Enantiomeric Fractions Research Articles

Enantiomeric analysis of polycyclic musks AHTN and HHCB and HHCB-lactone in sewage sludge by gas chromatography/tandem mass spectrometry.

Enantioselective analysis of chiral compounds is an interesting and challenging technique used to elucidate the degradation/transformation mechanisms of these compounds or understand their environmental processes. In this study, we have developed an effective separation and detection approach for the enantiomeric analysis of AHTN and HHCB, as well as a transformation product of HHCB (HHCB-lactone), in sludge samples. The analytical method was developed using a cyclodextrin-based enantioselective gas chromatography column combined with tandem mass spectrometry (GC/MS/MS). The GC oven temperature gradients, the linear velocity of the helium carrier gas, as well as the MS/MS parameters, including quantitative and qualitative ion pairs, dwell times, and collision energies, were optimized to achieve good separation and high sensitivity for all target enantiomers. Baseline separations of all target enantiomers were observed. Limits of quantification (LOQs) for all enantiomers ranged from 0.010 to 0.045 μg/L, and calibration linearity for all single enantiomers was higher than 0.99. The intra-day and inter-day precisions for all single enantiomers of AHTN, HHCB, and HHCB-lactone ranged from 0.8 to 3.8% and from 4.2 to 8.3%, respectively. The developed method was fully validated through enantioselective analyses of AHTN, HHCB, and HHCB-lactone in sludge samples collected from 17 WWTPs. The enantiomeric fractions (EFs) of HHCB and HHCB-lactone in sludge samples distinctly deviated from 0.50, indicating a significant enantioselective transformation of HHCB with preferential degradation of the 4S enantiomers. Significant positive correlations were found between the EF values of cis-HHCB enantiomers and cis-HHCB-lactone enantiomers in the sludge samples, implying that further efforts are still needed to clarify the degradation/transformation mechanism from HHCB to HHCB-lactone.

Legacy and Currently Used Organic Contaminants in Human Hair and Hand Wipes of Female E-Waste Dismantling Workers and Workplace Dust in South China.

Legacy organic contaminants, such as polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs), and several currently used organic contaminants, such as novel brominated retardants (NBFRs), organophosphate flame retardants (OPFRs), and Dechlorane Plus (DPs), were measured in the segmented hair and hand wipes of e-waste dismantling workers and in the dust from their workplace in an e-waste recycling site in South China to assess the accumulation and sources of organic contaminants in the hair shaft. The median concentrations of DPs, PBDEs, NBFRs, PCBs and OPFRs in hair samples were 23.5, 154, 156, 349, and 371 ng/g, respectively. A linear increase in organic contaminant concentrations was found along the hair shaft, with significant differences among each segment, while the age-related patterns were similar among the 7 hair segments. A linear relationship was found between the accumulation rates and the log KOW, indicating that the accumulation rates of organic contaminants along the hair shaft decreased with increasing log KOW values. Enantiomer fraction (EF) values of PCB-132 in distal segments were close to those in dust and air, while EFs in proximal segments were close to those in serum. The contributions of PCBs from external sources to hair increased with the distance from the scalp of hair segments, from 67.8% in 0-3 cm segments to 95.9% in 18-21 cm segments.

Enantioselective LC-MS/MS for anthropogenic markers of septic tank discharge

Households in rural locations utilize septic tanks for wastewater treatment and can cause surface water contamination. A new methodology was developed to help investigate the role septic tanks play in the dissemination of prescription and over-the-counter drugs, personal care products and stimulants in the aqueous environment. Simultaneous analysis of 16 chiral and achiral anthropogenic markers was achieved using a Chirobiotic V2® enantioselective column in polar ionic mode. The optimized method achieved quantitation limits for 16 compounds in the range 0.001–2.9 μg L−1 and 0.0002–0.43 μg L−1 for septic tank effluent and stream water, respectively. Application of the method to samples collected in North East Scotland found caffeine to be ubiquitous in all samples studied suggesting it as a good indicator of septic tank discharge. In rural streams studied, concentrations of all prescription drugs investigated were ≤0.02 μg L−1. However, analgesics and stimulants were at high concentration in one location indicating direct discharge of septic tank wastewater (i.e., not dissipated through a soak away). For example, paracetamol, cotinine and caffeine were measured at 1100 μg L−1, 31 μg L−1 and 200 μg L−1, respectively, which is comparable to septic tank effluents. Furthermore, S(+)-amphetamine and R(−)-amphetamine were present in this stream sample at 0.20 and 0.27 μg L−1. This corresponds to an enantiomeric fraction of 0.43, which is typical of untreated wastewaters in the UK. Findings illustrate further study on the diffuse impact of septic tanks to surface water is needed and can be supported using this new multi-residue enantioselective method.

Application and enantiomeric residue determination of diniconazole in tea and grape and apple by supercritical fluid chromatography coupled with quadrupole-time-of-flight mass spectrometry

A chiral separation and residue determination method for diniconazole enantiomers in tea, apple, and grape was developed and validated by supercritical fluid chromatography coupled with quadrupole-time-of-flight mass spectrometry (SFC-Q-TOF/MS). The two diniconazole enantiomers were separated on a Chiral CCA column, and the chromatographic conditions (mobile phase proportion and modifier, column temperature, backpressure, and auxiliary solvent) were optimized. The optimal SFC-Q-TOF/MS conditions were selected as a mobile phase of CO2/isopropanol (IPA) (v/v, 96/4), flow rate at 2.0 mL/min, automated back pressure regulator (ABPR) at 2000 psi, column temperature at 25 ℃ and under electrospray ionization positive mode with the best auxiliary solvent of 2 mmol/L ammonium acetate in methanol/water (v/v, 1/1) at 0.20 mL/min flow rate. Residues in tea and fruit samples were extracted by acetonitrile/water (v/v, 4/1 for fruit and 2/1 for tea), purified by Cleanert TPT or Pesti-Carb solid phase extraction column, then analyzed by SFC-Q-TOF/MS with matrix-matched external standard quantification method. The elution order of diniconazole enantiomers on CCA column was R-(-)-diniconazole at first, and S-(+)-diniconazole at second. The standard curve concentration levels of R-(-)-diniconazole and S-(+)-diniconazole in samples ranged from 0.01 mg/L to 1.00 mg/L with the correlation coefficients greater than 0.99. The spiked recoveries of R-(-)-diniconazole and S-(+)-diniconazole in apple and grape at three levels of 0.005, 0.05 and 0.25 mg/kg were in the range of 69.8% to 102.1%, with relative standard deviations (RSDs) (n = 6) between 3.5% and 10.4%, and the limits of quantitation (LOQs) below 0.005 mg/kg. The spiked recoveries in black tea at three levels of 0.01, 0.10, and 0.50 mg/kg were in the range of 85.6% to 90.6%, with the RSDs (n = 6) ranging from 3.9% to 9.5%, and LOQ of 0.01 mg/kg. This residue analysis and determination method for diniconazole enantiomers in apple, grape and tea samples is convenient, reliable, and meets the residue analysis requirement. Also it is applicatied for the residue fates of R-(-)-diniconazole and S-(+)-diniconazole during the fresh tea leaves growing, green tea processing and black tea processing. The degradation half-times (DT50) between R-(-)-diniconazole and S-(+)-diniconazole in the fresh tea leaves growing were 2.9 d and 3.1 d, respectively. The concentrations of R-(-)-diniconazole and S-(+)-diniconazole decreased gradually with time and on the 14th day after application were lower than 10% of the initial concentration. The average enantiomer fractions (EFs) of R-(-)-diniconazole and S-(+)-diniconazole at 2 h, 2, 5, 7, 10 and 14 d after application in fresh tea leaves were 0.505, 0.526, 0.523, 0.558, 0.453 and 0.489, respectively. This result is similar to the result of our last research for the enantiomers of cis-epoxiconazole-another triazole fungicide residues in fresh tea leaves. And in the whole black tea processing, 37.1%–49.3% and 35.9%–57.9% of R-(-)-diniconazole and S-(+)-diniconazole decreased, respectively. The total processing factors (PFs) of R-(-)-diniconazole and S-(+)-diniconazole for the black tea procedure were 0.507-0.629 and 0.421-0.641, respectively. The EFs of R-(-)-diniconazole and S-(+)-diniconazole in black tea processing ranged from 0.432 to 0.532. However, in the whole green tea processing, 22.3%–32.6% and 21.7%–40.3% of R-(-)-diniconazole and S-(+)-diniconazole decreased, respectively. The difference between black tea and green tea is nearly 15%, and in green tea is less decreased than in black tea. The total PFs of R-(-)-diniconazole and S-(+)-diniconazole for the green tea procedure were 0.674-0.777 and 0.597-0.783, respectively. The EFs of R-(-)-diniconazole and S-(+)-diniconazole in green tea processing ranged from 0.473 to 0.504. The PFs illustrated that for R-(-)-diniconazole and S-(+)-diniconazole decrease, the rolling and fermentation were the critical steps in black tea processing, and the rolling was the critical step in green tea processing, respectively.

Multi-milligram resolution and determination of absolute configuration of pentedrone and methylone enantiomers

The enantioresolution of pentedrone and methylone was carried out at a multi-milligram scale by liquid chromatography on a Chiralpak AS® stationary phase. The excellent enantioresolution using this column allowed to collect highly pure enantiomeric fractions, achieving enantiomeric ratios higher than 98%. An overall recovery of 72% was achieved for pentedrone enantiomers and 80% for methylone. Furthermore, the absolute configuration of the enantiomers of both cathinones was determined for the first time by electronic circular dichroism (ECD) spectroscopy, with the aid of theoretical calculations, as (+)‑(S) and (−)‑(R)-pentedrone, and (−)‑(S) and (+)‑(R)‑methylone.

Trace enantioselective determination of triazole fungicides in honey by a sensitive and efficient method

This work presents, for the first time, the simultaneous enantioselective determination of triazole fungicides (paclobutrazol, myclobutanil, diniconazole, and epoxiconazole) in honey samples by chiral liquid chromatography-tandem mass spectrometry (LC–MS/MS). An efficient procedure, solid-phase extraction (SPE) coupled with dispersive liquid-liquid microextraction (DLLME), was used for the extraction, purification, and preconcentration of target analytes. In order to obtain high extraction efficiency, several experimental parameters including the type of SPE cartridge, the pH of sample, the type and volume of elution solvent and extraction solvent, and salt concentration were optimized. Upon optimal conditions, good sensitivity was achieved with limits of detection ranging from 0.005 to 0.028 ng/g and limits of quantification ranging from 0.017 to 0.093 ng/g. Recoveries for eight enantiomers were satisfactory lying between 87.1% and 108.6% in four different honey samples. The intra- and inter-day relative standard deviations were all below 9.1%. This convenient, sensitive, and reliable method was applied to the enantioselective determination of triazole fungicides in 11 honey samples. As a result, the concentrations and enantiomeric fractions of paclobutrazol were determined successfully.

Occurrence and enantiomer profiles of β-blockers in wastewater and a receiving water body and adjacent soil in Tianjin, China

A total of 58 samples were collected from hospitals, municipal wastewater treatment plants (WWTPs), a receiving water body (Dagu Drainage Canal, DDC), and adjacent farmland in Tianjin City, China, in May and November 2013 and were analyzed for five common β-blockers (atenolol, sotalol, metoprolol, propranolol, and nadolol) to elucidate their source, occurrence and fate in a typical city in China. The profiles of the enantiomers of the β-blockers in some samples were examined. Sotalol, metoprolol and propranolol were frequently detected, atenolol was less frequently detected, and nadolol was mostly not detected. Generally, the concentrations in hospital wastewaters occurred from <LOQ to 10 μg/L, while concentrations in municipal WWTP water samples ranged from <LOQ to 5.2 μg/L. Hence, both hospitals and WWTPs acted as sources of β-blockers in the environment. Sotalol, metoprolol and propranolol were determined in soils adjacent to the DDC with concentrations up to hundreds of ng/kg in the topsoil and declining levels in the subsoil. Seasonal variation was observed with samples obtained in May showing higher concentrations, both in the canal and the adjacent soil, which could be ascribed to greater consumption of these drugs, lower temperature and less precipitation in the spring and the former winter. Enantiomeric fractions (EFs) of metoprolol and propranolol in soil samples showed a trend of enrichment of E1 (first-eluted) compared to E2 (second-eluted), while sotalol was almost racemic. In the DDC, no significant difference was found for the pair enantiomers of each β-blocker, while in hospital and WWTP wastewaters, E1 predominated.

Characterizing the Influence of Metabolism on the Halogenated Organic Contaminant Biomagnification in Two Artificial Food Chains Using Compound- and Enantiomer-Specific Stable Carbon Isotope Analysis.

Two artificial food chains, food tiger barb-oscar fish and food tiger barb-redtail catfish, were established in the laboratory. The species-specific biotransformation of ortho, para'-dichlorodiphenyltrichloroethane, 12 polychlorinated biphenyl, and five polybrominated diphenyl ether congeners were characterized by measuring the compound- and enantiomer-specific stable carbon isotope composition (δ13C), enantiomeric fraction of the chiral chemicals, and metabolites in the fish. Compound- and enantiomer-specific biotransformations were revealed by the alteration of δ13C and EF in both predator fish species. Significant correlations between the carbon stable isotope signatures and the depuration rates and biomagnification factors (BMF) were observed. Chemicals that exhibited changes in δ13C during the experiment have higher kd and lower BMF values than those with unchanged δ13C. Specifically, the difference between the predicted BMF based on the log Kow and the measured BMF, ΔBMF, was significantly positively and linearly correlated to the change in the δ13C (expressed by Δδ13C/δ13Cinitial, the percentage of Δδ13C: δ13Cending-δ13Cinitial to the initial δ13Cinitial) in both food chains. These results indicated that the impact of metabolism on the bioaccumulation potential of organic contaminants can be predicted by the stable carbon isotope fractionation of chemicals in the fish.

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.

Simultaneous determination of enantiomers of carfentrazone-ethyl and its metabolite in eight matrices using high-performance liquid chromatography with tandem mass spectrometry.

A reversed-phase simultaneous determination method for the enantiomers of carfentrazone-ethyl and its metabolite carfentrazone in agricultural and environmental samples was established using high-performance liquid chromatography-tandem mass spectrometry. A complete enantioseparation of carfentrazone-ethyl and its chiral metabolite carfentrazone enantiomers was obtained using a chiral column. The absolute configuration and specific optical rotation of carfentrazone-ethyl and carfentrazone enantiomers were first confirmed as peaks 1, 2, 3, and 4: S-(+)-carfentrazone, R-(-)-carfentrazone, S-(-)-carfentrazone-ethyl, and R-(+)-carfentrazone-ethyl, respectively. The specificity, matrix effect, linearity, precision, accuracy, and stability were surveyed to evaluate the feasibility of the method. The mean recovery was in the range of 77.5-102.8% with relative standard deviations of 0.4-9.8% for the samples. The limits of detection of the enantiomers were evaluated as 0.7 to 6.0 μg/kg, and the limits of quantification were 2.5 to 20 μg/kg. The stereoselective degradation of carfentrazone-ethyl and carfentrazone in rice plant was investigated, and there was no clear enantioselectivity for carfentrazone-ethyl. As for carfentrazone, the enantiomer fractions value reached 0.85 at 7 days after spraying. The developed method was simple and reliable enough for the corresponding risk assessment of carfentrazone-ethyl and its metabolite enantiomers in crop plants, cereal grains, and soil samples.

Stereoselective environmental behavior and biological effect of the chiral organophosphorus insecticide isofenphos‑methyl

The enantiomeric environmental behaviors, bioactivities and toxicities of isofenphos‑methyl enantiomers were characterized systematically in this study. (R)‑Isofenphos‑methyl was degraded preferentially in Yangtze River water and different types of vegetables with an enantiomeric fraction (EF) of 0.6 to 0.96. However, (R)‑isofenphos‑methyl was amplified in both Nanjing (EF = 0.32) and Nanchang (EF = 0.27) soil. Our investigations found that there no bidirectional chiral inversion occurred in either Yangtze River water or soils. The bioactivity of (S)‑isofenphos‑methyl was higher than that of its (R)‑enantiomer against different insect targets, such as Meloidogyne incognita, Nilaparvata lugens, Plutella xylostella and Macrosiphum pisi (3.7 to 149 times). (S)‑Isofenphos‑methyl showed higher toxicity for the nontarget organism (1.1 to 32 times). However, (R)‑isofenphos‑methyl possesses 4.0 times more potency than the (S)-form for the nontarget soil organism Eisenia foetida. This study generally could provide more scientific guidance for the corresponding risk assessments of pesticides in addition to providing a new theoretical basis for scientifically and rationally using isofenphos‑methyl.

Diastereoisomer-Specific Biotransformation of Hexabromocyclododecanes by a Mixed Culture Containing Dehalococcoides mccartyi Strain 195.

Hexabromocyclododecane (HBCD) stereoisomers may exhibit substantial differences in physicochemical, biological, and toxicological properties. However, there remains a lack of knowledge about stereoisomer-specific toxicity, metabolism, and environmental fate of HBCD. In this study, the biotransformation of (±)α-, (±)β-, and (±)γ-HBCD contained in technical HBCD by a mixed culture containing the organohalide-respiring bacterium Dehalococcoides mccartyi strain 195 was investigated. Results showed that the mixed culture was able to efficiently biotransform the technical HBCD mixture, with 75% of the initial HBCD (∼12 μM) in the growth medium being removed within 42 days. Based on the metabolites analysis, HBCD might be sequentially debrominated via dibromo elimination reaction to form tetrabromocyclododecene, dibromocyclododecadiene, and 1,5,9-cyclododecatriene. The biotransformation of the technical HBCD was likely diastereoisomer-specific. The transformation rates of α-, β-, and γ-HBCD were in the following order: α-HBCD > β-HBCD > γ-HBCD. The enantiomer fractions of (±)α-, (±)β-, and (±)γ-HBCD were maintained at about 0.5 during the 28 days of incubation, indicating a lack of enantioselective biotransformation of these diastereoisomers. Additionally, the amendment of another halogenated substrate tetrachloroethene (PCE), which supports the growth of strain 195, had a negligible impact on the transformation patterns of HBCD diastereoisomers and enantiomers. This study provided new insights into the stereoisomer-specific transformation patterns of HBCD by anaerobic microbes and has important implications for microbial remediation of anoxic environments contaminated by HBCD using the mixed culture containing Dehalococcoides.

Past and recent state of sediment contamination by persistent organic pollutants (POPs) in the Rhône River: Overview of ecotoxicological implications

Twenty-one sediment samples were taken from five dated sediment cores collected along the Rhône River from 2008 to 2011. A total of 17 polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), 7 polychlorinated biphenyls (PCBs), 8 polybrominated diphenyl ethers (PBDEs), 3 polybrominated biphenyls (PBBs), 3 hexabromocyclododecanes (HBCD) and 31 organochlorine pesticides (OCPs) were investigated to provide information on deposition dynamics in time and space, but also regarding the ecotoxicological risks associated with these contaminants. Median concentrations of total PBDEs are nine times lower than the levels of total PCBs along the entire studied stretch of the Rhône River. The results show that total PBDEs concentrations range from 0.06 to 239 μg·kg−1 DW with a median value of 3.81 μg·kg−1 DW and a maximum concentration measured in the years 2000s. These maximum concentrations are identical to those measured for total PCBs at the end of the 1990s, but show a different pattern of distribution. Abnormal dichlorodiphenyltrichloroethane (DDT) levels were also detected in the downstream section of the river, with a peak concentration of 147.5 μg·kg−1 DW measured at the GEC site from 2005 onwards. Analyses of the enantiomeric fractions reveal a fresh input resulting from a technical formulation. Sediments from the core sampled at the most downstream site (GEC) are found to be highly toxic to organisms living nearby, particularly because of the total PCDD/Fs, DDE and DDT levels. In addition, based on available sediment quality guidelines, there may be a potential bioaccumulation risk for humans not only for these three compounds of concern but also for total PCBs and 7 out of the 8 analysed PBDEs.

Direct chromatographic study of the enantioselective biodegradation of ibuprofen and ketoprofen by an activated sludge

The quantification of the enantiomeric fraction (EF) during the biodegradation process is essential for environmental risk assessment. In this paper the enantioselective biodegradation of ibuprofen, IBU, and ketoprofen, KET, two of the drugs most consumed, was evaluated. Biodegradation experiments were performed in batch mode using a minimal salts medium inoculated with an activated sludge (collected from a Valencian Waste Water Treatment Plant) and supplemented with the racemate of each compound. The inoculum activity was verified using fluoxetine as reference compound. The experimental conditions used (analyte concentration and volume of inoculum) were chosen according to OECD guidelines. In parallel, the optical density at 600 nm was measured to control the biomass growth and to connect it with enantioselectivity. Two RPLC methods for chiral separations of IBU and KET using polysaccharides-based stationary phases were developed. Novel calculations and adapted models, using directly the chromatographic peak areas as dependent variable, were proposed to estimate significant parameters related to the biodegradation process: biodegradation (BD) and EF values at given time, half-life times of (R)- and (S)-enantiomers, number of days to reach a complete BD and the minimum EF expected. The modelled BD and EF curves fitted adequately the data (R2 > 0.94). The use of these new equations provided similar results to those obtained using concentration data. However, the use of chromatographic peak areas data, eliminates the uncertainty associated to the use of the calibration curves. The results obtained in this paper indicate that an enantiorecognition towards IBU enantiomers by the microorganisms present in the activated sludge used in this study occurred, being the biodegradation of (R)-IBU higher than that of (S)-IBU. For KET, non-enantioselective biodegradation was observed.

Enantioselective Distribution, Degradation, and Metabolite Formation of Myclobutanil and Transcriptional Responses of Metabolic-Related Genes in Rats.

Myclobutanil (MT), a chiral fungicide, can be metabolized enantioselectively in organisms. In this work, the associated absorption, distribution, metabolism and transcriptional responses of MT in rats were determined following a single-dose (10 mg·kg-1 body weight) exposure to rac-, (+)- or (-)-MT. The enantiomer fractions (EFs) were less than 0.5 with time in the liver, kidney, heart, lung, and testis, suggesting preferential enrichment of (-)-MT in these tissues. Furthermore, there was conversion of (+)-form to (-)-form in the liver and kidney after 6 h exposure to enantiopure (+)-MT. Enrichment and degradation of the two enantiomers differed between rac-MT and MT-enantiomers groups, suggesting that MT bioaccumulation is enantiomer-specific. Interestingly, the degradation half-life of MT in the liver with rac-MT treatment was shorter than that with both MT-enantiomer treatments. One reason may be that the gene expression levels of cytochrome P450 1a2 ( cyp1a2) and cyp3a2 genes in livers treated with rac-MT were the highest among the three exposure groups. In addition, a positive correlation between the expression of cyp2e1 and cyp3a2 genes and rac-MT concentration was found in livers exposed to rac-MT. Simultaneously, five chiral metabolites were detected, and the enantiomers of three metabolites, RH-9090, RH-9089, and M2, were separated. The detected enantiomers of (+)-MT metabolites were in complete contrast with those of (-)-MT metabolites. According to the results, a metabolic pathway of MT in male rats was proposed, which included the following five metabolites: RH-9089, RH-9090, RH-9090 Sulfate, M1, and M2. The possible metabolic enzymes were marked in the pathway. The findings of this study provide more specific insights into the enantioselective metabolic mechanism of chiral triazole fungicides.

Assessing the use of sand, peat soil, and pine bark for the attenuation of polar pesticides from agricultural run-off: a bench-scale column experiment.

Biofilters have been shown to be efficient for removing pollutants from different water effluents, but little information is available about their capacity to remove highly polar pesticides from agricultural run-off waters. In this study, we assess the capacity of three different biofilter-supporting materials (sand, peat soil, and pine bark) to remove five phenoxyacid herbicides (mecoprop, dicamba, MCPA, dichlorprop and 2,4-D) and five non-ionic pesticides (atrazine, simazine, fenitrotion, diazinon, and alachlor) from real agricultural run-off waters. The experimental design included three columns 120cm in length and 15cm in diameter, each filled with 100cm of one of the selected supporting materials. After 30days of acclimation, the columns were fed with agricultural run-off water spiked at 10μgL-1 with each of the studied pesticides for 20days at a hydraulic loading rate (HLR) of 0.32mday-1. The results show that the sand filter was the best supporting material for removing phenoxyacid herbicides (77% on average), whereas peat soil and pine bark were best for removing non-ionic pesticides (72% on average). The attenuation of mecoprop and dichlorprop correlated negatively with the enantiomeric fraction. Therefore, this study shows that the use of waste-to-product materials in biofilter systems is a good solution for removing pollutants from agricultural run-off waters.

Trimeprazine is enantioselectively degraded by an activated sludge in ready biodegradability test conditions

A great number of available pharmaceuticals are chiral compounds. Although they are usually manufactured as racemic mixtures, they can be enantioselectively biodegraded as a result of microbial processes. In this paper, a biodegradability assay in similar conditions to those recommended in OECD tests of enantiomers of trimeprazine (a phenothiazine employed as a racemate) is carried out. Experiments were performed in batch mode using a minimal salts medium inoculated with an activated sludge (collected from a Valencian Waste Water Treatment Plant, WWTP) and supplemented with the racemate. The concentration of the enantiomers of trimeprazine were monitored by means of a chiral HPLC method using a cellulose-based chiral stationary phase and 0.5 M NaClO4/acetonitrile (60:40, v/v) mobile phases. Experiments were performed at three concentration levels of the racemate. In parallel, the optical density at 600 nm (OD600) was measured to control the biomass growth and to connect it with enantioselectivity. The calculated enantiomeric fractions (EF) offer the first evidence of enantioselective biodegradation of trimeprazine. A simplified Monod equation was used as a curve fitting approach for concentration (S), biodegradation (BD), and for the first time, EF experimental data in order to expand the usefulness of the results. Precision studies on S (repeatability conditions) and, for the first time, EF (intermediate precision conditions) were also performed.

Stereoselective accumulations of hexachlorocyclohexanes (HCHs) are correlated with Sphingomonas spp. in agricultural soils across China

The wide usage of hexachlorocyclohexanes (HCHs) as pesticides has caused soil pollution and adverse health effects through direct contact or bioaccumulation in the food chain. This study quantified major HCH isomers in farmland topsoils across China, and evaluated their correlations with microbial community structure, function, and abiotic variables (e.g., moisture, pH, and temperature). Recalcitrant β-HCH was more abundant than α-, γ-, and δ-HCHs, and α-HCH enantiomeric fractions (EF) were larger than 0.5, indicating preferential degradation of (−)-α-HCH. Sphingomonas was not only a predominant population (especially in samples collected in the south), but also a promising biomarker indicating total- and β-HCH residuals, and EF values of α-HCH. Soil moisture and temperature were among the most influential factors that structured the diversity and function of soil microbial communities. The results suggested that increasing soil moisture (in the range of 5–45%) would benefit the growth of HCH-degrading populations and the enrichment of HCH-degradation related pathways. Revealing the site-specific relationships between topsoil physical, chemical, and microbial properties will benefit the in situ bioremediation of farmlands with relatively low HCH residuals across the world.

Enantioselective analysis and degradation of isofenphos-methyl in vegetables by liquid chromatography-tandem mass spectrometry.

The enantioselective degradation of isofenphos-methyl in cowpea, cucumber, and pepper under field conditions was investigated to elucidate the enantioselective environmental behaviors of this pesticide. The concentrations of the enantiomers were determined by liquid chromatography-tandem mass spectrometry (LC-MS/MS). The degradation rates of isofenphos-methyl enantiomers were the fastest in cowpea, followed by cucumber and pepper, with half-lives ranging from 1.48 to 8.06days. The enantioselective degradation of isofenphos-methyl was characterized by calculating and comparing the values of enantiomer fraction (EF) and enantiomeric selectivity (ES). The degradation rates and enantioselectivities of isofenphos-methyl were different for the three vegetables. (R)-(-)-isofenphos-methyl was degraded faster than (S)-(+)-isofenphos-methyl in cowpea and cucumber, whereas (S)-(+)-isofenphos-methyl underwent preferential degradation in pepper. These results could serve as a reference for the study of enantioselective behavior of isofenphos-methyl in plants and further food safety evaluation, where the enantiomeric differences should be considered in the risk assessment.

Occurrence, elimination, enantiomeric distribution and intra-day variations of chiral pharmaceuticals in major wastewater treatment plants in Beijing, China

The occurrence, eliminations, enantiomeric distribution and intra-day variations of five chiral pharmaceuticals (three beta-blockers and two antidepressants) were investigated in eight major WWTPs in Beijing, China. The results revealed that metoprolol (MTP) and venlafaxine (VFX) were of the highest concentrations among the five determined pharmaceuticals with mean concentrations of 803 ng L−1 and 408 ng L−1, respectively in influents, and 354 ng L−1 and 165 ng L−1 in effluents, respectively. Their removal efficiencies, intra-day concentration changes and enantiomeric profiles during wastewater treatment were further analyzed. Loads of these two chiral pharmaceuticals were also studied to reveal drug use pattern. A/A/O+MBR (anaerobic/anoxic/oxic + membrane bio-reactor) followed by joint disinfection treatment process exhibited the high removal efficiencies. No or weak enantioselectivity was observed in most WWTPs. However, obvious enantiomeric fraction (EF) changing of MTP was observed in WWTP3 employing A/A/O+MBR. Intra-day concentration fluctuations of MTP were smaller than VFX. A quick response to sudden rise influent concentration of MTP was observed in WWTP1 effluent but EF response lagged behind. Similar bihourly EF variations in influents and effluents were also observed in most WWTPs for MTP and VFX in consideration of hydraulic residence time (HRT).