Stereoselective Bioaccumulation Research Articles

Stereoselective bioaccumulation and dissipation of four stereoisomers of cyproconazole in earthworm-soil microcosm

Cyproconazole is a representative and widely used triazole fungicide with four stereoisomers, which will bring some risks to non-target organisms. A fast analytical method on supercritical fluid chromatography-tandem mass spectrometry was established in 4 min, and the environmental hazards of chiral cyproconazole were studied in earthworm-soil microcosm, including stereoselective bioaccumulation and dissipation. In the process of bioaccumulation, the concentrations of cyproconazole stereoisomers in earthworms showed a trend of increasing first and then reaching a stable state at 6 mg/kg treatment, which was different from those at 0.6 mg/kg treatment (decease-increase-equilibrium). The concentration order was (2S,3R)- > (2S,3S)- > (2R,3R)- > (2R,3S)-cyproconazole and (2S,3S)- ≈ (2S,3R)- > (2R,3R)- > (2R,3S)-cyproconazole at 6 and 0.6 mg/kg treatments, respectively. The bioaccumulation factor (BAF) values were in the range of 0.018–0.55, showing weakly relative accumulation capacity. The dissipation of cyproconazole stereoisomers in artificial soil accorded with the first-order kinetics equation, and the half-lives were 20.1–23.6 and 7.66–8.28 days at 6 and 0.6 mg/kg treatments, respectively, without stereoselectivity and diastereoselectivity. In earthworms, the dissipation half-lives were 5.81–6.01 days with the preferential dissipation of (2R,3R)-cyproconazole. The study would help with the rational uses and risk assessments of cyproconazole.

Stereoselective bioaccumulation and dissipation of pyrisoxazole in earthworm-soil microcosm

Pyrisoxazole is a chiral fungicide with high sterilizing activity to the plant pathogenic bacteria. It has two chiral C atoms, which bring four stereoisomers. The present work was the first time to explore the stereoselective bioaccumulation behavior of pyrisoxazole in earthworms by chiral liquid chromatography coupled to quadrupole time-of-flight mass spectrometry (LC-Q-TOF/MS). The absolute configurations of pyrisoxazole stereoisomers were confirmed by circular dichroism (CD) coupled with calculated electronic circular dichroism (ECD) method, and the elution order in Lux Cellulose-3 column was as follows: (−)-3S, 5R-pyrisoxazole, (+)-3R, 5S-pyrisoxazole, (+)-3S, 5S-pyrisoxazole and (−)-3R, 5R-pyrisoxazole. The recoveries of pyrisoxazole stereoisomers in earthworm and soil samples ranged from 80.8 % to 101 % with the RSD lower than 6.3 %. In bioaccumulation progress, (+)-3R, 5S-pyrisoxazole was accumulated preferentially in earthworms, and the bioaccumulation concentrations of high-activity (−)-3S, 5R-pyrisoxazole were the lowest. There were no stereoselective bioaccumulation between (+)-3S, 5S-pyrisoxazole and (−)-3R, 5R-pyrisoxazole, while there was diastereoselectivity between Z-pyrisoxazole and E-pyrisoxazole with higher E-pyrisoxazole concentrations. In the whole bioaccumulation process, the BAF values of (+)-3R, 5S-pyrisoxazole were significantly higher than (−)-3S, 5R-pyrisoxazole, and the BAF values of (−)-3S, 5R-pyrisoxazole were the lowest. The dissipation of pyrisoxazole stereoisomers in the artificial soil was very slow and had no stereoselectivity, and the existence of earthworms had little effects on the dissipation of pyrisoxazole stereoisomers, which indicated that the stereoselective behaviors of pyrisoxazole in earthworms were caused by the stereoselective enrichment and dissipation of earthworms themselves. Taken together, (−)-3S, 5R-pyrisoxazole was recommend as a commercial product. This study played a positive role in guiding the development of environmentally friendly pesticides and provided database for the environmental and biological risk assessment of pyrisoxazole.

Enantioselectivity of new chiral triazole fungicide mefentrifluconazole: Bioactivity against phytopathogen, and acute toxicity and bioaccumulation in earthworm (Eisenia fetida)

Elaborating the environmental behavior of mefentrifluconazole, a novel triazole fungicide, in stereoselective level is of paramount importance for the application of the pesticide in agriculture. In this study, the enantioselective bioactivity, acute toxicity and stereoselective bioaccumulation of mefentrifluconazole in earthworm (Eisenia fetida) were investigated. Bioactivity tests against four pathogens revealed that R-(−)-mefentrifluconazole exhibited approximately 11–113 times higher bioactivity than its S-(+)-mefentrifluconazole. However, the LC50 of S-(+)-, rac- and R-(−)-mefentrifluconazole to earthworm was measured to be 4.1, 11.4 and 7.3 μg/cm2, respectively, indicating active ingredient R-(−)-mefentrifluconazole is less toxic than its racemate and S-form. Accumulation of mefentrifluconazole in earthworms was non-enantioselective and negatively related to its adsorption onto soils. The concentration of mefentrifluconazole in in situ pore water (CIPW) and CaCl2 extraction (CCaCl2) was closely related to its accumulation in earthworms, suggesting that CIPW and CCaCl2 could be appropriate indicators for estimation of the bioavailability of mefentrifluconazole in soil. Conclusively, our study provides necessary information for the risk assessment of mefentrifluconazole in agriculture.

Species-specific dechlorane plus isomer fractionation during bioaccumulation: phenomenon and potential mechanisms

The occurrence and behavior of dechlorane plus (DP), an additive chlorinated flame retardant, have been intensively studied since it was identified in 2006. The commercial products of DP are a mixture of two stereoisomers: syn-DP and anti-DP. Stereoselective bioaccumulation of DP isomers in biota was reported in field monitoring and laboratory experiments. This review summarizes stereoselective bioaccumulation of DP in biota samples and provides the potential mechanisms for this stereoselective bioaccumulation. Stereoselective enrichment of syn-DP was widely observed in fish, whereas selective enrichment of anti-DP was mainly found in some birds. This species-specific stereoselective enrichment of DP might reflect that two different types of DP isomer fractionation occurred in bioaccumulation between ectotherms and endotherms. Anti-DP is more readily metabolized through biotransformation in all animals. However, a preferential excretion of anti-DP in fish and syn-DP in birds was observed based on the available data. Both processes determine the DP isomer fractionation in bioaccumulation. A direct comparison in DP composition between biological samples and commercial products was conducted for most studies to determine the occurrence of stereoselective DP enrichment, which may lead to underestimating the potential stereoselective enrichment of DP in organisms. The factors which affected the DP isomer composition in organisms included the tissues or organs used, DP concentration, organisms’ trophic levels occupied, and sex. Inconsistent results were obtained considering the effects of these influence factors. The underlying cause of these inconsistent results is unclear based on present data. Further research on DP biotransformation and interactions between DP and biomacromolecule is needed.

Fractions Transformation and Dissipation Mechanism of Dechlorane Plus in the Rhizosphere of the Soil-Plant System.

The fractions transformation and dissipation mechanism of Dechlorane Plus (DP) in the rhizosphere of soil-plant system were investigated and characterized by a 150-day experiment using a rhizobox system. The depuration, accumulation, and translocation of DP in rice plants were observed. The contributions of plant uptake, microbial degradation, and bound-residue formation to DP dissipation under the rhizosphere effect were modeled and quantified. The gradients of DP concentrations correlated well with microbial biomass in the rhizosphere (R2 = 0.898). The rhizosphere facilitated the bioavailability of DP (excitation) and modified the bound-residue formation of DP (aging). DP concentrations in roots were positively correlated with the labile fraction of DP in soil (R2 = 0.852-0.961). There were spatiotemporal variations in the DP fractions. Dissolved and soil organic carbon were important influences on fraction transformation. Contributions to total DP dissipation were in the following ranges: microbial degradation (8.33-54.14%), bound-residue formation (3.64-16.43%), and plant uptake (0.54-3.85%). With all of these processes operating, the half-life of DP in the rhizosphere was 105 days. The stereoselectivity of DP isomers in both rice and DP fractions in soil were observed, suggesting a link between stereoselective bioaccumulation of DP in terrestrial organisms and dissipation pathways in soil.

Etoxazole stereoselective determination, bioaccumulation, and resulting oxidative stress in Danio rerio (zebrafish).

An environmentally-friendly and fast analytical method for the stereoselective determination of etoxazole was developed and then applied to estimate stereoselective bioaccumulation and elimination in zebrafish using SFC-MS/MS. Optimal enantioseparation conditions were determined using a Chiralpak IG-3 column and CO2/MeOH mobile phase (80/20, v/v), at 3.0mL/min within 1min, 30°Me and 18MPa. A modified QuEChERS method was developed for zebrafish sample pretreatment, and mean recoveries were 88.43-110.12% with relative standard deviations ranging from 0.32 to 5.34%. The enantioselectives of etoxazole enantiomers in zebrafish during uptake and depuration phases were evaluated. Significant enantioselective bioaccumulation was observed, with preferential accumulation of (-)-R-etoxazole compared to its antipode, during uptake at both low and high exposure concentrations. The toxic effects of etoxazole on zebrafish were further explored, and activities of antioxidant enzymes were determined in liver of zebrafish. Significant changes were observed in the SOD and GST activities and in the MDA levels, which indicated the occurrence of oxidative stress in liver of zebrafish. The toxic effects exhibited time- and dose-dependent properties. These results can facilitate the accurate risk evaluation of etoxazole and provide basic knowledge for further study of biotoxicity mechanisms.

Comparative study of dechlorane plus (DP) in adult chickens and developing embryos: Stereo-selective bioaccumulation of DP in chickens

Although isomer-specific bioaccumulation of dechlorane plus (DP) has been addressed in many studies, it remains unclear which factors determine this process and whether biotransformation of DP occurs in organisms. Comparative experiments were conducted in both in vivo and in ovo incubation using hens and eggs to identify the dominant factors determining the bioaccumulation of DP. Hens and fertilized eggs were exposed to DP isomers (syn- and anti-DP) by feeding and spiking, respectively, to investigate absorption, elimination, and metabolism. No significant differences were found between absorption efficiencies of DP isomers in the adult hens. Following first-order kinetics, anti-DP exhibited a slightly longer half-life than syn-DP as well as an elevated anti-DP fraction in laid eggs, thereby suggesting selective enrichment of anti-DP in adult hens. However, chicken embryos metabolized approximately 12% and 28% of the absorbed syn- and anti-DP, respectively, thereby verifying that anti-DP was preferably metabolized. This result indicated that stereo-selective excretion of syn-DP, rather than preferred metabolism of anti-DP, played a more prominent role in isomer-specific bioaccumulation of DP in chickens. Further studies on metabolites of DP are crucial to understanding the fate of DP in organisms.

Stereoselective bioaccumulation and elimination of chiral PCBs 95 and 149 in earthworm Eisenia fetida

The chiral signatures and environmental behaviors of chiral polychlorinated biphenyls (PCBs) have been extensively studied. However, information regarding chiral PCBs in invertebrates, especially earthworms, is limited. This study aimed to investigate the stereoselective bioaccumulation, elimination, and biotransformation of chiral PCBs 95 and 149 in an earthworm-soil system. Preferential enrichment of (+)-atropisomers and elimination of (−)-atropisomers were observed, for both PCBs 95 and 149, during the uptake and elimination phases, respectively, leading to higher enantiomer fractions (EFs). A significant linear correlation between the total concentrations of chiral PCBs and EF values was found in earthworms. The EF values increased with the increase in exposure time and further increased during the elimination phase, indicating the biotransformation of chiral PCBs. Hydroxylated metabolites of PCB 95 were found in earthworms for the first time, thus verifying the ability of earthworms to metabolize chiral PCBs. However, no methylsulfonyl metabolites were observed for PCBs 95 and 149. These findings might be helpful for understanding the biological processes of chiral PCBs in species at lower trophic levels.

Stereoselective bioaccumulation of chiral PCB 91 in earthworm and its metabolomic and lipidomic responses

Stereoselective bioaccumulation, elimination, metabolomic and lipidomic responses of earthworm Eisenia fetida exposed to chiral polychlorinated biphenyl (PCB) 91 in an earthworm-soil system were investigated. Preferential bioaccumulation of (−)-PCB 91 and elimination of (+)-PCB 91 were observed following 50 and 500 μg/kgdwt exposures. Enantiomer fraction (EF) values decreased over time during the uptake and elimination periods. Metabolomics and lipidomics techniques based on ultra-performance liquid chromatography/quadrupole time-of-flight mass spectrometry (UPLC-QTOF-MS) revealed significant changes in 108 metabolites after earthworms exposure to (+)-, (−)-, and (±)-PCB 91, compared to control groups. Forty two of these metabolites were identified as amino acids, nucleosides, fatty acids, dicarboxylic acids, vitamins or others. Lysophospholipids including six lysophosphatidylcholines (LPC), six lysophosphatidylethanolamine (LPE), eight lysophosphatidylinositol (LPI) and five lysophosphatidylserine (LPS) were also differentially expressed between exposure and control groups. Alterations in the levels of metabolites and lipids indicated stereoselective effects of chiral PCB 91 on earthworm amino acid, energy, and nucleotide metabolism, neurodevelopment and gene expression. Overall, the effects of (+)-PCB 91 were more pronounced than that of (−)- and (±)-PCB 91.

Stereoselective bioaccumulation of syn- and anti-Dechlorane plus isomers in different tissues of common carp (Cyprinus carpio)

Common carps (Cyprinus carpio) were exposed to syn- and anti-Dechlorane Plus (DP) isomers to investigate absorption, tissue distribution, and stereoselective bioaccumulation of DP isomers. The absorption efficiencies of anti-DP in the gastrointestinal system were higher than those of syn-DP. A linear accumulation was found for both isomers in all fish tissues except for serum; and the liver and gill exhibited the highest and lowest DP assimilation efficiency, respectively. The elimination of DP isomers in all tissues followed first-order kinetics, with the fastest depuration rate occurring in the liver and serum. The biomagnification factors (BMFs) of both isomers were less than one in all tissues, except for serum. Anti-DP was preferably accumulated in the liver, gill, and serum, whereas syn-DP was selectively accumulated in the carcass and gastrointestinal tract. As a whole, fish did not show selective accumulation of the syn- or anti-DP isomer in the uptake stage, whereas a selective accumulation of syn-DP in fish was observed during the depuration period, which could be due to a selective excretion of anti-DP. Metabolism cannot be ruled out as a possible reason considering the high fanti values and the high elimination rate of DPs in the liver.

Stereoselective Bioaccumulation of Water and Soil-Associated Dufulin Enantiomers in Tubifex.

In this study, the stereoselective bioaccumulation of rac-dufulin, pure S-(+)-dufulin, and pure R-(-)-dufulin in Tubifex (Oligochaeta, Tubificida) were analyzed in spiked-water and spiked-soil systems at low and high dose levels. In the bioaccumulation experiments treated with rac-dufulin, the enantioselective behaviors of the enantiomers show that the concentrations of R-(-)-dufulin are higher than those of S-(+)-dufulin at two dose levels. However, when treated with solely pure S-(+)-dufulin and R-(-)-dufulin, no significant difference of concentrations was detected in Tubifex. Furthermore, the calculated accumulation factors in Tubifex indicated that dufulin (racemic or the pure enantiomers) in the spiked-soil treatments had higher bioaccumulation potential than in the spiked-water treatments. The spiked-soil experiments revealed that the dissipation of dufulin in soil was not enantioselective at the enantiomer levels and Tubifex could reduce the concentrations of dufulin in the underlying solid matrix and accelerate its repair and detoxification process.

Effects on cranio-facial morphogenesis in embryos exposed in vitro to retinoic acid, valproic acid, and to the antifungal azoles cyproconazole, triadimefon and flusilazole

Elaborating the environmental behavior of mefentrifluconazole, a novel triazole fungicide, in stereoselective level is of paramount importance for the application of the pesticide in agriculture. In this study, the enantioselective bioactivity, acute toxicity and stereoselective bioaccumulation of mefentrifluconazole in earthworm (Eisenia fetida) were investigated. Bioactivity tests against four pathogens revealed that R-(−)-mefentrifluconazole exhibited approximately 11–113 times higher bioactivity than its S-(+)-mefentrifluconazole. However, the LC50 of S-(+)-, rac- and R-(−)-mefentrifluconazole to earthworm was measured to be 4.1, 11.4 and 7.3 μg/cm2, respectively, indicating active ingredient R-(−)-mefentrifluconazole is less toxic than its racemate and S-form. Accumulation of mefentrifluconazole in earthworms was non-enantioselective and negatively related to its adsorption onto soils. The concentration of mefentrifluconazole in in situ pore water (CIPW) and CaCl2 extraction (CCaCl2) was closely related to its accumulation in earthworms, suggesting that CIPW and CCaCl2 could be appropriate indicators for estimation of the bioavailability of mefentrifluconazole in soil. Conclusively, our study provides necessary information for the risk assessment of mefentrifluconazole in agriculture.

Stereoselective bioaccumulation, transformation, and toxicity of triadimefon in Scenedesmus obliquus.

In this study the stereoselective bioaccumulation and transformation of triadimefon and the toxicity of triadimefon and its metabolite triadimenol to the green algae Scenedesmus obliquus were studied. In growth inhibition experiments, triadimenol was more toxic than triadimefon, and (1S,2R)-triadimenol, which has the largest fungicidal activity, presented the highest toxicity to the algae. In bioaccumulation experiments, triadimefon was rapidly taken up by algae cells, and the decrease in the concentration of triadimefon was accompanied by an increase in triadimenol. The transformation of S-(+)- triadimefon was faster than that of the R-(-)-enantiomer, resulting in four triadimenol stereoisomers at different forming rates: B2 (1S, 2S)>B1 (1R, 2R)>A2 (1S, 2R)>A1 (1R, 2S). Thus, it is necessary to explore the enantioselective toxicology and ecological fate of these chiral pesticides in an environmental risk assessment. Also, their metabolites should be paid specific attention to since they may pose higher ecological risks.

Dechlorane Plus in paired hair and serum samples from e-waste workers: Correlation and differences

Dechlorane Plus (DP) and a dechlorinated product of DP were measured in 34 matched human hair and serum samples (19 males and 15 females) collected from e-waste recycling workers in South China. The DP (sum of syn- and anti-DP) concentrations in hair and serum samples ranged from 6.3 to 1100ngg−1 dry weight and from 22 to 1400ngg−1 lipid weight (lw). The levels of anti-Cl11-DP ranged from 0.02 to 1.8ngg−1 in hair and from not detected to 7.9ngg−1 lw in serum. Significant positive correlations for both DP and anti-Cl11-DP concentrations between hair and serum samples were found (p<0.05), indicating hair to be a suitable matrix for human DP exposure. However, a significant difference was found in the DP isomer composition between hair and serum, suggesting stereoselective bioaccumulation during the absorption of DP into hair. A sharp gender difference was found in the levels of DP in hair. Moreover, syn-DP, anti-DP and anti-Cl11-DP in hair significantly correlated with those in serum for male samples, but not for female samples. The observed gender differences in the present study may be, in part, ascribed to the much longer hair exposure time for females than males due to the difference in sampling distance from the scalp.

Stereoselectivity in bioaccumulation and excretion of epoxiconazole by mealworm beetle (Tenebrio molitor) larvae

Stereoselectivity in bioaccumulation and excretion of stereoisomers of epoxiconazole by mealworm beetle (Tenebrio molitor) larvae through dietary exposure was investigated. Liquid chromatography tandem mass spectrometry (HPLC−MS/MS) method that use a ChiralcelOD-3R[cellulosetris-Tris-(3, 5-dichlorophenyl-carbamate)] chromatography column was applied to carry out chiral separation of the stereoisomers. Wheat bran was spiked with racemic epoxiconazole at two dose levels of 20mg/kg and 2mg/kg (dry weight) to feed T. molitor larvae. The results showed that both the doses of epoxiconazole were taken up by Tenebrio molitor larvae rapidly at the initial stages. There was a significant trend of stereoselective bioaccumulation in the larvae with a preferential accumulation of (−)-epoxiconazole in the 20mg/kg dose. The stereoselectivity in bioaccumulation in the 2mg/kg dosage was not obvious compared to the 20mg/kg group. Results of excretion indicated an active excretion is an important pathway for the larvae to eliminate epoxiconazole which was a passive transport process with non stereoselectivity. The faster elimination might be the reason for the low accumulation of epoxiconazole, as measured by bioaccumulation factor (BAF).

Sources, gastrointestinal absorption and stereo-selective and tissue-specific accumulation of Dechlorane Plus (DP) in chicken

Dechlorane Plus (DP) isomers, along with two dechlorinated metabolites were measured in environmental matrices, chyme and digestive tract contents and tissues of chicken from an e-waste recycling site located in South China. Soil is proved to be the main source of DP in chicken rather than food because soil contributes more than 94% of total DP in chyme. In the gastrointestinal tract absorption processes, no selective absorption was observed for DP isomers during the ingestion processes. The tissue distribution of DP isomers in chicken exhibits complicated characteristics. The lipid contents in tissues are the main factors in the tissue distribution of DP, while the different blood perfusion state and the different tissue functions also seem to influence the tissue distribution of DP. The fat, brain, and liver exhibit higher fanti values (0.65, 0.64, and 0.64) than the other tissues (0.54–0.59). The elevated fanti values of DP from the contamination source (0.52 in soil) to chicken suggest stereoselective bioaccumulation of anti-DP in chicken. The similar ratios of anti-Cl11-DP to anti-DP between soil and chicken imply that anti-Cl11-DP mainly derives from the uptake from environment rather than in vivo dechlorination.

Bioavailability and tissue distribution of Dechloranes in wild frogs (Rana limnocharis) from an e-waste recycling area in Southeast China

Dechlorane Plus (DP), a flame retardant used as an alternative to decabromodiphenylether, has been frequently detected in organisms, indicating its bioaccumulation and biomagnification potential in aquatic and terrestrial species. However, little data is available on the bioaccumulation of DP in amphibians. Dechlorane Plus and its analogs (DPs) were detected in the liver, muscle and brain tissues of wild frogs (Rana limnocharis), which were collected from an e-waste recycling site, Southeast China. DP, Mirex, Dec 602 and a dechlorinated compound of DP (anti-Cl11-DP) varied in the range of 2.01–291, 0.650–179, 0.260–12.4, and not detected (nd)–8.67 ng/g lipid weight, respectively. No difference of tissue distribution was found for syn-DP, Mirex and Dec 602 between the liver and muscle tissue (liver/muscle concentration ratio close to 1, p > 0.05). However, higher retention was observed for anti-DP and anti-Cl11-DP in the frog muscle relative to the liver tissue (liver/muscle concentration ratio < 1, p < 0.05). Additionally, the blood-brain barrier was found to work efficiently to suppress these compounds entering brain tissues in this species (liver/brain concentration ratio > 1, p < 0.05), and the molecular weight was a key factor impacting the extent of the blood-brain barrier. Compared to levels in the muscle and brain tissue, a preferential enrichment of syn-DP was observed in the liver tissue, suggesting the occurrence of stereo-selective bioaccumulation in the wild frog.

Occurrence and biomagnification of organohalogen pollutants in two terrestrial predatory food chains

Organohalogen pollutants (OHPs), including dichlorodiphenyl trichloroethane and its metabolites (DDTs), polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), hexabromocyclododecanes (HBCDs), and dechlorane plus (DP), were determined in three raptor species, namely, the common kestrel (Falco tinnunculus), eagle owl (Bubo bubo), and little owl (Athene noctua), as well as in their primary prey items: Eurasian tree sparrow (Passer montanus) and brown rat (Rattus norvegicus). DDTs were the predominant pollutants in avian species followed by PBDEs and PCBs, then minimally contribution of HBCDs and DP. Inter-species differences in the PBDE congener profiles were observed between the owls and the common kestrels, with relatively high contributions of lower brominated congeners in the owls but highly brominated congeners in the kestrels. This result may partly be attributed to a possible greater in vivo biotransformation of highly brominated BDE congeners in owls than in kestrels. α-HBCD was the predominant diastereoisomer with a preferential enrichment of (−)-enantiomer in all the samples. No stereoselective bioaccumulation was found for DP isomers in the investigated species. Biomagnification factor (BMF) values were generally higher in the rat−owl food chain than in the sparrow−kestrel food chain. Despite this food chain-specific biomagnification, the relationships between the log BMF and log KOW of PCBs and PBDEs followed a similar function in the two food chains, except for BDE-47, -99, and -100 in the sparrow−kestrel feeding relationship.

Dechlorane Plus and its dechlorinated analogs from an e-waste recycling center in maternal serum and breast milk of women in Wenling, China

We measured Dechlorane Plus (DP) and its dechlorinated analogs in the blood and milk from women living in e-waste recycling sites in Wenling of Taizhou region, China (n = 49). Both syn-DP and anti-DP were detected in all samples. Another compound, Cl11-DP, was detected in 45% and 84% of milk and serum samples, respectively. DP levels in blood and milk from residents living in the local environment >20 yrs (R20 group) were significantly higher than those living in Taizhou <3 yrs (R3 group) (p < 0.05). The milk/serum partition coefficient from the same women was approximately 0.43 and 0.47 for syn-DP and anti-DP, respectively. A similar value in milk compared with anti-DP/∑DPs (fanti) in serum suggested that stereoselective DP bio-accumulation did not occur during the DP transport from blood to milk. This result indicate that DP can bio-accumulate in blood and milk with the low milk/serum partition coefficient and similar blood and milk stereoselective bio-accumulation profiles.

Growth of the human crystalline lens in childhood

Organohalogen pollutants (OHPs), including dichlorodiphenyl trichloroethane and its metabolites (DDTs), polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), hexabromocyclododecanes (HBCDs), and dechlorane plus (DP), were determined in three raptor species, namely, the common kestrel (Falco tinnunculus), eagle owl (Bubo bubo), and little owl (Athene noctua), as well as in their primary prey items: Eurasian tree sparrow (Passer montanus) and brown rat (Rattus norvegicus). DDTs were the predominant pollutants in avian species followed by PBDEs and PCBs, then minimally contribution of HBCDs and DP. Inter-species differences in the PBDE congener profiles were observed between the owls and the common kestrels, with relatively high contributions of lower brominated congeners in the owls but highly brominated congeners in the kestrels. This result may partly be attributed to a possible greater in vivo biotransformation of highly brominated BDE congeners in owls than in kestrels. α-HBCD was the predominant diastereoisomer with a preferential enrichment of (−)-enantiomer in all the samples. No stereoselective bioaccumulation was found for DP isomers in the investigated species. Biomagnification factor (BMF) values were generally higher in the rat−owl food chain than in the sparrow−kestrel food chain. Despite this food chain-specific biomagnification, the relationships between the log BMF and log KOW of PCBs and PBDEs followed a similar function in the two food chains, except for BDE-47, -99, and -100 in the sparrow−kestrel feeding relationship.