Optimization Of Solid-phase Microextraction Research Articles

Performance Evaluation of Extraction Coatings with Different Sorbent Particles and Binder Composition.

Binders are critical components used in the preparation of a range of extraction devices, including solid-phase microextraction (SPME) devices. While the main role of a binder is to affix the sorbent particles to the selected support, it is critical to select the optimal binder to ensure that it does not negatively impact the coating's particle sorption capability. This work presents the first comprehensive investigation of the interactions between binders and solid sorbent particles as these interactions can significantly impact the performance of the coating. Specifically, the findings presented herein provide a better understanding of the extraction mechanisms of composite coatings and new rules for predicting the particle adhesion forces and binder distribution in the coating. The influence of binder chemistry on coating performance is investigated by examining a selection of the most used binders, namely, polydimethylsiloxane (PDMS), polyacrylonitrile (PAN), poly(vinylidene difluoride) (PVDF), polytetrafluoroethylene amorphous fluoroplastics (PTFE AF 2400), and polybenzimidazole (PBI). The solid particles (e.g., hydrophilic-lipophilic balanced (HLB) and C18) used in this work were selected for their ability to provide optimal extraction coverage for a broad range of analytes. The results show that PDMS does not change the properties of the solid particles and that the binder occupies a negligible volume due to shrinking after polymerization, resulting in the solid particles making up most of the coating volume. Hence, the coating sorption characteristics correspond closely to the properties of the selected solid particles. On the other hand, the results also showed that PTFE AF 2400 can interact with the active surface of the sorbent, leading to the deactivation of the sorbent particles. Therefore, the extraction performance and permeability coefficients decrease as the size of the penetrant increases, indicating a rigid porous structure. The results of this study can aid in the optimization of SPME devices as they provide reference values that can be used to determine the optimal binder and the sorbent affinity for the targeted compounds. Finally, the present work also provides the broader scientific community with a strategy for investigating the properties of sorbent particle/binder structures and defines the characteristics of a good coating/membrane by analyzing all parameters such as kinetics, thermodynamic equilibria, and morphology.

Optimization of SPME\u2013GC\u2013MS and characterization of floral scents from Aquilegia japonica and A. amurensis flowers

BackgroundThe floral scents of plants play a key role in plant reproduction through the communication between plants and pollinators. Aquilegia as a model species for studying evolution, however, there have been few studies on the floral scents and relationships between floral scents and pollination for Aquilegia taxa.MethodsIn this study, three types of solid-phase micro-extraction (SPME) fiber coatings (DVB/PDMS, CAR/PDMS, DVB/CAR/PDMS) were evaluated for their performance in extracting volatile organic compounds (VOCs) from flowers of Aquilegia amurensis, which can contribute to the future studies of elucidating the role of floral scents in the pollination process.ResultsIn total, 55 VOCs were identified, and among them, 50, 47 and 45 VOCs were extracted by the DVB/CAR/PDMS fiber, CAR/PDMS fiber and DVB/PDMS fibers, respectively. Only 30 VOCs were detected in A. japonica taxa. Furthermore, the relative contents of 8 VOCs were significant different (VIP > 1 and p < 0.05) between the A. amurensis and A. japonica.ConclusionsThe results can be applied in new studies of the relationships between the chemical composition of floral scents and the processes of attraction of pollinator. It may provide new ideas for rapid evolution and frequent interspecific hybridization of Aquilegia.

Optimization of Solid Phase Microextraction (SPME) Coupled with Gas Chromatography Mass Spectrometry (GC-MS) for Fermented Perilla Leaves Jiaosu and Volatile Profiling Analysis During Fermentation

A method based on solid phase microextraction coupled with gas chromatography mass spectrometry was developed for volatile profiling fermented perilla leaves jiaosu (PFJ) during fermentation. Five fibers were firstly evaluated by the total peak areas and the number of volatile compounds. Secondly, a Plackett-Burman design was applied to screen for seven independent variables selected in literature. Three significant variables (extraction time, extraction temperature and equilibrium time) were therefore selected for the following optimization studies. A Box-Behnken design combined with a steepest ascent was then used to optimize the significant factors. Under optimal conditions, the changes of volatile profiles of PFJ at 7, 14, 21, 28, 91 and 140 d were analyzed. A total of fifty-one volatile compounds were identified, and alcohols (68.12–78.94%) were the main volatile components in PFJ, followed by methoxy-phenolic compounds (4.67–5.48%). Perilla alcohol and trans-Shisool were the major constituents during spontaneous fermentation, which accounted for 16.14–30.66% and 19.95–24.52%, respectively. The results showed that PFJ fermented into a health probiotic product with characteristic flavour and functional volatile compounds.

Multi-target optimization of solid phase microextraction to analyse key flavour compounds in wort and beer

Despite the literature comprises numerous studies dealing with the analysis of wort and beer flavour-related compounds by HS-SPME followed by GC–MS quantification, no generalized consensus exists regarding the optimal conditions for the extraction procedure. The complex chemistry nature of these matrices, the number of analytes, as well as the number and interactions among parameters affecting the extraction performance, requires the adoption of optimal experimental design protocols. This aspect is often overlooked and often not properly addressed in practice. Therefore, in the present work, the optimal conditions under which a range of wort and beer analytes can be extracted and quantified were analysed. The optimal extraction conditions were presented at two levels of aggregation: global (untargeted) and key-flavour analysis. Experimental data was generated by Definitive-Screening-Design, followed by model development and optimization. Both approaches were compared and critically analysed. For vicinal-diketones group, a complete validation study for the optimal conditions is presented.

Rapid and simultaneous analysis of tetrabromobisphenol A and hexabromocyclododecane in water by direct immersion solid phase microextraction: Uniform design to explore factors

Direct immersion solid phase microextraction (DI-SPME) coupled to liquid chromatography-tandem mass spectrometry (LC-MS/MS) is of significant research interest because of its low solvent consumption, simple design, and efficient, sensitive, fast performance. In this work, a combination of these two methods (DI-SPME-LC-MS) for the determination of tetrabromobisphenol A (TBBPA) and hexabromocyclododecane (HBCD) in water was developed. Important factors, which included temperature, stirring rate, salt concentration, pH value and adsorption time, were evaluated in for the optimization of solid phase microextraction (SPME) method. The method was developed using spiked natural waters in a concentration range of 0.1–10 ng mL−1, and showed notable linearity with regression coefficients ranging between 0.992 and 0.999. The limits of detection varied from 0.01 to 0.04 ng mL−1 (at S/N = 3) and relative standard deviation (RSD < 11%) were obtained showing that the precision of the method was reliable. Recoveries were in relatively high levels for both analytes and ranged from 88% to 108%. Moreover, in comparison with the performance time of traditional sample pretreatment methods such as solid-phase extraction (SPE), accelerated solvent extraction (ASE), and liquid-liquid extraction (LLE), DI-SPME-LC-MS takes only approximately 35 min to perform. The optimized method was successfully applied for monitoring concentrations of TBBPA and HBCD in water.

Implementing a central composite design for the optimization of solid phase microextraction to establish the urinary volatomic expression: a first approach for breast cancer.

Breast cancer (BC) is positioned as the second among all cancers remaining at the top of women´s diseases worldwide followed by colorectum, lung, cervix, and thyroid cancers. The main drawback of most the screening/diagnostic methods is their low sensitivity/specificity and in some cases the invasive procedure required to obtain the samples. On the present investigation, we report a statistical design was to evaluate by central composite design the influence towards the optimization of the most significant variables of solid-phase microextraction (SPME) procedure for the isolation of volatile organic metabolites (VOMs) from urine of BC patients (N = 31) and healthy individuals (CTL; N = 40). The establishment of the urinary volatomic composition, through gas chromatography-mass spectrometry (GC-MS) analysis, can boost the identification of volatile organic metabolites (VOMs) potential BC biomarkers useful to be used together or to complement the current BC diagnostics tools. Better early detection methods are needed to improve the outcomes of patients with BC. Several combinations of experiments were considered with a central composite design (CCD) of response surface methodology (RSM) for the urinary volatomic pattern. Three-level three-factor CCD was employed assessing the most important extraction-influencing variables-fiber coating, NaCl amount, extraction time and temperature. The optimal conditions were achieved using a carboxen/polydimethylsiloxane fiber with 15% (w/v) NaCl during 75min at 50°C. A total of ten VOMs belonging to sulfur compounds, terpenoids and carbonyl compounds presented the highest contribution towards discrimination of BC patients from CTL (variable importance in projection (VIP) > 1, p < 0.05). The discrimination efficiency and accuracy of urinary metabolites was ascertained by receiver operating characteristic (ROC) curve analysis that allowed the identification of some metabolites with highest sensitivity and specificity to discriminate the groups. The results obtained with this approach suggest the possibility to identify endogenous metabolites as a platform to discovery potential BC biomarkers and paves a way to explore the related metabolomic pathways in order to improve BC diagnostic tools.

Definitive Screening Designs and latent variable modelling for the optimization of solid phase microextraction (SPME): Case study - Quantification of volatile fatty acids in wines

In the present study, we apply the recently proposed Definitive Screening Designs (DSD) to optimize HS-SPME extraction in order to analyze volatile fatty acids (VFA) present in wine samples. This is the first attempt to apply this new class of designs to one of the most well-known and widely applied extraction techniques. The latent structure of the responses is also explored for defining the optimal extraction conditions. DSD is a new screening design with the potential to significantly reduce the number of experiments required to estimate the model parameters and to establish the optimum operation conditions. Therefore, there is an obvious interest in assessing the benefits of DSD in practice. In this work, this design framework is applied to the simultaneous optimization of seven extraction parameters (responses). Both qualitative and quantitative extraction parameters are considered, in order to test the flexibility of DSD designs: a two-level qualitative variable, the fiber coating, and six quantitative variables, namely the pre-incubation time, the extraction time and temperature, the headspace/sample volume, the effect of agitation during extraction and the influence of the ethanol content (sample dilution). Optimization of analytes' chromatographic responses was carried out both individually (response by response) and altogether, by modelling the responses in the latent variable space (i.e., explicitly considering their underlying correlation structure). In the end, a consensus analysis of all perspectives was considered in the definition of the overall optimal extraction conditions for the quantification of VFA in fortified wines. The solution found was to use a DVB/Car/PDMS fiber, 10 mL of samples in 20 mL vial, 40 min of extraction at 40 °C. The analysis also revealed that the factors incubation time, agitation and sample dilution do not play a significant role in explaining the variability of extraction parameters. Therefore, they were set to the most convenient levels. The methodology followed was thoroughly validated and the following figures of merit were obtained: good linearity (R2 > 0.999, for all compounds), high sensitivity (LOD and LOQ are close or below the values found in literature), recoveries of approximately 100% and suitable precision (repeatability and reproducibility lower than 7.21% and 8.61%, respectively). Finally, the optimized methodology was tested in practice. Several wine samples were analyzed and the odor activity value calculated to facilitate the identification of their importance as odor active compounds in different aged fortified wines. This work demonstrates the benefits of using DSD and latent variable modelling for the optimization of analytical techniques, contributing to the implementation of rigorous, systematic and more efficient optimization protocols.

Optimization of solid-phase microextraction using Taguchi design to quantify trace level polycyclic aromatic hydrocarbons in water

This article introduces a simple, rapid, and reliable solid-phase microextraction (SPME) method coupled with GC-MS for the quantitative determination of 16 polycyclic aromatic hydrocarbons in water. In this study, the Taguchi experimental design was used to optimize extraction conditions of polycyclic aromatic hydrocarbons using SPME method to obtain highly enriched analytes. Consequently, quantitative determination of polycyclic aromatic hydrocarbons in water was achieved by GC-MS technique. The selected parameters affecting enrichment of polycyclic aromatic hydrocarbons were sample extraction time, stirring speed, temperature, ionic strength, and pH. The study revealed that optimal operating conditions were found to be 90-min extraction time, 1400 rpm stirring speed, and 60°C sample temperature. The effect of ionic strength and pH were shown to be insignificant. Optimized conditions were also reevaluated by placing the 16 polycyclic aromatic hydrocarbons into several subgroups based on their molecular weight. The extraction efficiency of polycyclic aromatic hydrocarbons with low molecular weight was shown to be a function of only the extracting temperature. Satisfactory results were obtained for linearity (0.983-0.999), detection limits (2.67-18.02 ng/L), accuracy (71.2-99.3%), and precision (4.3-13.5%). The optimum conditions reported by other design approaches were evaluated and generalized optimum conditions were suggested.

Optimization of solid phase microextraction for non-lethal in vivo determination of selected pharmaceuticals in fish muscle using liquid chromatography–mass spectrometry

A new thin film microextraction (TFME) configuration based on C18 thin film was optimized to improve solid phase microextraction (SPME) sensitivity and extraction kinetics for in vivo determinations of trace pharmaceuticals in fish tissue. Optimization of SPME involved increasing sampler surface area and volume of extraction phase to improve performance within in vitro applications such as agarose gel matrix and spiked fish tissue, as well as in vivo determinations of pharmaceuticals in fish exposed to municipal wastewater. Rainbow trout (Oncorhynchus mykiss) were exposed for 4d to effluents from a municipal wastewater plant that was treated under three different configurations of a pilot plant. Fathead minnow (Pimephales promelas) were caged for 14d upstream and downstream of municipal wastewater effluent discharges along Grand River at near Kitchener, ON. TFME and regular C18 fibers were inserted into the dorsal-epaxial muscle of rainbow trout and fathead minnow, respectively, for 30min sampling intervals. Sample extracts obtained from fibers were desorbed in methanol:water (3:2) for 90min under 1500rpm agitation and analyzed using liquid chromatography coupled with tandem mass spectrometry (LC/MS–MS) to determine pharmaceutical bioconcentration. Most target pharmaceuticals were detected in the wastewater with the exception of norfluoxetine and paroxetine. C18 TFME phase successfully quantified fluoxetine, venlafaxine, sertraline, paroxetine, and carbamazapine in muscle of living fish at concentrations ranging from 1.7 to 259ng/g. Reproducibility of the method in spiked fish muscle was 9–18% RSD with limits of detection and quantification ranging from 0.08 to 0.21ng/g and 0.09 to 0.64ng/g (respectively) for the analytes examined. Ibuprofen and gemfibrozil were not detected in fish tissues, likely due to rapid excretion leading to low rates of bioconcentration. This study demonstrates improved in vivo SPME sensitivity (recovery) and extraction rates during pre-equilibrium sampling of target pharmaceuticals in fish tissue due to the improved C18 extraction phase geometry.

Solid phase microextraction coupled with comprehensive two-dimensional gas chromatography–time-of-flight mass spectrometry for high-resolution metabolite profiling in apples: Implementation of structured separations for optimization of sample preparation procedure in complex samples

Metabolomics currently represents one of the fastest growing high-throughput molecular analysis platforms that refer to the simultaneous and unbiased analysis of metabolite pools constituting a particular biological system under investigation. In response to the ever increasing interest in development of reliable methods competent with obtaining a complete and accurate metabolomic snapshot for subsequent identification, quantification and profiling studies, the purpose of the current investigation is to test the feasibility of solid phase microextraction for advanced fingerprinting of volatile and semivolatile metabolites in complex samples. In particular, the current study is focussed on the development and optimization of solid phase microextraction (SPME) – comprehensive two-dimensional gas chromatography–time-of-flight mass spectrometry (GC×GC–ToFMS) methodology for metabolite profiling of apples (Malus ×domestica Borkh.). For the first time, GC×GC attributes in terms of molecular structure–retention relationships and utilization of two-dimensional separation space on orthogonal GC×GC setup were exploited in the field of SPME method optimization for complex sample analysis. Analytical performance data were assessed in terms of method precision when commercial coatings are employed in spiked metabolite aqueous sample analysis. The optimized method consisted of the implementation of direct immersion SPME (DI-SPME) extraction mode and its application to metabolite profiling of apples, and resulted in a tentative identification of 399 metabolites and the composition of a metabolite database far more comprehensive than those obtainable with classical one-dimensional GC approaches. Considering that specific metabolome constituents were for the first time reported in the current study, a valuable approach for future advanced fingerprinting studies in the field of fruit biology is proposed. The current study also intensifies the understanding of SPME–GC×GC–ToFMS hyphenation and outlines the benefits of facilitating GC×GC for SPME method optimization. The obtained results clearly illustrate that acquisition of a more complete metabolome snapshot is only attainable under optimized conditions for both techniques.

Optimization of solid-phase microextraction (SPME) to determine airborne biogenic volatile organic compounds (BVOCs): An application for measurement of household cleaning products

Biogenic volatile organic compounds (BVOCs) in household cleaning products play key roles in indoor air quality (IAQ) because they are precursors for secondary pollutants formation. An accurate and rapid analytical technique for their measurement is of importance. This paper describes an optimization of a method for solid-phase microextraction (SPME) coupled with gas chromatography/mass spectrometry (GC-MS) for the determination of BVOCs. SPME fibers coated with Carboxen-PDMS are used to collect 12 individual BVOCs under standard conditions with a short exposure time of 5 min. Parameters influencing the extraction processes including sampling time, temperature and relative humidity are also investigated. All of the targeted BVOCs are shown to have limits of detection (LODs) in mixing ratios ranging from 0.31–0.50 ppbv, which are two magnitudes better than the LODs reported. The method precisions are between 1.1% and 6.7%. Comparison studies were carried out on a set of four floor cleaner extracts using the SPME method and traditional liquid injection method. Good agreement of the targeted BVOCs by the two methods was demonstrated. Our results indicated that SPME can serve as a simple and rapid sample collection approach to quantify BVOCs accurately and precisely in the indoor environment.

Optimization of SPME with GCMS Analysis of Volatile Organic Chemical Residues in Textiles

A fast testing procedure for the determination of VOCs in textile matrix using solid phase microextraction (SPME) and gas chromatography-mass spectrometry (GC-MS) was introduced. Samples were cut into small pieces and soaked in 5% methanol (v/v) saturated NaCl solution with supersonic pretreatment at 40±1°Cwater-bathing for 15 min and headspace exposure for 10 min at 50°C with stirring rate at 1100rmp. The influence of SPME adsorption time, stir speed, adsorption time and temperature, and gas chromatography (GC) inlet conditions for the SPME were investigated. Then the matrix solutions were extracted by headspace SPME and analysis by GC/MS. Under the optimized conditions, the limits of detection for target compounds were 0.005mg/kg with average recovery between 90.6-108.7%. The results obtained clearly showed the potential of SPME for efficient concentration of the target compounds and also demonstrated the reliability of this extraction technique for the monitoring of textile quality for the eco-marks.

The comparison of solid phase microextraction‐GC and static headspace‐GC for determination of solvent residues in vegetable oils

The objective of these investigations has been the determination of volatile organic compounds including residue solvents present in vegetable oil samples. Some olive oil, rape oil, sunflower oil, soy-bean oil, pumpkin oil, grape oil, rice oil as well as hazel-nut oil samples were analysed. Among residue solvents the following compounds have been mentioned: acetone, n-hexane, benzene, and toluene. Some experiments for the solid phase microextraction (SPME)-GC-flame ionisation detection (FID) were performed to examine extraction conditions such as fiber exposure time, temperature of extraction, and temperature of desorption. Various SPME fibers such as polydimethylsiloxane, Carboxen/polydimethylsiloxane and polydimethylsiloxane/divinylbenzene coatings were used for the isolation of tested compounds from vegetable oil samples. After optimisation of SPME, real vegetable oil samples were examined using SPME-GC/MS. Based on preliminary experiments the qualitative and quantitative analyses for the determination of acetone, n-hexane, benzene and toluene were performed by SPME-GC-FID and static head-space (SHS)-GC-FID methods. The regression coefficients for calibration curves for the examined compounds were R(2) > or = 0.992. This shows that the used method is linear in the examined concentration range (0.005-0.119 mg/kg for SPME-GC-FID and 0.003-0.728 mg/kg for SHS-GC-FID). Chemical properties of analysed vegetable oils have been characterised by chemometric procedure (cluster analysis).

Factorial experimental design optimization of solid phase microextraction (SPME) conditions for analysis of butylated hydroxytoluene (BHT) in bottled water

BHT is an antioxidant utilized as additive in some foods and in packaging plastics, and its presence in bottled mineral water is possible due to its migration from bottle walls to the contents. A factorial experimental design was utilized to obtain the optimum values for the main operational parameters in the analysis of butylated hydroxytoluene (BHT) in bottled water using headspace and direct solid-phase microextraction (SPME) in the pre-concentration step. The parameters optimized were sample pH, temperature and ionic strength. The separation, detection and quantitation of the extracts were performed by gas chromatography coupled to mass spectrometry. Preliminary experiments were made to select the best fiber for the extraction procedure. Polydimethylsiloxane (PDMS) fibers were selected, and the optimized methodology was successfully applied to the extraction and quantitation of BHT in real samples of mineral and mineralized bottled water.

Optimization of Solid-Phase Microextraction for the Gas Chromatography/Mass Spectrometry Analysis of Persistent Organic Pollutants

In this work, solid-phase microextraction (SPME) has been applied as an alternative for the selective extraction of 3 polybrominated diphenyl ethers (PBDEs), 2,2',4,4'-tetrabromodiphenyl ether (PBDE-47); 2,2',4,4',5-pentabromodiphenyl ether (PBDE-99); and 2,2',4,4',6-pentabromodiphenyl ether (PBDE-100), and 2 alkylphenols, 4-tert-OP and 4-NP, prior to their analysis by gas chromatography/mass spectrometry (GC/MS). The advantages of this technique are mainly its simplicity, cost-effectiveness, and time-saving sample preparation, as well as being a solvent-free technique. With the aim of optimizing the conditions for an efficient extraction of the studied compounds, different fiber coatings and the main parameters affecting the extraction procedure have been evaluated. The results obtained showed a good linearity in the range of concentrations investigated, and adequate relative standard deviation values were found according to the range accepted for SPME. Recovery values were in the range of 78-108%, and good detection and quantitation limits at ppt levels were obtained for both methods, allowing the determination of the selected compounds in samples at trace levels. The results obtained clearly show the potential of SPME for efficient concentration of the target compounds and also demonstrate the reliability of this extraction technique for their GC/MS analysis.

Determination of the disproportionation products of limonene used for the catalytic hydrogenation of castor oil

The direct determination by GC–MS analysis of the products from the limonene disproportionation obtained from the catalytic hydrogenation of castor oil is not possible since a transesterification of the oil is required before injection. Therefore, a method for the determination of those products is proposed here: a solid-phase microextraction (SPME) followed by GC–MS. With the optimization of SPME it was possible to isolate a great number of products of the disproportionation of limonene used as hydrogen donor in the catalytic hydrogenation of castor oil by Pd/C. This system also proved to be appropriate to monitor castor oil hydrogenation by following and identifying the limonene disproportionated products.

Optimisation of solid phase microextraction (SPME) for the analysis of volatile compounds in dry‐cured ham

AbstractSolid phase microextraction (SPME) has been shown to be an effective tool for analysing volatile compounds. The aim of this study was to optimise the conditions for the application of SPME in the analysis of volatile compounds in dry‐cured ham. The effects of exposure time and fibre coating were investigated while maintaining the dry‐cured ham at 30 °C to avoid artefact generation due to possible temperature effects. A divinylbenzene/Carboxen on polydimethylsiloxane (DVB/CAR/PDMS) coating showed the best extraction performance for medium‐ and high‐molecular‐weight analytes, whilst a Carboxen on polydimethylsiloxane (CAR/PDMS) coating gave the best results for low‐molecular‐weight compounds. A total of 70 different compounds were extracted by the two fibre coatings and identified. Sixty compounds were extracted by the DVB/CAR/PDMS fibre, whilst only 41 of these were found with the CAR/PDMS fibre. On the other hand, 10 additional volatile compounds were extracted by the CAR/PDMS coating, all of them being of low molecular weight. Two of the major compounds extracted, hexanal and 2‐pentanone, were found in high proportion in both fibre coatings. The extraction yields of dry‐cured ham volatile compounds varied according to the fibre coating used and the time of exposure. Therefore extraction conditions should be selected depending on the objective of the study.© 2002 Society of Chemical Industry

Optimization of Solid-Phase Microextraction (SPME) for the Recovery of Explosives from Aqueous and Post-Explosion Debris Followed by Gas and Liquid Chromatographic Analysis

Solid-phase microextraction (SPME) has been evaluated for the recovery of explosives residues from aqueous samples and real post-explosion solid debris samples and optimized using gas chromatography with an electron capture detector (GC-ECD) and high-performance liquid chromatography with ultraviolet detection (HPLC-UV). A modified SPME/HPLC interface utilizing dual six-port valves allowed for independent optimization of SPME desorption and injection variables that provided improved chromatographic resolution and sensitivity. A unique combination of cyano and octadecyl columns resulted in the complete separation of the 14 explosives in EPA method 8330 mixture using HPLC with good quantitative results. At the optimum SPME conditions, the limits of detection (LOD) were found to be of 5 ng/mL to 16 ng/mL of explosives in water and 10 microg/kg to 40 microg/kg of explosives from soil. The technique has been successfully applied to the analysis of real post-explosion debris and can be adapted for use in the field utilizing portable chromatographic instruments.

A Systematic Approach To Optimize Solid-Phase Microextraction. Determination of Pesticides in Ethanol/Water Mixtures Used as Food Simulants

The optimization of solid-phase microextraction (SPME) of several organochlorine and organophosphorus pesticides is presented, and the influence of variables is discussed. The optimized method is applied to several selected ethanol/water mixtures used as food simulants, and the influence of the ethanol content on the SPME performance is also discussed. Detection limits ranging from 0.02 to 0.04 ng/g for water simulant and from 38.7 to 205.5 ng/g for 95% ethanol simulant were obtained. The relative standard deviation (% RSD) was <20% in all cases. The optimized method is compared with classical liquid-liquid extraction (LLE).

Optimization of solid phase microextraction - capillary zone electrophoresis - mass spectrometry for high sensitivity protein identification.

We have previously described the use of a solid phase extraction (SPE) - capillary zone electrophoresis (CZE) - tandem mass spectrometry (MS/MS) system for protein analysis at the low femtomole to subfemtomole level. Here we describe the systematic optimization of a number of parameters which facilitate the use of the SPE-CZE-MS/MS system and further enhance its performance. Specifically, we describe a robust SPE cartridge design which can be assembled without the use of glue, the evaluation of procedures to chemically modify the inner wall of the fused-silica capillaries used in the system to improve separation and reproducibility, and the comparison of different reverse-phase (RP) resins used for the SPE cartridge. We also explored the effects of transient isotachophoresis with respect to system performance and compatibility with different fused-silica surface coatings, the RP resins used, and MS/MS. The enhanced performance of the optimized system is demonstrated by the analysis of calibrated tryptic digests of bovine serum albumin (BSA).