Jinling Diao

Enantioselective bioaccumulation and toxic effects of metalaxyl in earthworm Eisenia foetida.

Knowledge about the enantioselective bioavailability of chiral pesticides in soil invertebrates facilitates more accurate interpretation of their environmental behaviors. In this study, the acute toxicities of R-metalaxyl and rac-metalaxyl to earthworm (Eisenia foetida) were assayed by filter paper contact test. After 48 h of exposure, the calculated LC(50) values for R- and rac-metalaxyl were 0.052 and 0.022 mg cm(-2), respectively, resulting in a two fold difference in toxicity. For uptake experiment, earthworms were exposed in soil at two dose levels (10 and 50 mg kg(dwt)(-1)). The concentrations of two enantiomers in soil and earthworm were determined by high-performance liquid chromatography based on cellulose tri-(3,5-dimethylphenyl-carbamate) chiral stationary phase. The results showed that metalaxyl was taken up by earthworm rapidly, and the bioaccumulation of metalaxyl in earthworm was enantioselective with preferential accumulation of S-enantiomer. In addition, biota to soil accumulation factor (BSAF) used to express the bioaccumulation of metalaxyl enantiomers was investigated, and significant difference was observed between rac-metalaxyl and R-metalaxyl.

Environmental behavior of the chiral aryloxyphenoxypropionate herbicide diclofop-methyl and diclofop: enantiomerization and enantioselective degradation in soil.

In this study, the degradation of diclofop-methyl (DM) and its main metabolite, diclofop (DC), in two soils under aerobic and anaerobic conditions were investigated using enantioselective HPLC. Under aerobic or anaerobic conditions, rapid hydrolysis to the corresponding acid diclofop (DC)was observed. The results from this study revealed that the degradation of DM in the two soils is not enantioselective, and the calculated half-lives (t(1/2)) for the two soils were both less than 1 day. However, the degradation of DC in the two soils is enantioselective both under aerobic and anaerobic conditions, and the S-(-)-DC was preferentially degraded, resulting in relative enrichment of the R-(+)-form. The calculated t(1/2) values of the enantiomers of DC ranged between 8.7 and 43.3 days for aerobic incubation experiments and between 14.7 and 77.0 days for anaerobic incubation experiments, respectively. The enantiopure S-(-)- and R-(+)-DC were incubated under aerobic conditions, and it revealed significant enantiomerization with inversion of the S-(-)-enantiomer into R-(+)-enantiomer, and vice versa, and the S-(-)-DC showed a significantly higher inversion tendency than the R-(+)-DC.

Enantioselective Degradation in Sediment and Aquatic Toxicity to Daphnia magna of the Herbicide Lactofen Enantiomers

Many pesticides in use are chiral compounds containing stereoisomers. However, the environmental behavior and fate of such compounds with respect to enantioselectivity so far has received little attention. In this study, the degradation of lactofen and its main metabolites (acifluorfen, an achiral compound; desethyl lactofen, a chiral compound) in sediment were investigated under laboratory conditions using enantioselective HPLC, and the enantioselectivities of individual enantiomers of lactofen and desethyl lactofen in acute toxicity to Daphnia magna were studied. The calculated LC(50) values of S-(+)-, rac-, and R-(-)-lactofen were 17.689, 4.308, and 0.378 microg/mL, respectively, and the calculated LC(50) values of S-(+)-, rac-, and R-(-)-desethyl lactofen were 21.327, 13.684, and 2.568 mug/mL, respectively. Therefore, the acute toxicities of lactofen and desethyl lactofen enantiomers were enantioselective. In sediments, S-(+)-lactofen or S-(+)-desethyl lactofen was preferentially degraded, resulting in relative enrichment of the R-(-)-form. Lactofen and desethyl lactofen were both configurationally stable in sediment, showing no interconversion of S- to R-enantiomers or vice versa. Furthermore, the conversion of lactofen to desethyl lactofen proceeded with retention of configuration. These results for major differences in acute toxicity and degradation of the enantiomers may have some implications for better environmental and ecological risk assessment for chiral pesticides.

Influence of Soil Properties on the Enantioselective Dissipation of the Herbicide Lactofen in Soils

A scheme was developed to elucidate the dissipation behaviors of the two enantiomers of the herbicide lactofen in soils using a normal-phase high-performance liquid chromatograph (HPLC) with UV detector and a column with a cellulose-tri-(3,5-dimethylphenylcarbamate)-based chiral stationary phase (CDMPC-CSP). Eight soils with a wide range of soil properties were studied. Racemic and the enantiopure (S)-(+)- and (R)-(-)-lactofen were incubated under aerobic and anaerobic conditions. The data from sterilized controls indicated that the dissipation of lactofen was biological. The dissipation was shown to be enantioselective with (S)-(+)-enantiomer being degraded faster than the (R)-(-)-enantiomer, resulting in residues enriched with (R)-(-)-lactofen when the racemic compound was incubated. Lactofen was configurationally stable in soil, showing no interconversion of (S)-(+)- to (R)-(-)- enantiomer and vice versa. Significant correlations of the enantioselectivity, expressed as ES = (k((S)) - k((R)))/(k((S)) + k((R))) of lactofen with soil pH were observed under aerobic and anaerobic conditions. In addition, we found that the enantioselectivity correlated with the soil texture rather than the organic carbon.

Enantioselective toxic effects and biodegradation of benalaxyl in Scenedesmus obliquus.

Enantioselectivity in ecotoxicity and biodegradation of chiral pesticide benalaxyl to freshwater algae Scenedesmus obliquus was studied. The 96 h-EC(50) values of rac-, R-(-)-, S-(+)-benalaxyl were 2.893, 3.867, and 8.441 mg L(-1), respectively. Therefore, the acute toxicities of benalaxyl enantiomers were enantioselective. In addition, the pigments chlorophyll a and chlorophyll b, antioxidant enzyme activities catalase (CAT) and superoxide dismutase (SOD) as well as lipid peroxide malondialdehyde (MDA) were determined to evaluate the different toxic effects. Chlorophyll a was induced by S-(+)-benalaxyl but inhibited by R-(-)-benalaxyl at 1 mg L(-1). Chlorophyll b were both induced at 1 mg L(-1), but S-(+)-form was fourfold higher than R-(-)-form. S-(+)-benalaxyl inhibited more CAT activities at 3 mg L(-1) and 5 mg L(-1), induced less SOD activity and MDA content at 5 mg L(-1) than R-(-)-benalaxyl. Based on these data, enantioselectivity occurred in anti-oxidative stress when S. obliquus response to benalaxyl. In the biodegradation experiment, the half-lives of S-(+)-benalaxyl and R-(-)-benalaxyl were 4.07 d and 5.04 d, respectively, resulting in relative enrichment of the R-(-)-form. These results showed that toxic effects and biodegradation of benalaxyl in S. obliquus were enantioselective, and such enantiomeric differences must be taken into consideration in pesticide risk.

Enantioselective Toxic Effects and Degradation of Myclobutanil Enantiomers in Scenedesmus obliquus

Research on the enantioselective environmental behavior of chiral pesticides has been a hot spot of environmental chemistry recently. In this study, the acute toxicity of myclobutanil enantiomers was investigated with the aquatic algae Scendesmus obliquus. After exposure for 96 h, the EC50 values for (-)-myclobutanil, rac-myclobutanil and (+)-myclobutanil were 3.951, 2.760, and 2.128 mg/L, respectively. The photosynthetic pigment (chlorophyll a, chlorophyll b, and carotenoids) and antioxidant enzyme activities catalase (CAT) were determined to evaluate the different toxic effects when S. obliquus were exposed to 1.5, 5 and 15 mg/L of rac-myclobutanil, (-)-myclobutanil, and (+)-myclobutanil for 96 h, respectively. In addition, the degradation of myclobutanil enantiomers in S. obliquus was also studied. Myclobutanil in the medium inoculated with algae degraded faster than in the uninoculated medium. The degradation of (-)-myclobutanil was faster than that of (+)-myclobutanil at a concentration of 3 mg/L. On the basis of these data, the acute toxicity and toxic effects of myclobutanil against S. obliquus were concluded to be enantioselective, and such enantiomeric differences should be taken into consideration in pesticide risk assessment.

Stereoselective Bioaccumulation and Metabolite Formation of Triadimefon in Tubifex tubifex

Triadimefon, a chiral fungicide, could be metabolized to triadimenol which has two chiral centers. In this work, Tubifex tubifex was exposed to triadimefon through the aqueous and soil phase to explore the relative importance of the routes of uptake. Bioaccumulation of triadimefon in tubifex was detected in both treatments, and the kinetics of the accumulation processes were significantly different in these two experiments. In spiked water treatment, (S)-triadimefon was preferentially accumulated over the (R)-triadimefon, whereas the enantioselective bioaccumulation was not detected in the spiked soil microenvironment. Simultaneously, four stereoisomers of triadimenol were also found in the tubifex tissue. Although the amount of these stereoisomers were different from each other with relatively more accumulation of the most fungi-toxic stereoisomer (1S,2R), the abundance ratios in the two exposure treatments were similar at the same sampling, following the order (1S,2S) > (1R,2S) > (1R,2R) > (1S,2R). The bioaccumulation factor was calculated for parent compound triadimefon and metabolite enrichment factor for metabolite. The results showed that both uptake routes, epidermal contact in the aqueous phase and ingestion of solid particles in soil, were important to the bioaccumulation of the triadimefon and triadimenol in tubifex.

Enantioselective bioaccumulation of soil-associated fipronil enantiomers in Tubifex tubifex

Enantioselective behavior of chiral pesticides in the aquatic environment has been a subject of growing interest. In this study, the enantioselective bioaccumulation of fipronil enantiomers in Tubifex tubifex (Oligochaeta, Tubificida) was detected in both spike-water and spike-soil systems, respectively. For the spike-water treatment, a 9-day exposure experiment was employed and the enantiomer fraction in tubifex tissue was maintained approximately at 0.58 during the experiment. In addition, a 14-day bioaccumulation period was chosen for the spike-soil treatment and a more significant deviation of enantiomer fraction from 0.5 in tubifex tissue was detected, with concentrations of the R-form higher than that of the S-form. Therefore, the bioaccumulation of fipronil was enantioselective in tubifex tissue for the two treatments and the magnitude of enantioselectivity may be influenced by different exposure conditions. For the spike-soil treatment, the concentrations of fipronil in verlying water and soil were also determined. With the presence of tubifex worms, higher concentrations of fipronil in overlying water and lower concentrations in soil were detected than that in the absence of tubifex treatment during the whole 14-day exposure period. This means that tubifex has positive functions in fipronils diffusion from soil to overlying water and in the degradation of the soil-associated fipronil.

Enantioselective toxic effects of hexaconazole enantiomers against Scenedesmus obliquus.

Enantioselectivity in ecotoxicity of chiral pesticides in the aquatic environment has been a subject of growing interest. In this study, the toxicological impacts of hexaconazole enantiomers were investigated with freshwater algae Scenedesmus obliquus. After 96 h of exposure, the EC(50) values for rac-hexaconazole, (+)-hexaconazole, and (-)-hexaconazole were 0.178, 0.355, and 0.065 mg l(-1) , respectively. Therefore, the acute toxicities of hexaconazole enantiomers were enantioselective. In addition, the different toxic effects were evaluated when S. obliquus were exposed to 0.2, 0.5, and 1.0 mg l(-1) of rac-hexaconazole, (+)-hexaconazole, and (-)-hexaconazole during 96 h, respectively. The chlorophyll a and chlorophyll b contents of S. obliquus treated by (-)-hexaconazole were lower than those exposed to (+)-hexaconazole, whereas the malondialdehyde contents of S. obliquus treated by (-)-form were higher than those exposed to (+)-form at higher concentrations. In general, catalase activities were significantly upregulated by exposure to (-)-enantiomer than (+)-enantiomer at all three concentrations. However, superoxide dismutase activities exposed to (-)-hexaconazole were lower than that exposed to (+)-hexaconazole at 0.2 mg l(-1) and 0.5 mg l(-1) . On the basis of these data, the acute toxicity and toxic effects of hexaconazole against S. obliquus were enantioselective, and such enantiomeric differences must be taken into consideration in pesticide risk assessment.

Enantioselective environmental behavior of the chiral herbicide fenoxaprop-ethyl and its chiral metabolite fenoxaprop in soil.

The enantioselective degradation behavior of fenoxaprop-ethyl (FE) and its chiral metabolite fenoxaprop (FA) in three soils under native conditions was investigated. Two pairs of enantiomers were analyzed by high-performance liquid chromatography (HPLC) with an amylose tri-(3,5-dimethylphenylcarbamate) (ADMPC) chiral column. The degradation of racemic FE in three soils showed the herbicidally inactive S-(-)-enantiomer degraded faster than the active R-(+)-enantiomer. FE was configurationally stable in soils because no interconversion to the respective antipodes was observed during incubation of the enantiopure S-(-)- or R-(+)-FE. The main metabolites of FE were confirmed as FA and 6-chloro-2,3-dihydrobenzoxazol-2-one (CDHB), and the formation of the chiral metabolite FA showed enantioselectivity in soils. The degradation of rac-FA was also enantioselective with the S-(-)-FA preferentially degraded: the half-life (t(1/2)) of the S-form in the three soils ranged from 2.03 to 5.17 days, and that of R-form ranged from 2.42 to 20.39 days. The inversion of the S-(-)-enantiomer into the R-(+)-enantiomer occurred in two of the three soils when the enantiopure S-(-)- and R-(+)-FA were incubated. The data from sterilized control experiments indicated that the enantioselectivity of FE and FA was attributed to microbially mediated processes.