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S-421 is a synergist of pyrethroid and organophosphorus pesticides, which are used as termiticides or household insecticides. S-421 is stable and ubiquitous in the environment. Here we describe the concentrations of S-421 in domestic and imported commercial fish collected from 2009 to 2016. Samples were extracted with acetone/hexane and S-421 was purified on a silica gel column. Quantitative analysis was performed by GC-ECD. S-421 was detected in 78 of 116 samples of domestic fish and shellfish at levels of <0.2 to 2.6 ng/g (mean: 0.4 ng/g), and in 69 of 102 imported samples at a level of <0.2 to 1.5 ng/g (mean: 0.4 ng/g). The concentrations of S-421 in fish were lower than those of p,p'-DDE and similar to those of β-HCH.

A novel 7,10-diphenylfluoranthene grafted polysiloxane (DPFP) was synthesized and statically coated on a fused-silica capillary column. High column efficiency (3864 plates per m) was achieved for naphthalene at 120°C. Thermo-gravimetric analysis showed that the DPFP polymer began to decompose at 380°C. The chromatogram of polyethylene pyrolysis products indicated that the maximum allowable temperature of the DPFP column could reach 360°C. By relying on its specific π-π stacking and dipole-induced dipole interactions with aromatic solutes, the DPFP stationary phase achieved excellent resolution for substituted benzene and aromatic hydrocarbons with satisfactory peak shapes, as well as showed superiority to current stationary phases that failed to resolve some critical pairs. Moreover, DPFP also showed good selectivity and resolving ability for Grob test mixtures, fatty acid esters, and ethers., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Gas chromatographic analysis of polybrominated diphenyl ethers (PBDEs) has been evaluated in an attempt to achieve better control of the separation process, especially for highly substituted congeners. Use of a narrow-bore capillary column enabled adequate determination of tetra, penta, hexa, hepta, octa, nona and decaBDE congeners in only one chromatographic run while maintaining resolution power similar to that of conventional columns. A micro electron-capture detector (GC-microECD) was used. Chromatographic conditions were optimized by multifactorial experimental design, with the objective of obtaining not only high sensitivity but also good precision. In this way two different approaches to maximizing response and minimizing variability were tested, and are fully discussed. These optimum chromatographic conditions were then used to determine PBDEs extracted from domestic dust samples by microwave-assisted solvent extraction (MASE). Quantitative recovery (90-108%) was achieved for all the PBDEs and method precision (RSD < 13%) was satisfactory. Accuracy was tested by use of the standard reference material SRM 2585, and sub-ng g(-1) limits of detection were obtained for all compounds except BDE-209 (1.44 ng g(-1)). Finally, several samples of house dust were analysed by use of the proposed method and all the target PBDEs were detected in all the samples. BDE-209 was the predominant congener. Amounts varied from 58 to 1615 ng g(-1) and the average contribution to the total PBDE burden of 52%. The main congeners of the octaBDE mixture (BDE-183, BDE-197, BDE-207 and BDE-196) also made an important contribution (29%) to the total. These are the first data about the presence of these compounds in European house-dust samples. Finally, the sum of the main congeners in the pentaBDE commercial mixture (BDE-47, BDE-99, and BDE-100) contributed 14% to the total. Figure Polybrominated diphenyl ethers in House Dust.

A method based on gas chromatography (GC) separation followed by ion trap tandem mass spectrometry detection in EI mode (ITD-MS/MS), using isotope dilution, was developed for the determination of ten native polybrominated diphenyl ethers (PBDEs) and four (13)C(12)-labeled congeners in biological (fat tissue and human serum) and food samples. The highest-mass fragment ions were used as precursor ions for those congeners with molecular ions with m/z values higher than the maximum of the instrument. In these cases (hepta-BDEs and (13)C(12)-hexa-BDEs) no fragmentation was achieved under the experimental conditions employed. Repeatability (lower than 9%) and reproducibility (lower than 13%), expressed as relative standard deviation (RSD, n = 3 and 4, respectively), were satisfactory. Similarly, the coefficient of variation (n = 4) of the isotopic ratio between the two most abundant product ions was lower than 10 and 6% for native and labeled congeners, respectively. To evaluate the feasibility of the method, the optimized isotope dilution GC/ITD-MS/MS method was used for the quantitation of selected PBDE congeners in different samples including adipose tissue, human serum and foodstuff samples, from three inter-laboratory comparative exercises, covering a wide range of concentrations. A solid-phase extraction procedure, previously developed for PCB determination in small-size bird serum samples, was successfully applied to quantification of PBDEs in 1 mL samples of human serum.

The elution order of 126 polybrominated diphenyl ethers (PBDE) was determined for seven different gas chromatographic (GC) stationary phases. The resulting database facilitates selection of the most suitable GC columns for developing a quantitative, congener-specific BDE analysis and the testing of retention prediction algorithms based on structure relationships of GC phases and congener substitution patterns. In addition, co-elutions of the principal BDE congeners with other BDEs and/or with other brominated flame retardants were investigated and, as an application, the composition of two Bromkal mixtures (70-5DE and 79-8DE) was studied.

A simple procedure for the determination of methyl tert-butyl ether (MTBE), ethyl tert-butyl ether (ETBE), ethyl butyl ether (EBE), tert-amyl methyl ether (TAME), benzene, toluene, ethylbenzene, and xylenes (BTEX) in water using headspace (HS) solid-phase microextraction (HS-SPME) was developed. The analysis was carried out by gas chromatography (GC) equipped with flame ionization detector (FID) and 100% dimethylpolysiloxane fused capillary column. A 2 Plackett-Burman design for screening and a central composite design (CCD) for optimizing the significant variables were applied. Fiber type, extraction temperature, sodium chloride concentration, and headspace volume were the significant variables. A 65 microm poly(dimethylsiloxane)-divinylbenzene (PDMS-DVB) SPME fiber, 10 degrees C, 300 g/l, and 20 ml of headspace (in 40 ml vial) were respectively chosen for the best extraction response. An extraction time of 10 min was enough to extract the ethers and BTEX. The relative standard deviation (R.S.D.) for the procedure varied from 2.6 (benzene) to 8.5% (ethylbenzene). The method detection limits (MDLs) found were from 0.02 (toluene, ethylbenzene, and xylenes) to 1.1 microg/l (MTBE). The optimized method was applied to the analysis of the rivers, marinas and fishing harbors surface waters from Gipuzkoa (North Spain). Three sampling were done in 1 year from June 2002 to June 2003. Toluene was the most detected analyte (in 90% of the samples analyzed), with an average concentration of 0.56 microg/l. MTBE was the only dialkyl ether detected (in 15% of the samples) showing two high levels over 400 microg/l that were related to accidental fuel spill.

A headspace solid-phase microextraction (HS-SPME), in conjunction with gas chromatography-flame ionization detection for use in the determination of six frequently used glycol ethers at the microg/l level is described. A 75 microm Carboxenpolydimethylsiloxane fiber was used to extract the analytes from an aqueous solution. Experimental HS-SPME parameters such as extraction temperature, extraction time, salt concentration and sample volume, were investigated and optimized by orthogonal array experimental designs. The relative standard deviations for the reproducibility of the optimized HS-SPME method varied from 1.48 to 7.59%. The correlation coefficients of the calibration curves exceeded 0.998 in the microg/l range of concentration with at least two orders of magnitude. The method detection limits for glycol ethers in deionized water were in the range of 0.26 to 3.42 microg/l. The optimized method was also applied to the analysis of glycol ethers in urine and blood samples with the method detection limits ranged from 1.74 to 23.2 microg/l.

A system consisting of two columns with different separation mechanisms may be used for forensic chemical gas chromatographic analysis of glycols and their ethers: (1) with a polar immobile phase and (2) with a low-polar polymeric sorbent in gas adsorption or gas-liquid adsorption variants. Effects of other volatile solvents associated with glycols and their ethers, of components of technical liquids, blood substituting liquids, decay products on the results of gas chromatographic analysis of the said substances were revealed. The suggested method has been tried in expert studies.

A reliable method for the simultaneous determination of keto and non-keto bile acids in human serum was developed. Carbonyl substituents of bile acid ethyl esters were converted into methyloxime and hydroxyl substituents into dimethylethylsilyl ethers and the products were analysed directly by capillary gas chromatography with selected ion monitoring using [2H4]chenodeoxycholic and [2H4]3 alpha-hydroxy-7-oxo-5 beta-cholanoic acids as internal standards. The bile acid peaks on the selected ion chromatogram were separated without interference from endogenous substances present in serum. Recoveries of individual keto bile acids added to serum range from 74.4 to 94.7% with a mean of 87.1%. Eight kinds of keto bile acids not previously found in sera of normal subjects, namely 3-oxo-, 3-oxo-7 alpha-hydroxy-, 3-oxo-12 alpha-hydroxy-, 3 alpha-hydroxy-7-oxo, 3 alpha-hydroxy-12-oxo-, 3-oxo-7 alpha,12 alpha-dihydroxy-, 3 alpha,7 alpha-dihydroxy-12-oxo- and 3 alpha,12 alpha-dihydroxy-7-oxo-5 beta-cholanoic acids were identified and quantified. The total concentration of keto bile acids was found to be 0.16 +/- 0.08 nmol/ml and constituted 2.9 +/- 1.5% of that of the usual non-keto bile acids in peripheral venous serum.

The retention behaviour of over seventy terpenoids on three silicone polymer liquid phases under both isothermal and temperature-programmed conditions is reported. Terpenoids with conjugated unsaturation (e.g., carotenoids) were hydrogenated prior to analysis in order to prevent thermal decomposition. Analyses of the acetates and TMS ethers of both the natural hydroxycarotenoids and their perhydroderivatives are also reported. In addition, a system is described for the routine analysis of terpenols, including those whose pyrophosphates are intermediates in sterol and carotenoid biosynthesis.

A new cyanoalkylphenylsiloxane (SILAR 5CP) liquid phase is shown to possess sufficient polarity to permit improved GC separations of natural diacylglycerols based on unsaturation and positional placement of fatty acids as well as on molecular weight, which was previously possible only on ethylene glycol succinate polyesters. Unlike the polyesters, the polar siloxane polymer has moderate thermal stability and provides GC columns which can be used for several months without replacing the packing. The GC analyses were made with conventional columns containing 3% SILAR 5CP on Gas Chrom Q at 270 degrees C isothermally. The diacylglycerols were chromatographed as the TMS ethers. Excellent seperations were obtained for the 1,2(2,3)- and 1,3-diacyglycerols derived from corn, linseed, peanut and cod liver oils and for the 1,2-diacyl-sn-glycerols from hepatic glycerophospholipids.