Splitless Time Research Articles

Assessing the influence of neglected GC-FID variables on the multiple responses using multivariate optimization for the determination of ethanol and acetonitrile in radiopharmaceuticals

Analytical gas chromatography in line with a flame ionization detector (GC-FID) method was developed and validated for direct determination of organic solvents in [18F]fluoro-ethyl-tyrosine ([18F]FET), [18F]fluoromisonidazole ([18F]FMISO) and [18F]fluorothymidine ([18F]FLT). Variables of the splitless time (min) and injection temperature (°C) on the response of analysis time and resolution were optimized with the assistance of a two-level full factorial design and desirability function of Derringer. The proposed procedure was validated following the International Council for Harmonisation of Technical Requirements for Pharmaceuticals for Human Use (ICH) Q2 (R1) guideline. Excellent linearity, R2 > 0.990, indicated that approximately 99% of the response variance could be predicted from ethanol and acetonitrile concentrations ranging from 0.5 to 6.0 mg mL−1 and 0.1 to 0.8 mg mL−1, respectively. The proposed procedure has proved to be selective, sensitive, and accurate (90–110%), with excellent repeatability and precision (RSD < 2%). In the robustness analysis, the findings from the calculated Standardized Effects Values (SE) were insignificant (p > 0.05) and demonstrated that the proposed method was robust for a splitless time of 1.0 ± 0.5 min and an injection temperature of 210 ± 10 °C. The proposed method was also successfully used for the quantitative determination of ethanol and acetonitrile in [18F]FET, [18F]FMISO, and [18F]FLT. Both solvents were well separated (R, 4.1–4.3) within 4.5 min. Therefore, the proposed method is relevant for routine quality control analysis of all 18F-radiopharmaceutical derivatives for the direct determination of ethanol and acetonitrile.

A simple GC–MS method for the determination of diphenylamine, tolylfluanid propargite and phosalone in liver fractions

In this study, an accurate and robust gas chromatography/mass spectrometry method was developed for quantitative analysis of diphenylamine, tolylfluanid, propargite and phosalone in liver fractions. Different injector parameters were optimized by an experimental design technique (central composite design). An optimal combination of injector temperature (°C), splitless time (min) and overpressure (kPa) values enabled to maximize the chromatographic responses. Sample preparation was based on protein precipitation using trichloroacetic acid followed by liquid-liquid extraction (LLE) of the pesticides with hexane. All compounds and endrin as internal standard were quantified without interference in selected ion monitoring mode. The calibration curves for diphenylamine, tolylfluanid, propargite and phosalone compounds were linear over the concentration range of 0.1 to 25 μM with determination coefficients (R2) higher than 0.999. A lower limit of quantification of 0.1 μM was obtained for all analytes, i.e. 422.5, 868.0, 876.2 and 919.5 μg/kg of liver fraction (hepatocytes) for diphenylamine, tolylfluanid, propargite and phosalone, respectively. All compounds showed extraction recoveries higher than 93%, with a maximum RSD of 3.4%. Intra- and inter-day accuracies varied from 88.4 to 102.9% and, imprecision varied from 1.1 to 6.7%. Stability tests demonstrated that all pesticides were stable in liver extracts during instrumental analysis (20 °C in the autosampler tray for 72 h) following three successive freeze-thaw cycles and, at −20 °C for up to 12 months. This simple and efficient analytical procedure is thus suitable for metabolism studies or for assessing mammals liver contamination.

Simultaneous high-temperature gas chromatography with flame ionization and mass spectrometric analysis of monocarboxylic acids and acylglycerols in biofuels and biofuel intermediate products

Triacyl-, diacyl- and monoacylglycerols (TAGs, DAGs, MAGs) along with monocarboxylic acids (MCAs) are intermediate products in many triacylglycerol oil-to-biofuel conversion pathways. Accumulation of these compounds leads to poor biofuel characteristics and may result in fuel system damage. We developed a method for simultaneous identification and quantification of a wide range of MCAs (C4-C18), MAGs, DAGs, and TAGs. The method is based on trimethylsilylation followed by high temperature GC with programmed temperature vaporizer (PTV) injection coupled to parallel FID and MS detectors (HTGC-FID/MS).To minimize the discrimination of both low and high molecular weight species typically occurring on the injector, we optimized injection conditions using a central composite design. The critical variables were the time at initial temperature (40 °C), splitless time, and the interaction between these two parameters. Among three tested electron ionization source/quadrupole analyzer temperatures, a 350/200 °C setting provided the highest response and signal-to-noise ratio for TAGs and did not have an effect on MAGs and DAGs.Similar results were obtained when quantifying target analytes in intermediate products of soybean oil cracking with FID and MS (using specific acylglycerol fragmentation ions). The instrumental FID limits of detection (LODs) were 0.07–0.27 ng for most of the target analytes. Selected ion monitoring (SIM) LODs were 0.01–0.05 ng for MCAs and 0.03–0.14 ng for acylglycerols. For the total ion current (TIC), LODs observed increased with acyl chain length and degree of unsaturation, resulting in an increase from 0.05 to 0.18 ng for MCAs (C5 to C18) and from 0.03 to 1.8 ng for acylglycerols (TAGs C8 to C22). Deviations in the repeatability of sample preparation, intra- and inter-day analyses, including sample stability over an eight-day time period, did not exceed 10% variance. These results demonstrate that the developed method is accurate and robust for the determination of acylglycerols and MCAs produced during the processing of TAGs into biofuels.

Optimization of HS-SPME for GC-MS Analysis of Volatiles Compounds in Roasted Sesame Oil

This paper was to develop a simple and rapid headspace solid-phase microextraction (HS-SPME) method coupled with gas chromatography–mass spectrometry (GC-MS) for the determination of volatiles compounds from the roasted sesame oil (RSO). A HP-5MS capillary column (30 m × 0.25 mm I.D. × 0.25 mm film thick) was used for GC-MS, and a 50/30 μm divinylbenzene/carboxen/polydimethylsiloxane (DVB/CAR/PDMS) fiber was used to extract volatiles compounds. The condition was optimized by varying the sample-to-headspace ratio (0.5-2.5 g/15 ml), extraction time (10-50 min) and Splitless time (0.5-4 min). The results showed that the optimal operating conditions occurred at (extraction temperature:40°C, sample-to-headspace ratio: 1.5 g/15 ml, extraction time: 40 min, Splitless time: 1 min) for the analyze method.

Determination of ultraviolet filters in environmental aqueous samples by dispersive liquid-liquid microextraction with online derivatization-gas chromatography-mass spectrometry

A method of dispersive liquid-liquid microextraction (DLLME) combined with online derivatization-gas chromatography-mass spectrometry (GC-MS) was developed for the determination of benzophenone-type ultraviolet (UV) filers (BPs) in environmental aqueous samples. It is found that the online derivatization was superior to the off-line derivatization with its simplicity, high reaction efficiency and less consumption of potential poisonous reagents. The influential factors for online derivatization, including the temperature of the injection port, the splitless time, the proportion of derivatization reagent and sample solution, were initially optimized. In addition, the influential factors for DLLME, including the type of the extractant and dispersing solvent, the proportion of the extractant and the dispersing solvent, the volume of sample solution, the pH and the salt concentration of the sample solution were individually optimized in detail. Under the optimized derivatization and DLLME conditions, the limits of detection for the six BPs, benzophenone, 2,4-dihydroxybenzophenone, oxybenzone, 4- hydroxybenzophenone, octabenzone and 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, ranged from 0.011 to 0.15 μg/L. The intra-day and inter-day relative standard deviations varied from 0.7% to 16.6%. The method was applied to the analysis of lake and river water with good recoveries. It is cost effective, reliable, easy to operate, environment-friendly and promising in the real applications.

Determination of Concentration Levels of Organochlorine Pesticides in Water from the Mandacaru Stream in Maringá-Paraná-Brazil Employing Gas Chromatography-Mass Spectrometry

In this work, a method to determine the concentration levels of organochlorine pesticides in water samples from the Mandacaru stream in the region of Maringá- Paraná was validated, using the technique of solid phase extraction associated with gas chromatography coupled to mass spectrometry. In the optimization of the method, parameters such as injector temperature and splitless time were evaluated. The analytical curves showed linear correlation values greater than 0.99 (R2 > 0.99) for all compounds. The detection limits of 0.243 µg L−1 to 1.200 µg L−1 and quantification of 5.0 µg L−1 were obtained for pesticides and the recovery values were between 88.25 and 127.3%. Values of relative standard deviation were less than 6.79%. In the water samples analyzed were found four organochlorine pesticides, two with concentrations within the limits set by national legislation and two with concentrations above these limits.

Determination of polycyclic aromatic hydrocarbons and their oxy-, nitro-, and hydroxy-oxidation products

A sensitive method has been developed for the trace analysis of PAHs and their oxidation products (i.e., nitro-, oxy-, and hydroxy-PAHs) in air particulate matter (PM). Following PM extraction, PAHs, nitro-, oxy-, and hydroxy-PAHs were fractionated using solid phase extraction (SPE) based on their polarities. Gas chromatography–mass spectrometry (GC–MS) conditions were optimized, addressing injection (i.e., splitless time), negative-ion chemical ionization (NICI) parameters, i.e., source temperature and methane flow rate, and MS scanning conditions. Each class of PAH oxidation products was then analyzed using the sample preparation and appropriate ionization conditions (e.g., nitro-PAHs exhibited the greatest sensitivity when analyzed with NICI–MS while hydroxy-PAHs required chemical derivatization prior to GC–MS analysis). The analyses were performed in selected-ion-total-ion (SITI) mode, combining the increased sensitivity of selected-ion monitoring (SIM) with the identification advantages of total-ion current (TIC). The instrumental LODs determined were 6–34pg for PAHs, 5–36pg for oxy-PAHs, and 1–21pg for derivatized hydroxy-PAHs using electron ionization (GC-EI-MS). NICI–MS was found to be a useful tool for confirming the tentative identification of oxy-PAHs. For nitro-PAHs, LODs were 1–10pg using negative-ion chemical ionization (GC-NICI-MS). The developed method was successfully applied to two types of real-world PM samples, diesel exhaust standard reference material (SRM 2975) and wood smoke PM.

Needle microextraction trap for on‐site analysis of airborne volatile compounds at ultra‐trace levels in gaseous samples

Different capillary needle trap (NT) configurations are studied and compared to evaluate the suitability of this methodology for screening in the analysis of volatile organic compounds (VOCs) in air samples at ultra-trace levels. Totally, 22 gauge needles with side holes give the best performance and results, resulting in good sampling flow reproducibility as well as fast and complete NT conditioning and cleaning. Two different types of sorbent are evaluated: a graphitized carbon (Carbopack X) and a polymeric sorbent (Tenax TA). Optimized experimental conditions were desorption in the GC injector at 300°C, no make-up gas to help the transport of the desorbed compounds to the GC column, 1 min splitless time for injection/desorption, and leaving the NT in the hot injector for about 20 min. Cross-contamination is avoided when samples containing high VOC levels (above likely breakthrough values) are evaluated. Neither carryover nor contamination is detected for storage times up to 48 h at 4°C. The method developed is applied for the analysis of indoor air, outdoor air and breath samples. The results obtained are equivalent to those obtained with other thermal desorption devices but have the advantage of using small sample volumes, being simpler, more economical and more robust than conventional methodologies used for VOC analysis in air samples.

Odour-causing organic compounds in wastewater treatment plants: Evaluation of headspace solid-phase microextraction as a concentration technique

Odorous emissions from wastewater collection systems and treatment facilities affecting quality of life have given local populations reasons to complain for decades. In order to characterise the composition of such malodorous emissions, a method based on headspace solid-phase microextraction (HS-SPME) and gas chromatography coupled to mass spectrometry (GC–MS) has been developed to determine a list of compounds belonging to different chemical families, which have been previously described as potentially responsible for odour complaints, in wastewater matrices. Some parameters affecting the chromatographic behaviour of the target compounds were studied (e.g. splitless time). Experimental conditions affecting the extraction process (temperature, time and salt content) were evaluated by applying a factorial design at two levels. Using a DVB/CAR/PDMS fibre and the optimised HS-SPME conditions, calibration curves were constructed with detection limits in the range of 0.003–0.6 μg L −1. Recovery values higher than 70% and relative standard deviation values between 5 and 16% ( n = 5) were obtained for all compounds and found to be satisfactory. In wastewater samples, a decrease in the concentration of the analysed compounds through the different treatments was observed. Most of the target analytes were found in influent samples while only octanal and carvone were detected in samples from the plant effluent.

Influence of Gas Chromatographic Parameters on Determination of Decabromodiphenyl Ether

In this paper, we present a study on the influence of chromatographic parameters on determination of decabromodiphenyl ether in an attempt to arrive at optimum conditions that enhance its detection in environmental samples. Gas chromatography–electron capture detector (GC–ECD) equipped with digital pressure and gas flow control, ZB-5 capillary column of 15 and 30 m length (0.25 mm id, 0.25 μm df) are used. 1 μL of 20 ng μL−1 commercial decabromodiphenyl ether mixture dissolved in toluene is injected into the column in splitless mode and each parameter varied. Injection temperature of 290 °C, initial and final oven temperatures of 90 °C and 300–310 °C, respectively, 1.0 min splitless time and 2.5 mL min−1 flow rate found to be optimum on 15 m column. Under optimum condition, entrance of BDE209 into the column is improved; retention time reduced by a factor of three and high repeatability with almost no degradation observed. Finally, the developed method is validated using standard reference material and applied to indoor dust samples. The average concentrations of decabromodiphenyl ether found from dust analysis in ng g−1 are 118 ± 6.6, 103 ± 11 and 26 ± 1.6 in hotel, office and computer room, respectively.

Optimization of large volume injection-programmable temperature vaporization-gas chromatography–mass spectrometry analysis for the determination of estrogenic compounds in environmental samples

Large volume injection-programmable temperature vaporization-gas chromatography–mass spectrometry (LVI-PTV-GC–MS) was optimized for the determination of estrone (E1), 17β-estradiol (E2), 17α-ethynyl estradiol (EE2), mestranol (MeEE2) and estriol (E3) for their determination in environmental samples (estuarine water, wastewater, fish bile and fish homogenate) after derivatization with 25 μL (BSTFA + 1% TMCS) and 125 μL of pyridine. Experimental designs such as Plackett–Burman (PBD) and central composite designs (CCDs) were used to optimize the LVI-PTV variables (cryo-focusing temperature, vent time, vent flow, vent pressure, injection volume, purge flow to split vent, splitless time and injection speed). Optimized conditions were as follows: 45 μL of n-hexane extract are injected at 60 °C and 6 μL/s with a vent flow and a vent pressure of 50 mL/min and 7.7 psi, respectively, during 5 min; then the split valve is closed for 1.5 min and afterwards the injector is cleaned at 100 mL/min before the next injection. The method was applied to the determination of estrogenic compounds in environmental samples such as estuarine water, wastewater, and fish homogenate and bile. Limits of detection (0.04–0.15 ng/L for water samples, 0.04–0.67 ng/g for fish bile and 0.1–7.5 ng for fish homogenate) obtained were approx. ten times lower than those obtained by means of a common split/splitless inlet.

OPTIMIZATION OF LARGE VOLUME INJECTION FOR IMPROVED DETECTION OF POLYCYCLIC AROMATIC HYDROCARBONS (PAH) IN MUSSELS

Detection of PAH of six benzene rings is somewhat troublesome and lowering the limits of detection (LODs) for these compounds in food is necessary. For this purpose, we optimized a Programmable-Temperature-Vaporisation (PTV) injection with Large Volume Injection (LVI) with regard to the GC-MS detection of anthracene, benz[a]anthracene, benzo[a]pyrene, indeno[1,2,3-cd]pyrene and dibenzo[a,e]pyrene. The optimization of PTV-LVI for GC-MS analysis included the choice of liner, solvent venting, splitless time, split flow and initial inlet temperature for injection of 25 μ L standard solution and spiked mussel samples. Samples were extracted with Accelerated Solvent Extraction (ASE) followed by two semi-automatic clean-up steps; gel permeation chromatography (GPC) on S-X3 and solid phase extraction (SPE) on pre-packed silica columns, prior to gas chromatography-mass spectrometry (GC-MS) detection. In comparison to traditional splitless injection, LODs were lowered for eighteen PAHs by the use of PTV-LVI ranging from 0.05 μ g kg −1 to 1.0 μ g kg−1 fresh weight. In particular, the LOD of dibenzo[a,e]pyrene was improved by a factor of ten when using the validated PTV-LVI method.

Pressurized hot water extraction coupled to solid-phase microextraction–gas chromatography–mass spectrometry for the analysis of polycyclic aromatic hydrocarbons in sediments

A fully automated, environmentally friendly, simple, and sensitive method was developed for the analysis of polycyclic aromatic hydrocarbons (PAHs) in sediment samples. The procedure is based on pressurized hot water extraction (PHWE) followed by solid-phase microextraction (SPME) and determination by gas chromatography–mass spectrometry. For PHWE, parameters such as organic modifier, percentage of organic modifier, temperature, and static extraction time were studied. For SPME, extraction temperature and time, desorption temperature and time, splitless time, ionic strength adjustments, and effect of an organic modifier were studied. When these parameters were selected, the figures of merit were calculated. The detection and quantification limits were between 0.4–15 μg kg −1 and 1.2–51 μg kg −1, respectively. The linearity of the method was assessed spiking sediment samples at seven levels of concentration ranged between 2.5 μg kg −1 and 500 μg kg −1 for most of the studied PAHs. The method was validated by two concentration levels reference marine sediment materials (SRM 1944 and SRM 1941b). The obtained results are in very good agreement with the certificate materials. The developed method seems to be suitable for the analysis of PAHs at ultratrace levels in environmental matrices as sediment samples.

Solid-phase microextraction–gas chromatographic–tandem mass spectrometric analysis of polycyclic aromatic hydrocarbons: Towards the European Union water directive 2006/0129 EC

This article presents a solid-phase microextraction (SPME) procedure to determine 27 parent and alkylated polycyclic aromatic hydrocarbons (PAHs) with diverging polarities and molecular masses in various types of water samples (tap, well, superficial, and seawater). A 65-μm polydimethylsiloxane–divinylbenzene (PDMS/DVB) fiber was used, and parameters affecting the extraction procedures such as extraction temperature and time, desorption temperature and time, splitless time, effect of an organic modifier or ionic adjustment were studied. The linearity and precision of the proposed method were satisfactory. The use of GC–MS determination in the full scan mode, in the selected ion monitoring (SIM) mode, and in the GC–MS–MS mode provided the unequivocal identification and quantification of the target analytes. Moreover, the proposed SPME–GC–MS–MS method, extracting only 18 ml of sample, reached the very restrictive limits fixed by the 2006/0129 EC proposal for a new water directive to be achieved by 2015. The matrix effects were evaluated through the analysis of tap, well, superficial, and seawater. A discussion on different behaviors, a result of the matrix effects, was included. Analytical recoveries were satisfactory in all cases. The novelty of this work consisted in the wide range of analyzed PAHs, the very low detection limits that were reached, the coupling of SPME–GC–MS–MS, and the study of the matrix effect on water samples. With this developed procedure, detection limits between 0.07 and 0.76 ng l −1 and quantification limits between 0.10 and 0.98 ng l −1 were obtained with MS–MS detection. Moreover, the analytical recoveries for different aqueous matrices were near 100% in all cases.

Determination of hydrolytic degradation products of nerve agents by injection port fluorination in gas chromatography/mass spectrometry for the verification of the Chemical Weapons Convention

Retrospective detection and identification of markers of chemical warfare agents are important aspects of verification of the Chemical Weapons Convention. Alkyl alkylphosphonic acids (AAPAs) and alkylphosphonic acids (APAs) are important markers of nerve agents. We describe the development and optimization of a new gas chromatography/mass spectrometry (GC/MS) injection port fluorination method for the derivatization of AAPAs and APAs. The process involved the injection of acids with trifluoroacetic anhydride in GC/MS, where acids are converted into their corresponding volatile fluorides. Various reaction conditions such as fluorinating agent, injection port temperature and splitless time were optimized. The maximum reaction efficiency of the acids with trifluoroacetic anhydride was observed at 230 degrees C injection port temperature with a splitless time of 2 min. APAs showed best analytical efficiencies at 400 degrees C injection port temperature, while the other conditions were similar to those of AAPAs. The linearities of response for APAs and AAPAs were in the range of 1-25 and 5-100 microg mL(-1), respectively, with limits of detection ranging from 500 pg to 800 ng mL(-1).

Optimization of a preparative capillary gas chromatography–mass spectrometry system for the isolation and harvesting of individual polycyclic aromatic hydrocarbons

Operation parameters of a preparative capillary gas chromatography (pcGC) system were optimized to facilitate clean and efficient harvesting of individual polycyclic aromatic hydrocarbons (PAHs) for subsequent compound-specific radiocarbon analysis. For PAHs, the recommended optimized settings of the specially-designed pcGC cooled injection system (CIS) and preparative fraction collector (PFC) are: 5 s CIS solvent venting time, deactivation of CIS “stop flow” injection mode, autoinjector “fast injection” mode, 60 s CIS splitless time, 340 °C PFC switch temperature, and 30 °C (ambient) trapping temperature. These optimized conditions yielded highly reproducible, pure, and efficient pcGC harvesting of six PAHs with mass recoveries of 90–100% and purity of the isolates of 97–100%.

GC analysis of trichloroacetic acid in water samples by large-volume injection and thermal decarboxylation in a programmed-temperature vaporizer

AGC method has been developed for the analysis of tricholoroacetic acid (TCA) in water samples. It entails large-volume injection (LVI) and programmed-temperature vaporization (PTV) of water samples, thermal decarboxylation of TCA to chloroform in the injector, and GC-ECD analysis of the decarboxylation product. Conditions such as final injector temperature, splitless time, and injection volume were optimized. The limit of detection is approximately 0.1 μg L−1 Several real samples were analyzed. The method presented is an easy means of determination of TCA and eliminates sample-preparation steps such as extraction and derivatization.

Optimization and application of the PTV injector for the analysis of pesticide residues

The applicability of PTV splitless and solvent vent injection to the gas chromatographic analysis of 26 pesticides representing different chemical classes was evaluated. All parameters related to optimum injector performance in PTV splitless and PTV solvent vent (split vent) injection modes were tested. For PTV splitless injection of small sample volumes (1 μL), the inlet temperature program (initial inlet temperature, heating rate, final temperature), splitless time, and starting oven temperature were optimized. Parameters identified as optimal were then applied in PTV solvent vent injection. In the case of the PTV solvent vent technique, all injections were performed with pesticides dissolved in a binary mixture of cyclohexane-ethyl acetate (1 : 1, v/v). This solvent is used as a mobile phase in the HPGPC clean-up step involved in our multi-residue method. For the PTV solvent vent technique the following parameters were tested: maximum single injection volume, inlet temperature, vent flow, vent time, and vent period were determined for a single injection of 10 μL of sample. Thermodegradation and/or adsorption of some pesticides occurred as long as glass wool packed liner was used. To achieve lower detection limits, multiple injection concept was employed: 30 μL of standard solution were injected in three subsequent steps. Under optimized conditions even higher sample volumes could be injected. Good responses were obtained also for the compounds possessing relatively higher volatility compared to other tested analytes.

Use of a PTV injector to achieve inverse-large volume injection: Injection of volatile analytes in a semi-volatile solvent

Large volume injection of volatile analytes in a semi-volatile solvent, termed inverse-LVI, has been accomplished using a programmable-temperature vaporizing (PTV) injector. It was found that simple optimization of the time the split valve remained closed allowed complete analyte transfer to the column, while venting most of the solvent. Increasing the PTV temperature ramp from 10 K/s to 15 K/s was found to improve peak shapes, especially of the early eluting peaks, by decreasing the injection bandwidth. In addition, the optimum splitless time was found to be independent of injection volume (up to solvent limits) meaning only a single optimization was necessary for quantitative analyte transfer from each solvent. The ability to quantitatively transfer the analyte to the column was also found to be solvent independent (propylene carbonate, tridecane, and Butyl CARBITOL® Solvent were evaluated). Excellent data were obtained for injection volumes up to 15 μL of propylene carbonate and 36 μL of tridecane using an unpacked fritted PTV liner.

Use of a PTV injector to achieve inverse-large volume injection: Injection of volatile analytes in a semi-volatile solvent

Large volume injection of volatile analytes in a semi-volatile solvent, termed inverse-LVI, has been accomplished using a programmable-temperature vaporizing (PTV) injector. It was found that simple optimization of the time the split valve remained closed allowed complete analyte transfer to the column, while venting most of the solvent. Increasing the PTV temperature ramp from 10 K/s to 15 K/s was found to improve peak shapes, especially of the early eluting peaks, by decreasing the injection bandwidth. In addition, the optimum splitless time was found to be independent of injection volume (up to solvent limits) meaning only a single optimization was necessary for quantitative analyte transfer from each solvent. The ability to quantitatively transfer the analyte to the column was also found to be solvent independent (propylene carbonate, tridecane, and Butyl CARBITOL® Solvent were evaluated). Excellent data were obtained for injection volumes up to 15 μL of propylene carbonate and 36 μL of tridecane using an unpacked fritted PTV liner.