Oven Transfer Adsorption Desorption 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.

Analysis of polycyclic aromatic hydrocarbons in aqueous samples by large volume injection gas chromatography–mass spectrometry using the through oven transfer adsorption desorption interface

A new procedure for the determination of 17 polycyclic aromatic hydrocarbons (PAHs) in aqueous samples by large volume injection–gas chromatography–mass spectrometry (LVI–GC–MS) using the Through Oven Transfer Adsorption Desorption (TOTAD) interface with nitrogen for solvent elimination is developed and validated. Up to 75mL of aqueous samples were injected to be sure that good solvent elimination were achieved, although 500µL were sufficient to achieve the required sensitivity.The performance of the developed method can be considered good: the relative standard deviation (RSD), (n=3) was lower than 13.8% for all the target analytes, the concentration of each PAH being 0.25μgL−1, the limit of detection and limit of quantitation ranged from 21.5 to 211.0 ng L−1 and from 71.7 to 703.3ngL−1 respectively, and the correlation coefficients (R2) were all higher than 0.9764 in the 1–16μgL−1 range.

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.

On-line derivatization with on-line coupled normal phase liquid chromatography–gas chromatography using the through oven transfer adsorption desorption interface: Application to the analysis of total sterols in edible oils

In the present work on-line derivatization is combined with on-line normal phase liquid chromatography–gas chromatography (NPLC–GC) to analyze total sterols in edible oils. The method uses the TOTAD interface with an additional LC injection valve to automatically introduce the derivatization reagent. The derivatization reaction takes place in the adsorbent material located inside the liner of the TOTAD interface. The samples were saponified with potassium hydroxide in an ethanolic solution and the unsaponifiable fraction was extracted with diethyl ether. The extract was then analyzed by on-line derivatization with on-line NPLC–GC, avoiding the laborious thin layer chromatography and off-line derivatization steps used in the Official European Union (EU) method. The relative standard deviations (RSDs) from the absolute peak area were lower than 14% except for campestanol. No variability in retention time was observed. Limits of detection (LODs) were less than 8.82mg/kg. Different edible oils were analyzed using the proposed method and the results obtained were compared with those obtained using the Official EU method. There was good agreement between both methods for all the sterols analyzed.

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.

Analysis of free and esterified sterols in edible oils by online reversed phase liquid chromatography–gas chromatography (RPLC–GC) using the through oven transfer adsorption desorption (TOTAD) interface

An online reversed phase liquid chromatography-gas chromatography (RPLC-GC) method is proposed to quantify free, total and esterified sterols of edible oils. To determine free sterols the diluted oils are injected into the liquid chromatograph, where free sterols are separated from triglycerides and the sterol fraction is automatically transferred to the gas chromatograph to be analysed. To determine total sterols the samples were saponified with potassium hydroxide in ethanolic solution and the unsaponifiable fraction was extracted with diethyl ether. The extract was then analysed by RPLC-GC, avoiding the laborious thin layer chromatography step used in the Official European Union (EU) Method. The relative standard deviations (RSDs) from the absolute peak area varied from 7.6% to 15.8%. Limits of detection (LODs) were less than 8.5 mg/kg. No variability in retention time was observed. The method was applied to the determination of total sterols in edible oil samples and the results were compared with those obtained with the Official EU Method. Good agreement was found between both methods, except in the case of campesterol.

Chiral analysis by online coupling of reversed-phase liquid chromatography to gas chromatography and mass spectrometry

Enantiomeric composition of selected chiral compounds present in complex mixtures is determined by using the online coupling of reversed-phase liquid chromatography (LC) to gas chromatography (GC) and mass spectrometry. Integration of sample preparation into GC analysis, in a completely automated way, is achieved by means of the effective clean-up resulting from both the LC fractionation step and the eluent elimination provided by the through oven transfer adsorption desorption system used for LC-GC interfacing. The possibilities of the technique are illustrated through some examples concerning the stereodifferentiation in essential oils of major and minor chiral compounds via LC-GC transfer of different volume fractions, ranging from 0.5 to 1.9 ml, which show the significance of the window size for the determination of enantiomeric profiles.

Rapid recognition of irradiated dry-cured ham by on-line coupling of reversed-phase liquid chromatography with gas chromatography and mass spectrometry.

The use of on-line coupling of reversed-phase liquid chromatography and gas chromatography (RPLC-GC) with the through oven transfer adsorption desorption (TOTAD) interface and mass spectrometry (MS) was proposed for testing different types of commercial Spanish dry-cured ham for irradiation treatment at various doses (0, 1.5, 2, and 4 kGy). The qualitative analysis of radiation-specific compounds (e.g., n-pentadecane, 1-hexadecene, 1,7-hexadecadiene, n-heptadecane, 8-heptadecene, and 2-dodecylcyclobutanone) can be simultaneously established in a single run with samples that have or have not been irradiated. The overall analysis, which takes less than 100 min, includes a rapid extraction step using a small amount of dichloromethane-methanol (1:1, vol/vol) and anhydrous sodium sulfate, the subsequent fractionation of the sample in the first dimension of the system (RPLC), the transfer of the target fraction to the second dimension, the GC separation, and the MS detection. The calculated limits of detection in ham were lower than 22 ng/g. Repeatability studies provided relative standard deviation values of 0.8 to 13.5%.

Wax ester composition of monovarietal olive oils from Designation of Origin (DO) “Campos de Hellin”

The wax ester composition of six monovarietal olive oils (Arbequina, Benizal, Cornicabra, Cuquillo, Manzanilla, and Picual) from Designation of Origin (DO) “Campos de Hellin” (Spain) were analysed, to obtain a more complete characterisation of these varietal oils. The analyses were carried out by on-line liquid chromatography–gas chromatography (LC–GC) using the Through Oven Transfer Adsorption Desorption (TOTAD) interface. The oil made with Arbequina variety had the highest content of total wax ester (84.4 ± 4.3 mg/kg) and Picual oil the lowest (35.5 ± 3.7 mg/kg). The data obtained were analysed statistically; significant differences in C40, C44, C46 and total wax esters were found, with a level of confidence of 95%.

Analysis of wax esters in edible oils by automated on-line coupling liquid chromatography–gas chromatography using the through oven transfer adsorption desorption (TOTAD) interface

An automated method for the direct analysis of wax esters in edible oils is presented. The proposed method uses the TOTAD (through oven transfer adsorption desorption) interface for the on-line coupling of normal phase liquid chromatography and gas chromatography. In this fully automated system, the oil with C32 wax ester as internal standard and diluted with heptane is injected directly with no sample pre-treatment step other than filtration. The proposed method allows analysis of different wax esters, and is simpler and faster than the European Union Official Method, which is tedious and time-consuming. The obtained results closely match the certified values obtained from the median of the analytical results of the inter-labs certification study. Relative standard deviations of the concentrations are less than 5%. The method is appropriate for routine analysis as it is totally automated.

Applications of large-volume injection for environmental analysis

Large-volume injection (LVI) in capillary gas chromatography (CGC) was developed for determining the trace components in environmental samples and for reducing (or even eliminating) the need for cleanup step, also for on-line connection of liquid chromatography (LC) with CGC. The key features of the LVI include sample retained by a large capacity volume liner or a retention gap, and solvent vapor eliminated by solvent vapor exit. There are many kinds of LVI techniques for different analyses, capillary columns and purposes. This review summarizes the recent developments of LVI for environmental analysis, include on column injection (OCI), programmed temperature vaporizer (PTV), AT-column, direct sample introduction/difficult matrix injection, concurrent solvent recondensation large volume splitless injection, and also through oven transfer adsorption desorption interface for on-line connection of LC with CGC.

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.

Development of a method based on on-line reversed phase liquid chromatography and gas chromatography coupled by means of an adsorption–desorption interface for the analysis of selected chiral volatile compounds in methyl jasmonate treated strawberries

A method based on the use of the through oven transfer adsorption–desorption (TOTAD) interface in on-line coupling between reversed phase liquid chromatography and gas chromatography (RPLC–GC) for the determination of chiral volatile compounds was developed. In particular, the method was applied to the study of the influence of methyl jasmonate (MJ) treatment on the production and enantiomeric composition of selected aroma compounds in strawberry. The compounds studied were ethyl 2-methylbutanoate, linalool and 4-hydroxy-2,5-dimethyl-3(2 H)-furanone (i.e. furaneol), which were examined on days 3, 6 and 9 after treatment. The method developed resulted in relative standard deviations (RSDs) of 21.6%, 8.1% and 9.8% and limits of detection (LD) of 0.04, 0.07 and 0.02 mg/l for ethyl 2-methylbutanoate, linalool and furaneol, respectively. The application of the RPLC–TOTAD–GC method allowed higher levels of ethyl 2-methylbutanoate, linalool and furaneol to be detected, particularly after 9 days of treatment. Besides, MJ demonstrated to affect the enantiomeric distribution of ethyl 2-methylbutanoate. On the contrary, the enantiomeric composition of linalool and furaneol kept constant in both control and MJ-treated strawberries throughout the study. These results are discussed.

Use of absorbent materials in on-line coupled reversed-phase liquid chromatography–gas chromatography via the through oven transfer adsorption desorption interface

The use of absorbents as retaining materials in the through oven transfer adsorption desorption interface (TOTAD) of an on-line coupled reversed-phase liquid chromatography–gas chromatography system (RPLC–GC) is proposed for the first time. A comparative study of an adsorbent (Tenax TA) and two absorbents, namely polydimethylsiloxane and poly(50% phenyl/50% methylsiloxane) is performed to establish the best experimental conditions for the automated and simultaneous determination of 15 organophosphorus and organochlorine pesticide residues in olive oil. The proposed method provides satisfactory repeatability (RSDs lower, in general, than 8.5%) and sensitivity (limits of detection ranging from 0.6 to 81.9 μg/L) for the investigated compounds.

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.