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

Summary 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.     

Water pollution screening by large-volume injection of aqueous samples and application to GC/MS analysis of a river Elbe sample

The large-volume sampling of aqueous samples in a programmed temperature vaporizer (PTV) injector was used successfully for the target and non-target analysis of real samples. In this still rarely applied method, e.g., 1 mL of the water sample to be analyzed is slowly injected direct into the PTV. The vaporized water is eliminated through the split vent. The analytes are concentrated onto an adsorbent inside the insert and subsequently thermally desorbed. The capability of the method is demonstrated using a sample from the river Elbe. By means of coupling this method with a mass selective detector in SIM mode (target analysis) the method allows the determination of pollutants in the concentration range up to 0.01 μg/L. Furthermore, PTV enrichment is an effective and time-saving method for non-target analysis in SCAN mode. In a sample from the river Elbe over 20 compounds were identified. Received: 17 June 1996 / Revised: 22 November 1996 / Accepted: 25 November 1996     

Water pollution screening by large-volume injection of aqueous samples and application to GC/MS analysis of a river Elbe sample

The large-volume sampling of aqueous samples in a programmed temperature vaporizer (PTV) injector was used successfully for the target and non-target analysis of real samples. In this still rarely applied method, e.g., 1 mL of the water sample to be analyzed is slowly injected direct into the PTV. The vaporized water is eliminated through the split vent. The analytes are concentrated onto an adsorbent inside the insert and subsequently thermally desorbed. The capability of the method is demonstrated using a sample from the river Elbe. By means of coupling this method with a mass selective detector in SIM mode (target analysis) the method allows the determination of pollutants in the concentration range up to 0.01 μg/L. Furthermore, PTV enrichment is an effective and time-saving method for non-target analysis in SCAN mode. In a sample from the river Elbe over 20 compounds were identified. Received: 17 June 1996 / Revised: 22 November 1996 / Accepted: 25 November 1996     

Performance of programmed temperature vaporizer, pulsed splitless and on-column injection techniques in analysis of pesticide residues in plant matrices.

A programmed temperature vaporizer (PTV) injection technique has been recently implemented in our laboratory. In present paper its performance is compared with other GC injection techniques commonly used in trace analysis of organic contaminants. Twenty-six pesticides representing different chemical classes were selected for the study. This group comprised compounds typically subjected to discrimination in the injection port of the gas chromatograph, e.g., polar organophosphorus pesticides and thermolabile carbamates. In the first set of experiments standards in pure solvent were injected into GC systems employing different types of injection, i.e., (i) on-column, (ii) pulsed splitless, (iii) PTV solvent split, (iv) PTV splitless, and the responses of analytes were compared. Discrimination of troublesome compounds was significantly decreased with the application of PTV solvent split injection. In the second set of experiments repetitive injections of purified wheat samples were performed, with aims to evaluate the long-term stability of responses, as well as matrix effects in different stages of system contamination for each injection technique. The tolerance of the GC system to co-injected matrix components was increased in the order: on-column相似文献   

Optimisation of programmable temperature vaporizer-based large volume injection for determination of pesticide residues in fruits and vegetables using gas chromatography-mass spectrometry

The applicability of programmable temperature vaporizer (PTV) solvent vent injection to the gas chromatographic (GC) determination of pesticide residues in fruits and vegetables was evaluated with the aim of miniaturizing the current multiresidue method. For that purpose 24 pesticides representing different chemical classes were initially chosen for optimisation of the large volume injection (LVI) parameters. Various parameters related to the optimum injector performance were tested for several types of packed and empty liners using both fast (at-once) and speed-controlled PTV solvent vent injection of standard solutions in ethyl acetate. In the next step, several packed and empty liners were evaluated for their suitability for pesticide multiresidue analysis. Parameters identified as optimal were then applied for PTV solvent vent injection of sample extracts prepared using the miniaturized multiresidue method to assess the long-term stability of the system. The combined use of large volume injection of 10 microl ethyl acetate extract into an empty multi-baffled or a CarboFrit packed liner using PTV injectors and GC-MS analysis enabled the detection and quantification of 124 pesticides in fruit and vegetable samples at the 0.01 mg/kg level using miniaturized reversed-phase solid-phase extraction (RP-SPE) of diluted acetone extract and clean-up on a small anion-exchange SPE column.     

大体积进样技术在环境分析中的应用

在毛细管气相色谱法(CGC)中,采用大体积进样技术(LVI),即使用能够容纳大体积样品的进样装置以及增加可控时间的溶剂蒸汽放空装置,可以满足环境样品中超痕量组分的分析要求,简化样品浓缩步骤以及实现液相色谱(LC)与CGC的在线联用。针对分析物的性质、毛细管柱的规格和分析的目的已发展了多种LVI。本文总结了几种常见的LVI,包括柱头进样(OCI)和程序升温进样(PTV),以及近年来发展的一些新技术,如在柱同时溶剂浓缩进样、样品直接引入进样/复杂基质进样和同时溶剂冷凝无分流进样,阐述了各种进样技术的基本原理及其与样品提取、LC纯化在线联用的方法在环境分析应用中的一些最新研究进展。     

Headspace-programmed temperature vaporizer-fast gas chromatography-mass spectrometry coupling for the determination of trihalomethanes in water

A new method based on the use of a headspace autosampler in combination with a GC equipped with a programmable temperature vaporizer (PTV) and an MS detector has been developed for the screening and quantitative determination of trihalomethanes (THMs) in different aqueous matrices. The use of headspace generation to introduce the sample has the advantage that no prior sample treatment is required, thus minimizing the creation of analytical artifacts and the errors associated with this step of the analytical process. The PTV inlet used was packed with Tenax-TA. The injection mode was solvent vent, in which the analytes are retained in the hydrophobic insert packing by cold trapping, while the water vapour is eliminated through the split line. This allows rapid injection of the sample in splitless mode, very low detection limits being achieved without the critical problem of initial sample bandwidth. The capillary column used allowed rapid separations with half-height widths ranging from 1.68 s (chloroform) to 0.66 s (bromoform). The GC run time was 7.3 min. The use of mass spectrometry allows the identification and quantification of the analytes at the low ppt level. The S/N ratio was at least 10-fold higher when the SIM mode was used in data acquisition as compared to the scan mode. The proposed method is extremely sensitive, with detection limits ranging from 0.4 to 2.6 ppt.     

Programmable Temperature Vaporizer (PTV) Applied to the Triglyceride Analysis of Milk Fat

The PTV (Programmable Temperature Vaporizer) is a split/splitless injector which allows the sample to be introduced at a relatively low temperature, thus affording accurate and reproducible sampling. After injection the PTV is rapidly heated to transfer the vaporized components into the capillary column. This type of injector has proved to be an efficient tool for the evaluation of fatty acids, essential oils, and pesticides in food analysis. In this work the suitability of PTV for the analysis of milk fat purity by the Official EU method was evaluated. This method is based on the gas chromatographic determination of triglycerides only according to their total number of carbon atoms followed by the application of formulae deriving from multiple linear regressions. The analysis is currently carried out with a packed column or a short capillary column and an on-column injection system. Several samples of pure milk fat and mixtures of milk fat with foreign fat were analyzed with the same capillary column and by using both PTV and on-column injection systems. The results show that the gas chromatographic profile obtained by PTV is comparable with that obtained by the on-column injector, while repeatability and reproducibility data meet the requirements indicated in the Official Method. Therefore, this study demonstrates that it is possible to use the PTV instead of the on-column injector to determine the purity of milk fat with this method.     

Trace analysis of pesticide residues in water by high-speed narrow-bore capillary gas chromatography-mass spectrometry with programmable temperature vaporizer

A method for the rapid trace analysis of 17 residual pesticides in water by narrow-bore capillary (I.D. 100 microm) gas chromatography-mass spectrometry (GC-MS) using a programmable temperature vaporizer (PTV) was discussed. The method consisted of a large-volume injection (40 microl) by a PTV, high-speed analysis using a narrow-bore capillary column and MS detection. The PTV with solvent vent mode was very useful for large-volume injection into a narrow-bore capillary column because the injected solvent volume could be reduced to less than 2 microl. The analysis time was 8.5 min [less than 50% of the analysis time using conventional columns (I.D. 250 microm)]. A 10-ml volume of river water was extracted by dichloromethane (4 ml), and then the extract was condensed to 1 ml. This extract was analyzed. Mean recoveries for river water spiked at 100 pg/ml ranged from 83.4 to 96.7%. The limit of detections of the 17 pesticides ranged from 1 to 100 pg/ml.     

Influence of the injection technique and the column system on gas chromatographic determination of polybrominated diphenyl ethers

In this paper, we present an investigation of the influence of the gas chromatographic separation system on the determination of polybrominated diphenyl ethers (PBDEs). Capillary columns, retention gaps and press-fit connectors, as well as different injection techniques have been evaluated with respect to yield and repeatability. The split/splitless injection has been optimized and compared to on-column injection, the septum equipped temperature programmable injector (SPI) and the programmable temperature vaporizing (PTV) injector. Furthermore, a comparison of the different operational modes of the PTV injector is presented. The results show that there are large variations in the yield of PBDEs depending on the column and the injection systems. Especially the high molecular weight BDE congeners can be subject to severe discrimination. Unfavorable conditions can lead to a complete loss of nona and deca substituted BDE congeners.     

PTV vapor overflow — principles of a solvent evaporation technique for introducing large volumes in capillary GC

The concept of a GC solvent evaporation technique is outlined that involves a modified Programmed Temperature Vaporizing (PTV) injector. The vapor overflow technique is intended for introducing samples in large volumes of solvent by syringe injection of strongly diluted samples or by coupled LC-GC. The liquid is introduced into a packed vaporizing chamber kept above the solvent boiling point at a pressure which is near or below ambient. The carrier gas is essentially switched off. Evaporation and discharge of the solvent vapors occurs by expansion of the vapors, driven by the solvent vapor pressure. For transferring the sapmple into the column, the carrier gas is switched on again and the vaporizing chamber heated. Compared to PTV solvent split injection, vapor overflow offers the following advantages: It automatically optimizes operational parameters, therefore facilitating its application. Losses of volatile materials are minimized by a minimal flow rate through the injector. Vapor overflow is a promising technique for transferring watercontaining eluents in coupled LC-GC since no wettability is required and leaching of pre-column surfaces is avoided.     

Investigations on analyte losses in systems suited for large-volume on-column injections

Summary Use of a large-volume injection system with a solvent vapour exit (SVE) requires optimisation. An appropriate strategy is to determine the evaporation rate by increasing the injection time at a fixed injection speed, injection temperature and head pressure. When measuring the flow rate in the carrier gas supply line to the on-column injector, optimisation can be very rapid: some five injections of pure solvent will be sufficient. When working under partially concurrent solvent evaporation conditions, loss of volatiles is often observed if no retaining precolumn is used between the retention gap and the SVE. To investigate the requirements (length and stationary phase) of the retaining precolumn, C8–C18n-alkanes inn-hexane were used. The minimum length of the retaining precolumn (0.32 mm diameter) needed to prevent substantial losses of volatiles was 2 m. Experiments with retaining precolumns with and without stationary phase gave identical results. This shows that there is no need to coat the capillary as it only acts as a restrictor.     

Splitless injection of up to hundreds of microliters of liquid samples in capillary GC: Part 1, concept

If a sample evaporates by flash vaporization in an empty injector insert, the solute material is well mixed with the expanding solvent vapors and the maximum injection volume is determined by the requirement that no vapors must leave the vaporizing chamber. If evaporation occurs from a surface (e.g., of Tenax packing), however, the solvent evaporates first. The site of evaporation is cooled to the solvent's boiling point, and the cool island formed in the hot injector retains solutes of at least intermediate boiling point (visually observed for perylene). Solvent vapors, free from such solutes, may now expand backwards from the injector insert and leave through the septum purge exit. When solvent evaporation is complete, the site of evaporation warms up, causing the high boiling solutes to evaporate and to be carried into the column by the carrier gas. The technique somewhat resembles PTV injection, but is performed using a classical vaporizing injector.     

Determination of multiclass pesticide residues in apple juice by gas chromatography-mass spectrometry with large-volume injection

This study presents two GC-MS SIM methods, in combination with large-volume injection programmed-temperature vaporization (LVI-PTV) injection, for the determination of 141 pesticide residues in apple juice. The sample was extracted with ACN, and coextractives were removed with primary/secondary amine sorbent. ACN extract (20 microL) was injected into a PTV injection port in solvent vent mode, and the pesticides were determined by GC-MS using retention time locking software. Deuterium-labeled pesticides (surrogate standards) were used for analytical quality control. In the validation experiments, pesticides recoveries were found to be 70-121% with RSDs of 4.6-21% (n = 6).     

Rapid gas chromatographic analysis of less abundant compounds in distilled spirits by direct injection with ethanol–water venting and mass spectrometric data deconvolution

The principal trace secondary compounds common to fermentation-derived distilled spirits can be rapidly quantified by directly injecting 5 μL of spirit without sample preparation to a narrow-bore 0.15 mm internal diameter capillary column. The ethanol–water is removed in an initial solvent venting step using a programmed temperature vapourization injector, followed by splitless transfer of the target analytes to the column. The larger injection facilitates trace analysis and ethanol–water removal extends column lifetime. Problems of coelution between analytes or with sample matrix were surmounted by using mass spectral deconvolution software for quantification. All operations in the analysis from injection with solvent venting to data reduction are fully automated for unattended sequential sample analysis. The synergy of the various contributory steps combines to offer an effective novel solution for this analysis. Applications include quantification of low ppm amounts of acids and esters and sub-ppm profiling of trace compounds from both the raw material malt and the ageing in wood barrels.     

Direct aqueous injection with backflush thermal desorption for wastewater monitoring by online GC-MS

A gas chromatography—mass spectrometry system with a novel injector type, which is designed for direct aqueous injection of wastewater, is presented. The system is used for online monitoring of the influent of the wastewater treatment plant at BASF’s main chemical production site in Ludwigshafen, Germany. The purpose of monitoring is to protect the biological treatment process and the receiving water body, the Rhine. The modular system is primarily based on commercial equipment, but utilizes a special injection system, which is connected to a Deans switch. The two-stage injector consists of a programmable temperature vaporizer (PTV) injector with a small volume insert for vaporization and a dual sorbent packed second PTV for analyte adsorption/desorption. The Deans switch allows a backflush/thermal desorption operation which enables the direct injection of filtered, crude wastewater. About 170 volatile and semivolatile compounds are calibrated with approximate detection limits of 1 mg/L, which are sufficient for the analysis of untreated wastewater. The quantitative results are transferred to a database which is connected to a process control system. If the wastewater does not meet the required specification, an alarm is generated and the wastewater is diverted into a storage basin. Special software programs and routines allow for reliable, unattended operation and remote instrument control. Data quality is automatically controlled in each run and through the daily analysis of quality control samples. The current design allows for analysis of volatile compounds, such as methanol, whereas an earlier injector setup restricted the range of analytes to less volatile compounds (of size C₄ or greater).     

Multiresidue analysis of acidic and polar organic contaminants in water samples by stir-bar sorptive extraction-liquid desorption-gas chromatography-mass spectrometry

The feasibility of stir-bar sorptive extraction (SBSE) followed by liquid desorption in combination with large volume injection (LVI)-in port silylation and gas chromatography-mass spectrometry (GC-MS) for the simultaneous determination of a broad range of 46 acidic and polar organic pollutants in water samples has been evaluated. The target analytes included phenols (nitrophenols, chlorophenols, bromophenols and alkylphenols), acidic herbicides (phenoxy acids and dicamba) and several pharmaceuticals. Experimental variables affecting derivatisation yield and peak shape as a function of different experimental PTV parameters [initial injection time, pressure and temperature and the ratio solvent volume/N-(tert-butyldimethylsilyl)-N-methyltrifluoroacetamide (MTBSTFA) volume] were first optimised by an experimental design approach. Subsequently, SBSE conditions, such as pH, ionic strength, agitation speed and extraction time were investigated. After optimisation, the method failed only for the extraction of most polar phenols and some pharmaceuticals, being suitable for the determination of 37 (out of 46) pollutants, with detection limits for these analytes ranging between 1 and 800 ng/L and being lower than 25 ng/L in most cases. Finally, the developed method was validated and applied to the determination of target analytes in various aqueous environmental matrices, including ground, river and wastewater. Acceptable accuracy (70-130%) and precision values (<20%) were obtained for most analytes independently of the matrix, with the exception of some alkylphenols, where an isotopically labelled internal standard would be required in order to correct for matrix effects. Among the drawbacks of the method, carryover was identified as the main problem even though the Twisters were cleaned repeatedly.     

Application of programmable temperature vaporisation injection with resistive heating-gas chromatography flame photometric detection for the determination of organophosphorus pesticides

The combination of a programmable temperature vaporisation (PTV) injector with resistive heating GC (RH-GC), a form of fast GC, has been applied to the analysis of organophosphorus (OP) pesticides. The PTV injector was optimised in the 'at-once' solvent vent mode for the injection of ethyl acetate (10-40 microL) or ACN (10 microL). The short RH-GC column (5 m x 0.25 mm ID) with fast temperature ramps (up to 153 degrees C/ min) allowed the separation of a total of 20 OP pesticides in less than 6 min. Average recoveries between 67 and 119% were obtained for pesticides spiked at 0.01 mg/kg into apple and pear matrix. Extraction of orange juice with ACN provided higher recoveries (92-104%) for methamidophos, acephate and omethoate compared to ethyl acetate (62-73%). Results for analysis of OP pesticides in samples containing incurred residues were in good agreement with those obtained using GC-MS. The overall method was rapid, allowing 20 samples to be analysed in 4 h.     

Vaporising systems for large volume injection or on-line transfer into gas chromatography: Classification, critical remarks and suggestions

Techniques for large volume introduction of liquid samples into capillary gas chromatography (GC) follow a small number of principals. Vaporising systems, vapour discharge modes and methods for solvent-solute separation are classified and evaluated.

Presently, programmed temperature vaporising (PTV) solvent split injection is the preferred method if on-column techniques cannot be applied. Critical re-evaluation suggests, however, that solvent evaporation and solvent-solute separation should be performed in separate compartments and optimized individually. Permanently hot chambers offer the highest capacity for solvent evaporation. The preferred techniques for solvent-solute separation are stationary phase focusing in a coated capillary or solvent trapping in an uncoated capillary precolumn. The vaporising chamber-precolumn solvent split-gas discharge system is proposed for large volume injection and on-line transfer of water-containing solvent mixtures, and in-line vaporiser-precolumn solvent split-overflow system for most on-line transfer applications.     

Injector-internal thermal desorption from edible oils performed by programmed temperature vaporizing (PTV) injection

Injector-internal thermal desorption is a promising technique for the analysis of a wide range of food components (e.g., flavors) or food contaminants (e.g., solvent residues, pesticides, or migrants from packaging materials) in edible oils and fats or fatty food extracts. Separation from the fatty matrix occurs during injection. Using programmed temperature vaporizing (PTV) injection, the oily sample or sample extract was deposited on a small pack of glass wool from which the components of interest were evaporated and transferred into the column in splitless mode, leaving behind the bulk of the matrix. Towards the end of the analysis, the oil was removed by heating out the injector and backflushing the precolumn. The optimization dealt with the gas supply configuration enabling backflush, the injector temperature program (sample deposition, desorption, and heating out), separation of the sample liquid from the syringe needle and positioning it on a support, deactivation of the support surface, holding the plug of fused silica wool by a steel wire, and the analytical sequence maintaining adsorptivity at the desorption site low. It was performed for a mixture of poly(vinyl chloride) (PVC) plasticizers in oil or fatty food. Using MS in SIM, the detection limit was below 0.1 mg/kg for plasticizers forming single peaks and 1 mg/kg for mixtures like diisodecyl phthalate. For plasticizers, RSDs of the concentrations were below 10%; for the slip agents, oleamide and erucamide, it was 12%. The method of incorporating PTV injection was used for about one year for determining the migration from the gaskets of lids for glass jars into oily foods.