The effect of follicullar fluid pesticides and polychlorinated biphenyls concentrations on intracytoplasmic sperm injection (ICSI) embryological and clinical outcome.

OBJECTIVES: The present study evaluated the correlation between the concentrations of polychlorinated biphenyls (PCBs) and pesticides in the follicular fluid (FF) obtained during intracytoplasmic sperm injection (ICSI) with the ovarian response, endometrial thickness, and embryological and clinical outcomes. DESIGN: Cross-sectional observational study. MATERIALS AND METHODS: Women aged 20 to 38 years (300 infertile couples) presenting to a university-affiliated fertility center were approached to participate in the study. Only 150 couples that underwent ICSI for male factor infertility agreed to participate, and 94 of them had retrieved enough FF samples suitable for laboratory testing. The FF sample was obtained, centrifuged, and stored in liquid nitrogen. Two organochlorine pesticides (OCPs), Lindane and DDT;three organophosphates (OPs);chlorpyrifos;Diazinon; malathion; one Chloroacetanilide (Pretilachlor);two pyrethroids(Bioallethrin and ß-cyfluthrin); and the concentrations of four PCBs, 28, 52, 138, 180, were estimated in the obtained FF samples by using gas chromatography/mass spectrometry. SPSS statistical analysis program (version 17) was used for analysis. Multiple regression analysis was used to correlate the PCBs and pesticides with ICSI outcomes. RESULTS: There were significant negative correlations between FF concentrations of the eight examined pesticides and the four PCBs on the endometrial thickness. However, Pretilachlor, chlorpyrifos, ß-cyfluthrin, and Diazinon were the only toxic agents that negatively correlated with the number of the oocytes retrieved. Fertilization and early embryo cleavage rates were negatively correlated with Pretilachlor and ß-cyfluthrin. Moreover, high concentrations of Lindane,DDT, Diazinon,and chlorpyrifos were significantly associated lower implantation rate. PCB 28 and 180 concentration in the FF was associated with a lower number of retrieved oocytes and fertilization rate, respectively. The number of implanted embryos was negatively correlated with PCB 52 FF concentration. However, the clinical pregnancy rate did not reach the level of significance. CONCLUSION: Higher concentrations of any studied PCBs and pesticides are associated with thinner endometrial thickness. The higher the level of Pretilachlor, ß-cyfluthrin, PCB 28 and 180, the lower the retrieval, fertilization, and embryo cleavage rates. High PCB and pesticide concentrations in the FF adversely affected embryological ICSI outcomes. However, more data are needed to evaluate their effect on the clinical outcome.

A capillary micellar electrokinetic chromatography method for the stereoselective quantitation of bioallethrin in biotic and abiotic samples.

A capillary micellar electrokinetic chromatography (MEKC) method was developed enabling the stereoselective separation of the insecticide bioallethrin. The use of sodium deoxycholate bile salt and acetyl-ß-cyclodextrin (acetyl-ß-CD) made possible the separation of bioallethrin stereoisomers with a high enantioresolution (7.4) in a short analysis time (6.5min). The analytical characteristics of the developed method were evaluated in terms of linearity, accuracy, precision, and limits of detection (LOD) and quantitation (LOQ) showing a good performance for the quantitation of bioallethrin stereoisomers with LODs of 0.2 and 0.3mg/L. The developed method was applied to the stereoselective analysis of a commercial bioallethrin pediculicide formulation and to evaluate the toxicity of bioallethrin stereoisomers on the growth of the unicellular freshwater green alga Pseudokirchneriella subcapitata and on the germination of the higher plant Sorghum bicolor (non-target organisms). The analysis of the commercial pediculicide showed a good agreement between the contents determined for the two stereoisomers and those labelled in the commercial samples. Different toxic responses and biodegradation profiles were found for each stereoisomer in ecotoxicity assays. The mixture of S/R stereoisomers of bioallethrin resulted more toxic than S-bioallethrin for green algae, with EC50 values of 1.10±0.06 for the mixture and of 1.73±0.05mg/L for the pure S-biallethrin (esbiol). Germination of plants seeds was also affected.

Analysis of Pesticides and Toxic Heavy Metals Contained in Mosquito Coils.

In this study, 10 mosquito coils manufactured in China were obtained in Suriname, South America, where they are used extensively. The coils were analyzed for organics (allethrin, permethrin, and butylated hydroxytoluene) and heavy metals (Cr, Co, As, Cd, and Pb) by GC-MS and ICP-MS, respectively. Allethrin was the only target organic compound detected in all mosquito coils with concentrations ranging from ~1900 to ~4500 µg/g. The concentrations of heavy metals varied as follows (in µg/g): Cr: 2.9-9.4, Co: 0.1-1.2, Cu: 0.7-16.1, Se: 0.10-0.4, Ni: 2.1-5.8, As: 0.10-2.2, Cd: 0.10-0.2, and Pb: 1.1-3.6.

Sampling free and particle-bound chemicals using solid-phase microextraction and needle trap device simultaneously.

The possibility of sampling the free and particle-bound concentrations of organic compounds was studied using two different sampling techniques at the same time: needle trap device (NTD) and solid-phase microextraction (SPME). In this study, a mosquito coil was used to produce gaseous (free) and particle-bound compounds. Allethrin, the active ingredient in mosquito coils, was chosen as the target analyte. Under the same sampling conditions, the amount of allethrin extracted from the mosquito-coil smoke was higher for the NTD compared to the SPME fiber, while the extracted amounts were almost the same for both devices when sampling gaseous samples of allethrin. These results can be explained by the fact that the SPME fiber can only extract free molecules (based on diffusion), whereas the NTD, an exhaustive sampling device, collects both free and particle-bound allethrin. Breakthrough for NTD and carryover for both NTD and SPME were negligible under the given sampling and desorption conditions.

Profiling the spatial concentration of allethrin and piperonyl butoxide using passive sorptive sampling and thermal desorption capillary GC-MS.

Spatial concentration distribution of a chemical in an indoor environment is an important factor in the evaluation of chemical nuisances. However, straightforward techniques for the determination of this distribution are not very common and usually limited in their application. Sorptive sampling using polydimethylsiloxane-coated stir bars and the combination of active and diffusive sampling were shown to allow uncomplicated spatial concentration profiling of multiple compounds in an indoor environment. The validity of the approach was demonstrated in the analysis of the spatial concentration distribution of a pyrethroid insecticide in a common bedroom. The relative concentrations of allethrin and piperonyl butoxide were profiled throughout the room upon the application of an insecticide vaporizer.

Maternal hair--an appropriate matrix for detecting maternal exposure to pesticides during pregnancy.

The detection of exposure of pregnant women to toxicants in the environment is important because these compounds can be harmful to the health of the woman and her fetus. The aim of this study was to analyze for pesticides/herbicides in paired maternal hair and blood samples to determine the most appropriate matrix for detecting maternal exposure to these compounds. A total of 449 pregnant women were prospectively recruited at midgestation from an agricultural site in the Philippines where a preliminary survey indicated significant use at home and on the farm of the following compounds: propoxur, cyfluthrin, chlorpyrifos, cypermethrin, pretilachlor, bioallethrin, malathion, diazinon, and transfluthrin. Paired maternal hair and blood samples were obtained from each subject upon recruitment into the study (midgestation) and at birth and were analyzed for the above compounds, as well as lindane and DDT [1,1,1-trichloro-2-2-bis(p-chlorophenyl) ethane], and some of their known metabolites by gas chromatography/mass spectrometry. The highest exposure rate was seen for propoxur and bioallethrin and maternal hair analysis provided the highest detection rate for these two compounds, compared to blood, at both time periods: (1) At midgestation, 10.5% positive for propoxur in hair compared to 0.7% in blood (P<0.001) and for bioallethrin, 11.9% positive in hair compared to 0% in blood (P < or = 0.001), and (2) at birth, 11.8% positive for propoxur in hair compared to 4% in blood (P < or = 0.001) and for bioallethrin, 7.8% in hair compared to 0% in blood (P < or = 0.001). A small number of maternal hair samples were also positive for malathion, chlorpyrifos, pretilachlor, and DDT. Only a few of the pesticide metabolites were detected, principally 3-phenoxybenzoic acid, malathion monocarboxylic acid, and DDE [1,1,dichloro-2-2-bis(p-chlorophenyl)ethylene], and they were mostly found in maternal blood. There was a significant association between the use of the home spray pesticide, Baygon, and propoxur in maternal hair at birth (P=0.001) and between the use of a slow-burning mosquito coil and the presence of bioallethrin in maternal hair at midgestation and at birth (P=0.001, P < or = 0.041, respectively). There is significant exposure of the pregnant woman to pesticides, particularly to pesticides that are used at home. Our study demonstrates the advantages of analyzing maternal hair as a readily available biologic matrix for studying maternal exposure to toxicants in the environment, compared to blood. For propoxur, there was a 3- to 15-fold higher detection rate of the pesticide in maternal hair as compared to blood. As for the other pesticides, bioallethrin, malathion, chlorpyrifos, and DDT were exclusively found in maternal hair compared to blood. On the other hand, pesticide metabolites were infrequently found in maternal hair or maternal blood. Pesticides in blood most likely represent acute exposure, whereas pesticides in hair represent past and/or concurrent exposure. The high sensitivity, wide window of exposure, availability, and ease of hair collection are distinct advantages in using hair to detect exposure to pesticides among pregnant women. However, pesticides in maternal hair may also be secondary to passive exposure and therefore not truly representative of the internal pesticide dose. Finally, the analysis of maternal hair for pesticides as an index of maternal exposure to pesticides in the environment allows the institution of measures to prevent further exposure during pregnancy.

Stereoselective determination of allethrin by two-dimensional achiral/chiral liquid chromatography with ultraviolet/circular dichroism detection.

A two-dimensional achiral/chiral HPLC method with circular dichroism (CD) detection was optimized for the stereochemical resolution and determination of the elution order of the eight stereoisomers of synthetic allethrin. A monolithic silica HPLC column (Chromolith, Merck, 100 mm x 4.6 mm i.d.) was put orthogonally to an enantioselective OJ Daicel column (250 mm x 4.6 mm i.d.) by means of a switching valve. The resolution of cis and trans diastereoisomers on the silica column was obtained by using a mobile phase consisting of n-hexane:tert-butyl methyl ether (96:4) (v/v) at a flow rate of 1 ml min(-1). The cis and trans peaks were then switched to the enantioselective OJ column separately in two subsequent injections. The resolution of the four trans stereoisomers was accomplished by using n-hexane:tert-butyl methyl ether (90:10) (v/v), while the mobile phase composition for the four cis stereoisomers consisted of n-hexane:isopropanol (99.3:0.7) (v/v). The CD based detection system allowed the determination of the elution order on the basis of the CD signals of the single stereoisomers, together with the injection of pure stereoisomers. Under the final conditions, the validated method was applied to the determination of stereoisomeric composition and absolute configuration of the prevailing stereoisomers of real samples, i.e. commercial batches of different sources of d-allethrin.

Impact of long-term exposure to mosquito coils: residual deposition and dissipation of D-trans-allethrin in a room.

A D-trans-allethrin-based mosquito repellent coil formulation was used continuously in a room for 30 d. Two different experiments were conducted and the deposition of residues on different surfaces of the room was determined. Studies were conducted continuously for a period of 30 d in a fully closed room and in another room kept open for 14 h per day. The residues deposited on different surfaces, ceiling, side walls and floor, were measured. The results showed the accumulation of high concentrations of allethrin on all the surfaces of the room when the room was in a fully closed condition. Samples collected from the ceiling showed residues of D-trans-allethrin of 6.34-148.63 microg m(-2) during the 30 d study, the side walls 4.68-170.72 microg m(-2) and the floor 20.00-184.52 microg m(-2) Maximum residues were observed in 30 d samples collected from the ceiling and floor. The residual concentrations were nearly 10 times higher in samples collected from the closed room. Discontinuation of the use of the mosquito repellent after 30 d led to a gradual decrease in the concentrations of residues on all the surfaces. The influence of environmental parameters on the dissipation of residues was also studied.

Aliphatic aldehydes and allethrin in mosquito-coil smoke.

Presence of aliphatic aldehydes and allethrin in the smoke produced by two brands of mosquito-coil was determined by high performance liquid chromatography. It was observed that burning mosquito-coil produces a greater amount of formaldehyde, acetaldehyde and acrolein in the gaseous phase, whereas lesser amount of particulate-bounded aldehydes. Aldehydes bounded in particulates were, however, enriched in terms of concentration. Allethrin was found to occur only in particulates of 0.1-1.0 micron size. The results reveal that allethrin may not be capable of attacking the mosquitoes effectively.

[Rapid determination of allethrin, permethrin and piperonyl butoxide in insecticidal aerosol for household by gas chromatography].

A method of quantitative analysis for allethrin, permethrin and piperonyl butoxide in insecticidal aerosol for household has been studied by GC-FID. The gas chromatographic conditions were as follows. column:packed with 5% QF-1 on Chromosorb W HP, column temperature: 215 degrees C, temperature of injector and detector 250 degrees C and carrier gas: N2 15 mL/min. Diphenyl phthalate was used as the internal standard. All components and internal standard were separated in 7 min. For allethrin, permethrin and piperonyl butoxide, the recovery were 100%, 102% and 99.9%, and the coefficients of variation were 0.13, 0.56 and 0.48 respectively. The method is simple, rapid and accurate.

Toxic effects of mosquito coil (a mosquito repellent) smoke on rats. I. Properties of the mosquito coil and its smoke.

The physical and chemical properties of the mosquito coil, a commonly used mosquito repellent in Asia and South America, were analysed. The smoke emitted from the burning mosquito coil consists of submicron particles (diameter less than 1 micron) coated with a considerable amount of heavy metals, allethrin and a wide range of organic vapors, such as phenol and o-cresol. Therefore, a lengthy exposure to this smoke will cause adverse effects on the consumers.