Through Oven Transfer Adsorption Desorption Interface Research Articles

TOTAD interface: A review of its application for LVI and LC-GC

Abstract Large volume injection (LVI) in gas chromatography (GC) and online liquid chromatography-gas chromatography (LC-GC) are useful techniques for analyzing the compounds present at very low concentrations in complex samples since they substantially increase the sensitivity of the analysis and simplify sample preparation. LVI avoids the need to concentrate the extract and even the extraction step itself by directly injecting the sample. In online LC-GC, the liquid chromatography (LC) step acts as the sample preparation and/or fractionation step. The main problem in both techniques is the selective elimination of the large volume of solvent without losing the analytes. The TOTAD (through oven transfer adsorption–desorption) interface, based on a widely modified PTV (programmed temperature vaporizer) injector, allows large volumes to be injected into the gas chromatograph using both nonpolar and polar solvents, including water. Consequently, online LC-GC can be carried out whether the LC step is in the normal phase or the reversed phase. Various methods for analyzing trace compounds in food and environmental samples have been developed for LVI and online LC-GC using the TOTAD interface. Such analysis methods require the optimization of several variables common to LVI and online LC-GC and specific variables involved in online LC-GC, which must be optimized by taking into account the nature of the analytes and the characteristics of the sample matrix. This article reviews how each of these variables affects the performance of the analysis.

New Analytical Method for Determination of Phthalates in Wastewater by on Line LC-GC-MS Using the TOTAD Interface and Fraction Collector

There is an increasing demand for automatic, reliable and sensitive analytical methods for determining trace levels of phthalic acid esters (PAEs) in environmental samples. While on line coupled liquid chromatography-gas chromatography (LC-GC) has been proof to be a powerful tool for trace-level analyses in complex matrices, the present work presents a new totally automated on line LC-GC method, using the Through Oven Transfer Adsorption Desorption (TOTAD) interface, for the analysis of four of the main phthalates, dibuthyl phthalate (DBP), diethyl phthalate (DEP), dimethyl phthalate (DMP) and diethylhexyl phthalate (DEHP), in a matrix as complex as leachate. The sample is directly injected into the LC injector valve with no sample pretreatment other than simple filtration. The LC step separates the target analytes from matrix interference. Two different LC fractions are collected in a purposely designed fraction collector and then transferred to the TOTAD interface, which concentrates the analytes, totally eliminates the solvent and transfers the analytes to the GC-MS system, where the analysis is carried out. The LOD of the method varied from 0.1 µg/L (DEHP) to 1.4 µg/L (DMP), RSD for retention time below 0.14% and for absolute peak areas below 12% and linearity from 1 µg/L to 1000 µg/L (R2 > 0.99), except in the case of DEHP (linearity from 1 to 250 µg/L, R2 = 0.94). The method was applied to the analysis of the target analytes in samples collected from a municipal solid waste (MSW) landfill in Rosario (Argentina).

Improving enantiomeric resolutions by avoiding peak distortion effects in on-line coupled liquid chromatography to gas chromatography.

In this work, we study the effect of different variables affecting elution profile distortion on the enantiomeric resolution eventually achievable when working with on-line coupled liquid chromatography to gas chromatography (LC-GC). Specifically, the proposed configuration combines achiral reversed-phase liquid chromatography (RPLC) and chiral gas chromatography (enantio-GC), with heptakis-(2,3,6-tri-O-methyl)-β-cyclodextrin as enantioselective stationary phase to analyse target fractions transferred (from LC to GC) via the through oven transfer adsorption desorption (TOTAD) interface. The high degree of orthogonality resulting from the combination of two chromatographic columns having very different separation mechanisms (and also requiring mobile phases in distinct physical states), as well as integration of the sample preparation step in the first dimension of the system, significantly contributed to exploit the performance of the proposed two-dimensional approach. Occasional adverse effects, which may result in severe peak distortions during LC-GC analysis and could be explained by flow instabilities due to viscous fingering, are circumvented by using the outstanding capacity of the TOTAD interface for achieving effective elimination of the eluent arriving from the LC preseparation.

Use of nitrogen to remove solvent from through oven transfer adsorption desorption interface during analysis of polycyclic aromatic hydrocarbons by large volume injection in gas chromatography

The through oven transfer adsorption desorption (TOTAD) interface allows large volume injection (LVI) in gas chromatography and the on-line coupling of liquid chromatography and gas chromatography (LC–GC), enabling the LC step to be carried out in normal as well as in reversed phase. However, large amounts of helium, which is both expensive and scarce, are necessary for solvent elimination. We describe how slight modification of the interface and the operating mode allows nitrogen to be used during the solvent elimination steps. In order to evaluate the performance of the new system, volumes ranging from 20 to 100μL of methanolic solutions of four polycyclic aromatic hydrocarbons (PAHs) were sampled. No significant differences were found in the repeatability and sensitivity of the analyses of standard PAH solutions when using nitrogen or helium. The performance using the proposed modification was similar and equally satisfactory when using nitrogen or helium for solvent elimination in the TOTAD interface. In conclusion, the use of nitrogen will make analyses less expensive.

Large volume injection in gas chromatography using the through oven transfer adsorption desorption interface operating under vacuum.

The present work describes a modification of the Through Oven Transfer Adsorption Desorption (TOTAD) interface, consisting of coupling a vacuum system to reduce the consumption of the helium needed to totally remove the eluent for large volume injection (LVI) in gas chromatography (GC). Two different retention materials in the liner of the TOTAD interface were evaluated: Tenax TA, which was seen to be unsuitable for working under vacuum conditions, and polydimethylsiloxane (PDMS), which provided satisfactory repeatability as well as a good sensitivity. No variability was observed in the retention times in either case. Solutions containing organophosphorous pesticides in two different solvents, a polar (methanol/water) and a non-polar (hexane) solvent, were used to evaluate the modification. The vacuum system coupled to the TOTAD interface allowed up to 90% helium to be saved without affecting the performance.

On-line coupled reversed phase liquid chromatography and gas chromatography: A new sealing design for the TOTAD interface

Total elimination of the eluent resulting from the pre-separation step is the critical point when coupling LC to GC. As a helium flow is applied during transfer to eliminate the solvent, the interface used for linking the two chromatographic systems must be properly sealed to prevent gas leaks and to achieve an effective evaporation of the eluent. The aim of this work was to improve the performance of the Through Oven Transfer Adsorption Desorption (TOTAD) interface to remove the eluent coming from LC by modifying the way in which the injector sealing system is held in place. As with the original design, the new approach makes it possible to transfer high volumes at a high rate, but the proposed modification also simplifies the experimental work because the displacement risk of the sealing system is reduced. Analyses of an ester mixture by RPLC-GC were performed to confirm the applicability of the system modification. In this work, volumes of up to 5 ml, at flow rates as high as 2 ml/min, were transferred from LC to GC with almost complete solvent removal even when working in reversed phase mode in the LC step.

Analysis of polychlorinated biphenyls in transformer oils by automated on-line coupling reversed phase liquid chromatography-gas chromatography using the through oven transfer adsorption desorption (TOTAD) Interface

An automated method for the direct analysis of polychlorinated biphenyls (PCBs) in transformer oil is presented. The proposed method uses the TOTAD (through oven transfer adsorption desorption) interface for the on-line coupling of reversed phase liquid chromatography and gas chromatography (RPLC-GC). In this fully automated system, the oil is injected directly with no sample pre-treatment step other than dilution with n-propanol and filtration. In the LC step, PCBs are separated from other components of the oils using methanol/water (90:10 v/v) as mobile phase, at a flow rate of 1 mL min−1. The LC fraction containing the PCBs is automatically transferred to the GC by the TOTAD interface and GC analysis enables the separation of the PCB congeners. The proposed method is compared with two other methods: the European Norm (UNE-EN-61619) and that of the American Society for Testing and Materials (ASTM) (D4059-00). The proposed method practically eliminates the time-consuming sample preparation step and avoids errors caused by sample manipulation. The total PCB concentrations obtained with the three methods are similar.

Analysis of steroids in human urine by on line liquid chromatography–gas chromatography–mass spectrometry using the Through Oven Transfer Adsorption Desorption interface and a fraction collector

Anti-doping laboratories accredited by the WADA (World Anti-Doping Agency) must have available methods capable of detecting synthetic steroids at concentrations below 10ngmL−1 and, at the same time, be able to quantify endogenous steroids with accuracy. The unequivocal identification of the steroids must be carried out by GC–MS. In this manuscript we describe a new method by on-line coupled liquid chromatography–gas chromatography (LC–GC) using the Through Oven Transfer Adsorption Desorption (TOTAD) interface and mass spectrometer (MS) detector. By this means, all the analyte eluted in the LC stage are automatically transferred to the GC, avoiding the contamination associated with manipulation of the sample. A newly designed fraction collector is described for the first time. The collector permits the different fractions eluted in LC to be stored and sent individually to the GC by means of the TOTAD interface. The detection limits attained, measured in gas chromatography–mass spectrometry (GC–MS) in SCAN mode, vary between 0.5 and 3.4ngmL−1, and the method, once the sample is derivatized, is completely automatic.

Large volume injection of water in gas chromatography–mass spectrometry using the Through Oven Transfer Adsorption Desorption interface: Application to multiresidue analysis of pesticides

In the present work, the potential of the Through Oven Transfer Adsorption Desorption (TOTAD) interface for the large volume injection (LVI) of aqueous samples in gas chromatography (GC) using a mass spectrometry (MS) detector is demonstrated. To this end, a new method for the determination of pesticides in water is presented, being the first developed method in which injection of large amounts of polar solvents using the TOTAD interface and an MS detector are combined, is applied to the determination of pesticides in water. Water samples, as large as 5 ml, were directly injected into a capillary GC. No sample pre-treatment step other than simple filtration was needed. The TOTAD interface allows the introduction of several millilitres of water, while maintaining good chromatographic characteristics. The water is almost entirely eliminated, so that LVI of aqueous samples and an MS detector can be used without problems. Organophosphorus, organochlorine, and triazine pesticides were determined in one run. Calibration curves were linear in the range tested and the sensitivity achieved injecting 5 ml of water sample was sufficient for most of the target pesticides but not for all of them. Sensitivity of the analysis can be improved by increasing the sample volume. No variability was observed in the retention times and relative standard deviations from absolute peak areas were good, considering that they corresponded to the overall analysis. The method was applied to the analysis of pesticide residues in real water samples.

Through oven transfer adsorption–desorption interface for the analysis of methyl jasmonate in aromatic samples by on‐line RPLC‐GC

A fully automated method for the determination of medium volatility compounds in aromatic samples was developed. Specifically, the determination of methyl jasmonate in jasmine fragrances was performed by using the through oven transfer adsorption-desorption (TOTAD) interface for the on-line coupling between RPLC-GC. A study of the most relevant variables involved in the performance of the TOTAD interface for medium volatility compounds was carried out by testing different values of helium flow (100, 300, 400, and 500 mL/min), transfer speed (0.1, 0.3, 0.5, and 2.0 mL/min), and methanol/water percentages (86:14, 85:15, 83:17, 80:20, and 70:30). The method developed provided satisfactory repeatability (RSD for retention times of 0.15% and for peak areas of 9.4%) and recovery (71%) as well as excellent LOD (0.01 mg/L) for methyl jasmonate in commercial jasmine essence under the experimental conditions selected as optimum. Additional advantages of the automated RPLC-TOTAD-GC method proposed in the present work are its rapidness, reliability, and the possibility of directly introducing the sample with no further pretreatment.

Analysis of Unsaponifiable Compounds of Edible Oils by Automated On-Line Coupling Reversed-Phase Liquid Chromatography−Gas Chromatography Using the Through Oven Transfer Adsorption Desorption Interface

An automated method for analysis of unsaponifiable compounds in edible oils is presented. The method involves the on-line coupling of reversed-phase liquid chromatography and gas chromatography (LC-GC) using the through oven transfer adsorption desorption (TOTAD) interface. The oil is injected directly with no sample pretreatment step other than filtration. It may also be considered to dilute the oil sample. In the LC step, a short C4 column using a methanol/water eluent separates analytes from the other components of the oils, which are made up of mainly triglycerides. A LC fraction of up to 1.6 mL containing the analytes is transferred to GC at a flow rate of 0.1-2 mL/min. The TOTAD interface allows solvent venting and the introduction of the analytes into the GC column. The proposed fully automated method allows the analysis of different groups of compounds (free sterols, tocopherols, squalene, and erythrodiol and uvaol) in one chromatographic run or the analysis of these compounds in different groups. Sensitivity is more than necessary, and repeatability is good, the CV ranging from 3 to 12% for the full analysis.

Determination of organophosphorus and triazine pesticides in olive oil by on-line coupling reversed-phase liquid chromatography/gas chromatography with nitrogen-phosphorus detection and an automated through-oven transfer adsorption-desorption interface.

A method is described for the simultaneous determination of organophosphorus and triazine pesticides in olive oil, whereby reversed-phase liquid chromatography (LC) is coupled to gas chromatography by means of an automated through-oven transfer adsorption-desorption (TOTAD) interface. The olive oil needs to be filtered only before it is loaded into the liquid chromatograph, where preseparation of the pesticide residues from the other olive oil components is carried out by using methanol-water as the eluant. The LC fraction containing the pesticides is automatically transferred to the gas chromatograph by using the TOTAD interface, which almost totally eliminates the solvent, so that water-sensitive detectors such as the nitrogen-phosphorus detector can be used. Detection limits range from 0.07 to 0.38 microg/L for organophosphorus pesticides and from 6.0 to 7.0 microg/L for triazines. The results were compared with those obtained by flame ionization detection.

Very-Large-Volume Sampling ofWater in Gas Chromatography Using the Through Oven Transfer Adsorption Desorption (TOTAD) Interface for Pesticide-Residue Analysis

The Through Oven Transfer Adsorption Desorption (TOTAD) interface is used to directly introduce large volumes of water (1 mL or more) into a capillary gas chromatograph. The TOTAD interface is a greatly modified programmed temperature vaporizer injector incorporating changes that affect the pneumatics, sample introduction, solvent elimination, and operation mode. The system can easily be automated. The technique is applied to the analysis of pesticide residue in standard solutions and real water samples from the Ebro River (northeastern Spain). The speed of sample introduction was 1 mL/min, and the solvent elimination was almost complete. A nitrogen phosphorous detector is used, and the relative standard deviation varied from 5.7% to 11.7% for the absolute peak areas. The sensitivity achieved by introducing 1 mL of the sample is sufficient for most pesticide-residue analyses in water. The limits of detection ranged from 0.5 to 8.1 ng/L.

On-line reversed phase LC-GC by using the new TOTAD (Through Oven Transfer Adsorption Desorption) interface: Application to parathion residue analysis

A new interface named TOTAD (Through Oven Transfer Adsorption Desorption) for on-line coupling reversed phase liquid chromatography to gas chromatography (RPLG-GC) is presented. TOTAD interface is a great modification of a programmable temperature injector (PTV). Changes affect pneumatics, sample introduction, solvent elimination, and operation mode. The volume of the LC fraction that can be transferred (with a very strong eluent flow during the transfer step) is very high. Manufacturing this system is not difficult, operation mode is easy and automatization is possible. Analysis of parathion residues in water samples has been carried out in order to illustrate the applicability of the system. The analysis of pesticide residue is performed by off-line SPE and on-line RPLC-GC using the new interface presented. The extract (50 μL) is injected in the LC system. Eluent fraction containing parathion is sent to the TOTAD interface at the same LC column flow. Analytes are retained by a sorbent placed in the insert of the interface and thermally desorbed to the capillary column. A nitrogen-phosphorus detector (NPD) is used. ©1999 John Wiley & Sons, Inc. J Micro Sep 11: 582–589, 1999