Focused microwave-assisted micellar extraction combined with solid-phase microextraction--gas chromatography/mass spectrometry to determine chlorophenols in wood samples

This work describes the utilization of the focused microwave-assisted micellar extraction in combination with the solid-phase microextraction (SPME) to determine chlorophenols in wood samples. The influence of the nature of the surfactant in the extraction process, the optimization of the variables of the focused-microwave system, and the effect of the ageing time of the samples in the extraction efficiency of the method, have been assessed in this study. The overall method using the non-ionic surfactant POLE as extracting medium allows us to determine chlorophenols in wood samples achieving an average extraction efficiency of 104.1%, limits of detection ranging from 2 to 120 ng g⁻¹, and intermediate precision values ranging between 3.5 and 13.2%. The proposed method is also characterized by short analysis times (around 5 min for the microwaves extraction step) and by avoiding the use of organic solvents.     

Determination of major aroma impact compounds in fermented cucumbers by solid-phase microextraction--gas chromatography--mass spectrometry--olfactometry detection

Purge-and-trap, solid-phase extraction, and solid-phase microextraction-gas chromatography-mass spectrometry (SPME-GC-MS) sample preparation techniques for the analysis of odor impact chemicals in fermented cucumber brine are compared. SPME-GC-MS is coupled with detection frequency olfactometry experiments to determine key impact odor compounds in the brine. The most potent odorants that define the typical characteristic brine aroma are trans-4-hexenoic acid and cis-4-hexenoic acid. Confirmation of key impact odorants in brine is confirmed by recombination experiments.     

The use of gas-liquid-solid chromatography in environmental and trace analysis

Summary The separation of industrial trace products such as bischloromethyl ether and phthalide on particular gas-liquid-solid chromatography columns are shown. Separations of environmental interest are also reported. The column characteristics are discussed to obtain the best separation power.     

Pesticide analysis in tomatoes by solid-phase microextraction and micellar electrokinetic chromatography

The analysis of a group of seven pesticides (i.e. six fungicides: pyrimethanil, procymidone, nuarimol, fenarimol, benalaxyl and penconazole and one insecticide: pirimicarb) in tomato samples by micellar electrokinetic chromatography is investigated. For this purpose, reversed electrode polarity stacking mode and solid-phase microextraction (SPME) have been used as on-line and off-line preconcentration procedures, respectively. Tomato samples were first homogenized and extracted with acetone. After suitable evaporation and reconstitution of the extract in water, a SPME procedure using poly(dimethylsiloxane)/divinylbenzene fibers was used. Due to the strong influence of the sample matrix in the extraction, a matrix matched calibration of spiked tomato samples was developed. The method was found to be linear between 0.5 and 2.5 mg/kg. Limits of detection achieved are below the maximum residue limits established by the European Union and Spain legislation as well as by the Codex Alimentarius (except for penconazole). The potential of the method was demonstrated by analyzing 12 tomato samples (of ecological and non-ecological production) taken from regional cultivars. No residues of the selected pesticides were detected in any of the samples.     

The use of thin-layer chromatography in the analysis of lubricating oils

Summary A report is given on the application of thin-layer chromatography to the analysis of additives in lubricating oils. The separation and identification of antioxidants, phenates, sulphonates, zinc dialkyl dithiophosphates and polymeric additives is described. A measurement of additive depletion in used oils is possible by comparison of corresponding chromatograms.

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Zusammenfassung Es wird über die Verwendung der Dünnschicht-Chromatographie bei der Analyse der Additive von Schmierölen berichtet. Die Abtrennung und Identifizierung von Antioxydantien, Phenolaten, Sulfonaten, Zinkdialkyldithiophosphaten und polymeren Additiven wird beschrieben. Eine Messung der Abnahme der Additivkonzentration in gebrauchten Ölen ist durch Vergleich entsprechender Chromatogramme möglich.

     

Automated in-tube solid-phase microextraction-high-performance liquid chromatography for carbamate pesticide analysis

In-tube solid-phase microextraction (SPME) is an automated version of SPME that can be easily coupled to a conventional HPLC autosampler for on-line sample preparation, separation and quantitation. It has been termed "in-tube" SPME because the extraction phase is coated inside a section of fused-silica tubing rather than coated on the surface of a fused-silica rod as in the conventional syringe-like SPME device. The new in-tube SPME technique has been demonstrated as a very efficient extraction method for the analysis of polar and thermally labile analytes. The in-tube SPME-HPLC method used with the FAMOS autosampler from LC Packings was developed for detecting polar carbamate pesticides in clean water samples. The main parameters relating to the extraction and desorption processes of in-tube SPME (selection of coatings, aspirate/dispense steps, selection of the desorption solvents, and the efficiency of desorption solvent, etc.) were investigated. The method was evaluated according to the reproducibility, linear range and limit of detection. This method is simple, effective, reproducible and sensitive. The relative standard deviation for all the carbamates investigated was between 1.7 and 5.3%. The method showed good linearity between 5 and 10000 microg/l with correlation coefficients between 0.9824 and 0.9995. For the carbamates studied, the limits of detection observed are lower than or similar to that of US Environmental Protection Agency or National Pesticide Survey methods. Detection of carbaryl present in clean water samples at 1 microg/l is possible.     

Multi-residue analysis of N-methylcarbamate pesticides and their hydrolytic metabolites in environmental waters by use of solid-phase extraction and micellar electrokinetic chromatography

A method for the simultaneous separation and determination of N-methylcarbamate pesticides and their hydrolytic metabolites by micellar electrokinetic chromatography (MEKC) was developed. A mixture of five pesticides (carbaryl, propuxur, carbofuran, aminocarb, and methiocarb) and their corresponding phenols was studied to optimize the separation of its components in terms of various electrophoretic parameters such as buffer type, pH and concentration, sodium dodecyl sulfate concentration, injection conditions, and applied voltage. Excellent separation of all ten analytes was achieved within about 20 min. The optimized method was used for determinations in environmental water samples. Sample volumes of 250 mL were first preconcentrated in the pesticides and metabolites by passage through a LiChrolut EN sorbent column and then further enriched by on-column stacking. Dynamic ranges of 40 ng/L - 6 microg/L, limits of detection at the nanogram-per-liter level, and relative standard deviations from 2.6 to 7.4% were obtained. The proposed method surpasses high-performance liquid chromatography (HPLC) in separation efficiency. In fact, it provides more expeditious separations and allows more flexible adjustment of the selectivity. Also, it enables the quantification for the analytes studied in this work with decreased limits of detection.     

On-fibre solid-phase microextraction coupled to conventional liquid chromatography versus in-tube solid-phase microextraction coupled to capillary liquid chromatography for the screening analysis of triazines in water samples

This paper compares the advantages and disadvantages of two different configurations for the extraction of triazines from water samples: (1) on-fibre solid-phase microextraction (SPME) coupled to conventional liquid chromatography (LC); and (2) in-tube SPME coupled to capillary LC. In-tube SPME has been effected either with a packed column or with an open capillary column. A critical evaluation of the main parameters affecting the performance of each method has been carried out in order to select the most suitable approach according to the requirements of the analysis. In the on-fibre SPME configuration the fibre coating was polydimethylsiloxane (PDMS)-divinylbenzene (DVB). The limits of detection (LODs) obtained with this approach under the optimized extraction and desorption conditions were between 25 and 125 microg/L. The in-tube SPME approach with a C18 packed column (35 mm x 0.5 mm I.D., 5 microm particle size) connected to a switching micro-valve provided the best sensitivity; under such configuration the LODs were between 0.025 and 0.5 microg/L. The in-tube SPME approach with an open capillary column coated with PDMS (30 cm x 0.25 mm I.D., 0.25 microm of thickness coating) connected to the injection valve provided LODs between 0.1 and 0.5 microg/L. In all configurations UV detection at 230 nm was used. Atrazine, simazine, propazine, ametryn, prometryn and terbutryn were selected as model compounds.     

Development of a novel solid-phase extraction element for thermal desorption gas chromatography analysis

A novel solid-phase extraction element is developed for sorptive enrichment of dilute analytes from liquid samples with high extraction efficiencies due to its larger amounts of polydimethylsiloxane (PDMS) absorbent than the conventional syringe type of solid-phase microextraction (SPME). The extraction element is made of titanium (Ti) open tubular tube (30 mm x 1.2 mm i.d. x 1.6 mm o.d.) coated with a chemically bonded layer of PDMS (500 microm in thickness). The extraction element combined with thermal desorption-gas chromatography-mass spectrometry using a pyrolysis-gas chromatography-mass spectrometry system was used to extract and analyze a typical herbicide, bethrodine in water samples over a concentration range from 2.5 to 2.5 x 10(4) ng/l. Thus obtained calibration curve showed good linearity for the tested whole concentration range with regression coefficient of 0.992. Detection limit of 0.5 ng/l level was achieved and the reproducibility of the measurements for bethrodine at 10 ng/l level was found to be fairly good with relative standard deviation below 7.5%.     

The use of recurrent equations in chromatography

Recurrent equations A(x + k) = aA(x) + b were shown to be applicable to the approximation not only of virtually arbitrary properties of organic compounds (A) in homologous series (A = n _C, k = 1 or 2) but also of the dependences of chromatographic retention parameters on the number of carbon atoms in homologue molecules (A = t _R). The same equations described the temperature dependences of retention times of arbitrary compounds under isothermal separation conditions in gas chromatography (x = T, k = ΔT = const) and the dependences of retention times on the concentration of an organic solvent as an eluent component (x = C, k = ΔC = const) under isocratic separation conditions in high performance liquid chromatography.     

Fast gas chromatography and its use in trace analysis

There is revived interest in the development and implementation of methods of faster GC. The paper summarises the advantages of faster GC analysis, general approaches to faster GC method development and practical aspects of fast gas chromatography with the utilisation of open tubular capillary columns with the stress on trace analysis. There are a number of ways to take the advantage of the improved speed of analysis by faster GC. Numerous options exist for pushing the speed of capillary gas chromatography (CGC) analysis. The scope of this paper is also to give an overview of the present state of faster GC instrumentation which is already available for trace analysis. The practicality of fast CGC is a function of sample preparation and the matrix interferences and how they affect the resultant resolution that may be achieved. Researchers have demonstrated the applicability of fast GC to trace and ultratrace analysis of volatile and semivolatile compounds also with narrow bore columns and difficult sample matrices (such as food, and soil extract). The main development of faster GC methods has been observed in the field of environmental analysis. Practical applications are presented. Both optimised sample preparation and experimental conditions for faster GC are the future perspective of trace analysis.     

The determination, in forensic toxicology, of metallic poisons by paper chromatography

Summary Precipitation of ThFe(CN)₆ from a solution of thorium nitrate with potassium ferrocyanide at varius concentrations has been carried out for the estimation of thorium. The precipitate was filtered and the excess of ferrocyanide was titrated with standard ceric sulphate solution. The amount of potassium ferrocyanide thus used was obtained and the amount of thorium calculated.Having established by the physico-chemical methods that the formula for thorium ferrocyanide is ThFe(CN)₆, under all conditions, it has now become possible to estimate thorium volumetrically by the ferrocyanide method.     

固相微萃取气相色谱法(SPME-GC)测定水体中邻苯二甲酸酯

选用85μm PA纤维,考证了萃取温度、萃取时间、搅拌、离子强度及解析时间等影响因素,最后确立了65℃萃取温度、60min萃取时间、稳定的磁力搅拌、5min解析时间、用带电子捕获检测器的毛细管气相色谱（CGC—ECD）分离测定、外标标准曲线法定量分析水体中邻苯二甲酸酯（PAEs）的方法。该方法具有较好的精密度（RSD≤16％）和较低的检出限（DLDBP=0．003μg/L,DLDEDEHP=0．05μg/L）,水样加标回收率在70％～130％之间。用该法测定了长江水样、太湖水样、自来水及蒸馏水的PAEs含量,DBP在0．1～0．4μg/L,DEHP在0．2～1．2μg/L,DMP、DEP、DOP均未检测到。     

Mechanisms effecting analysis of volatile flavour components by solid-phase microextraction and gas chromatography.

Quantitative properties of solid-phase microextraction (SPME) have been studied in order to investigate a simple and reliable method for analysing volatile flavour components in strawberries. Monitoring the chemical composition profile of berries will be of interest for the producers in order to optimise growth and storage conditions. By the use of SPME and capillary gas chromatography selected standard components were quantified with accuracy within +/-7% and a linear response were found in all concentration ranges studied, covering three orders of magnitude. Equilibrium constants that describe how various components are distributed between the three phases present, sample, headspace and fibre coating were determined. In the system studied, the majority of analytes remained in the sample. This means that repeated analysis can be performed from a single sample without significantly changing the results. The mass transfers of the flavour components, from the sample and into the fibre, were fitted to a transport model assuming that the rate-controlling step is diffusion within the fibre. The experimental results agreed well with the model for most of the components studied. The response for three of the components (geraniol, linalool and trans-2-hexenyl butanoate) did not agree with the model. These components were present in the gas phase in only minute amounts explaining the deviation from the model. Such components will require a long absorption time (longer than 30 min). For quantitative analysis, it is important to use a very precise pre-determined absorption period and well defined sampling conditions. Internal standards can be omitted.     

Trace analysis of vinclozoline by gas chromatography with electrolytic conductivity detection and solid-phase extraction

A procedure for the analysis of vinclozoline in tap and surface water by GC and Hall detector has been developed. Each step — the analysis of vinclozoline in acetone standard solution, in deionized water and in tap water after solid-phase extraction — was checked by statistical tests (variance homogeneity, linearity test, residue analysis, runaway tests, F-test, t-test). The detection limits and determination limits were calculated from the calibration curve and its prediction interval (according to the DFG). The detection limit for vinclozoline in tap water was found to be 0.03 g/l and the determination limit is 0.06 g/l by a recovery rate of 89%.     

High-performance liquid chromatography systems for the analysis of analgesic and non-steroidal anti-inflammatory drugs in forensic toxicology

High-performance liquid chromatography retention data are presented for over 40 analgesic drugs on an ODS-silica packing material to assist in the identification of these compounds. Three isocratic eluents prepared from isopropanol, formic acid and an aqueous phosphate buffer have been used. One eluent has been used for the analysis of paracetamol in whole blood.     

Pesticide analysis in herbal infusions by solid-phase microextraction and gas chromatography with atomic emission detection

A direct immersion solid-phase microextraction (SPME) procedure was used in combination with capillary gas chromatography with atomic emission detection (GC-AED) for the determination of 10 pesticides (organochlorines, organophosphorus compounds and pyrethrins) in herbal and tea infusions. Ionic strength, sample dilution and time and temperature of the absorption and desorption stages were some of the parameters investigated in order to select the optimum conditions for SPME with a 100 μm PDMS fiber-coating. Element-specific detection and quantification was carried out by monitoring the chlorine (479 nm) and bromine (478 nm) emission lines, which provided nearly specific chromatograms. Calibration was carried out by using a spiked sample infusion. The detection limits varied between 11.9 ng ml⁻¹ for deltamethrin and 0.03 ng ml⁻¹ for p,p′-DDE and p,p′-DDD. The recoveries ranged from 73.5% for deltamethrin to 108.3% for p,p′-DDT in a spiked white tea infusion. Two of the eight samples analyzed contained low levels of some the pesticides considered.