 mg kg-1), the heavy metals result in strong inhibition of the activity of the enzymes present on soil, jeopardizing the biodegradation by the microbiome and which may inhibit the degradation of α-cypermethrin.

Dynamics of Isomeric and Enantiomeric Fractions of Pinene in Essential Oil of Picea abies Annual Needles during Growing Season.

Norway spruce (Picea abies (L.) H. Karst.) is one of the most important commercial tree species distributed naturally in the Boreal and subalpine forest zone of Europe. All parts of spruce trees, including needles, accumulate essential oils with a variety of chemical properties and ecological functions, such as modulating plant–insect communication. Annual needle samples from 15 trees (five from each of three habitats) of 15–17 years old were assayed for essential oils and their major compounds, including α-pinene, β-pinene, (1S)-(−)-α-pinene, and (1R)-(+)-α-pinene across a growing season. Results showed strong positive correlation between percentages of α- and β-pinene isomers (r = 0.69, p < 0.05) and between pinene isomers and essential oils: α-pinene correlated with essential oil stronger (r = 0.62, p < 0.05) than β-pinene (r = 0.33, p < 0.05). Correlation analyses performed with some weather conditions, including average monthly temperature, growing sum of effective temperatures over 5 °C, duration of sunshine, accumulated precipitation, relative humidity, and pressure, showed that temperature is the most important weather condition related to pinene dynamics: negative correlations of moderate strength were established between percentages of α- and β- pinenes and average monthly temperatures (r = −0.36, p < 0.01, n = 75 and r = −0.33, p < 0.01, n = 75, respectively). Out of pinene enantiomers, only (1S)-(−)-α-pinene showed some negative correlation with monthly temperature (r = −0.26, p < 0.05, n = 75). Different patterns of essential oil and pinene dynamics during growing season within separate habitats suggested that some genetic variables of Picea abies might be involved.

Supercritical fluid chromatography-mass spectrometric determination of chiral fungicides in viticulture-related samples

Supercritical fluid chromatography (SFC), combined with mass spectrometry (MS), was employed for the determination of five chiral fungicides, from two different chemical families (acylalanine and triazol) in wine and vineyard soils. The effect of different SFC parameters (stationary phase, chiral selector, mobile phase modifier and additive) in the resolution between enantiomers and in the efficiency of compounds ionization at the electrospray source (ESI) was thorougly described. Under final working conditions, chiral separations of selected fungicides were achieved using two different SFC-MS methods, with an analysis time of 10 min and resolution factors from 1.05 to 2.45 between enantiomers. In combination with solid-phase extraction and pressurized liquid extraction, they permitted the enantiomeric determination of target compounds in wine and vineyard soils with limits of quantification in the low ppb range (between 0.5 and 2.5 ng mL−1, and from 1.3 to 6.5 ng g−1, for wine and soil, respectively), and overall recoveries above 80%, calculated using solvent-based standards. For azolic fungicides (tebuconazole, myclobutanil and penconazole) soil dissipation and transfer from vines to wines were non-enantioselective processes. Data obtained for acylalanine compounds confirmed the application of metalaxyl (MET) to vines as racemate and as the R-enantiomer. The enantiomeric fractions (MET-S/(MET-S+MET-R)) of this fungicide in vineyard soils varied from 0.01 to 0.96; moreover, laboratory degradation experiments showed that the relative dissipation rates of MET enantiomers varied depending on the type of soil.

Monitoring the behavior of imazalil and its metabolite in grapes, apples, and the processing of fruit wine at enantiomeric level.

Imazalil is widely used in agriculture, which may pose a threat to food safety. This study aimed to investigate the fate of imazalil and its main metabolite, R14821 (imazalil-M), in field grapes and apples, and in the processing of fruit wine at the enantiomeric level. Analysis method was established to determine imazalil and imazalil-M enantiomers in grape, apple, fruit wine and pomace. The method showed acceptable recoveries of 71.6-99.9% and precision with relative standard deviation of 0.3-11.7%. Processing factors (PFs) were 0.15-0.40 (for imazalil enantiomers) and <0.13-0.83 (for imazalil-M enantiomers) during the wine-making process. The PFs after individual steps including washing, peeling, fermentation, and clarification were all less than 1. No enantioselective dissipation of imazalil was found in grapes under field conditions with half-lives of 23.82-24.49 days. R-(-)-imazalil degraded slightly faster than S-(+)-imazalil in apples under field conditions with half-lives of 9.82-10.09 days. S-(+)-imazalil-M preferentially degraded in field grapes and apple. No significant enantioselectivity of imazalil and imazalil-M was observed during the wine-making process. The enantiomeric fraction (EF) values of imazalil were 0.484-0.511 and 0.509-0.522 in grape wine and cider, respectively. The EFs were 0.484-0.501(in grape wine) and 0.484-0.504 (in cider) for imazalil-M. The results showed that the wine-making process could reduce imazalil and imazalil-M residues in grapes and apples. The finding of non-enantioselectivity of imazalil during the processing of fruit wine was useful for accurate risk assessment for imazalil in raw and processing fruits. © 2021 Society of Chemical Industry.

Toxicity and fate of chiral insecticide pyriproxyfen and its metabolites in zebrafish (Danio rerio).

Pyriproxyfen is a juvenile hormone analogue insecticide used worldwide. At present, the potential threat of pyriproxyfen to aquatic organism has not been well explored. In this work, the bioaccumulation, metabolic profile and toxicity of pyriproxyfen and its metabolites to zebrafish were studied, and the enantioselectivity of pyriproxyfen and the major chiral metabolites were also determined. Sixteen metabolites of pyriproxyfen in zebrafish were identified. Hydroxylation, ether linkage cleavage and oxidation in phase I metabolism, followed by sulfate and glucuronic acid conjugation. The bioconcentration factors ranged from 1175 to 1246. Hydroxylation metabolites of pyriproxyfen showed enantioselective behavior in zebrafish with enantiomer fractions (EFs) of 4'-OH- pyriproxyfen and 5″-OH- pyriproxyfen ranged from 0.50 to 0.71. Toxicological indexes including acute toxicity, joint toxicity and oxidative stress were tested. Among all the metabolites, 4'-OH- pyriproxyfen was found 2 folds more toxic to zebrafish than pyriproxyfen. (-)-Pyriproxyfen was found 2 folds more toxic than rac- and (+)-pyriproxyfen. Antagonistic effects were found in binary joint toxicity of pyriproxyfen and its hydroxylated metabolites. Pyriproxyfen and its metabolites also showed oxidative stress damage by inhibiting the activity of CAT and SOD and increasing MDA. This work provided deep insight into the metabolism and the potential risks of pyriproxyfen to aquatic organisms.