Determination of leucine and isoleucine/allo-isoleucine by electrospray ionization-tandem mass spectrometry and partial least square regression: Application to saliva samples.

Herein we propose, for the first time, a rapid method based on flow injection analysis, electrospray ionization-tandem mass spectrometry (FIA-ESI-MS/MS) and multivariate calibration for the determination of l-leucine, l-isoleucine and L-allo-isoleucine in saliva. As far as we know, multivariate calibration has never been applied to the data from this non-separative approach. The possibilities of its use were explored and the results obtained were compared with the corresponding ones when using univariate calibration. Partial least square regression (PLS1) multivariate calibration models were built for each analyte by analyzing different saliva samples, and were subsequently applied to the analysis of another set of samples which had not been used in any calibration step. For Leu, the model worked satisfactorily with root mean square errors in the prediction step of 17%. This error can be considered acceptable and is common in methodologies that do not include a separation step. Results were compared with those obtained when univariate calibration was used, using the m/z transition 132.1 â†’ 43.0 as the quantitation variable. In this case, the obtained results were not acceptable, with RMSEP of 236%, due to the fact that saliva samples contained another compound, different to the target analytes, which also shared the same transition. Ile and aIle have the same fragmentation patterns, so quantification of the sum of both compounds was performed, with RMSEP of 14% using a PLS1 model. Similar results were obtained when a univariate calibration model using the m/z transition 132.1 â†’ 69.0 was employed. However, the use of this transition should be carefully examined when other compounds present in the matrix contribute to the analytical signal. The method increases sample throughput more than one order of magnitude compared to the corresponding LC-ESI-MS/MS method and is especially suitable as screening. When abnormally high or low concentrations of the analytes studied are obtained, the use of the method that includes separation is recommended to confirm the results.

Non-separative method based on a single quadrupole mass spectrometer for the semi-quantitative determination of amino acids in saliva samples. A preliminary study.

Amino acids have been of great interest in clinical studies since variation in their concentration may provide information about different disorders. For the first time, a non-separative method based on single quadrupole mass spectrometry (qMS) for the simultaneous semiquantitative determination of sixteen amino acids in saliva samples has been developed. The method includes derivatisation of amino acids with ethyl chloroformate-pyridine-ethanol to obtain volatile products, liquid-liquid extraction (LLE) and further analysis using a programmed temperature vaporizer (PTV) coupled to qMS. This method could be applied to the analysis of a great number of saliva samples, limiting the use of separative methods only when abnormal concentrations of amino acids were found, reducing analysis time and cost. The results obtained in the determination of amino acids using the non-separative method were compared to those obtained when a separative method based on gas chromatography (GC) was used, providing values of average relative predictive error (E %) ranging between 2 and 48%. Repeatability and reproducibility were tested, obtaining relative standard deviation (RSD) values equal to or lower than 11% and 16%, respectively. Detection limits were in the range of 0.076-8.747 mg L-1 for the non-separative method.

Multiple headspace sampling coupled to a programmed temperature vaporizer to improve sensitivity in headspace-gas chromatography. Determination of aldehydes.

The improvement of sensitivity in headspace (HS) sampling of not very volatile analytes constitutes a challenge that has usually been approached through coupling with additional techniques. Here we propose a new methodology for increasing sensitivity through a multistep approach. This proof of concept is based on direct coupling of a headspace sampler with a programmed temperature vaporizer (PTV) and a gas chromatograph (GC), with mass spectrometry (MS) detection. Analytes are extracted from the same vial in a stepwise procedure, splitting the headspace generation time of conventional HS into four periods and using the PTV to cryogenically trap the analytes during the successive HS samplings. Solvent vent mode is mandatory in order to retain the analytes, purging the gas solvent at an adequate initial low temperature and flash-heating the PTV liner in a quick ramp (720 °C/min), once the HS samplings are finished. Linear aldehydes, from pentanal to decanal, possible biomarkers of several diseases have been selected as model compounds. This multiple HS method has been compared with conventional HS, and it has been validated in terms of linearity, limits of detection, repeatability, reproducibility and accuracy. The limits of detection (LOD) ranged from 0.004 to 0.159 µg/L. Enrichment factors (EF) in relation to the conventional HS method ranged from 3.0 to 6.7, except for pentanal (EF: 0.8), which is too volatile and polar to be trapped in the PTV with the multiple HS methodology. Similar enrichment factors were obtained in a urine sample.

Determination of polyamines and related compounds in saliva via in situ derivatization and microextraction by packed sorbents coupled to GC-MS.

Here we show the determination of different polyamines (putrescine, cadaverine, spermidine) and related compounds (gamma-aminobutyric acid and l-ornithine) in saliva samples. These compounds are known to be biomarkers for several diseases. We have optimised an in situ derivatization process using ethyl chloroformate, an automated microextraction by packed sorbent and the determination of the corresponding products using a programmed temperature vaporizer coupled to a gas chromatograph - mass spectrometer. After finding that saliva matrix has an effect on the analysis, quantitation was performed using the one-point standard additions method and normalization to IS. This allows the detection of the analytes in the range of µg/L within a matrix obtained by a non-invasive procedure. The method has been successfully validated and it has been used in the determination of these compounds in six saliva samples finding that putrescine and cadaverine present the highest concentrations in the subject diagnosed with rheumatoid arthritis. For ornithine and spermidine, the highest concentrations were found for male subjects, especially heavy smokers. All concentrations found for the compounds were in good agreement with data found in bibliography.

Development of a screening and confirmatory method for the analysis of polar endogenous compounds in saliva based on a liquid chromatographic-tandem mass spectrometric system.

In this paper, a high-throughput approach is proposed for the sensitive screening and the confirmatory analysis of polar compounds in saliva using a two-step approach based on a liquid chromatographic system coupled to a triple quadrupole mass spectrometer. A reversed-phase chromatographic column was used in both steps and changes in the composition of the mobile phase allowed the screening and the confirmatory analyses to be performed with the same instrumental configuration. The proposed strategy has been tested for the determination of a multiclass group of polar endogenous compounds (creatinine, polyamines and amino acids) in saliva samples. The validation of the entire procedure showed consistent results for all the compounds in both steps. Repeatability and reproducibility were evaluated for both procedures, with values below 8% in the case of repeatability and 17% in the case of reproducibility. The instrumental limits of detection were found to be between 1.22 × 10-3 and 46.1 × 10-3 mg/L for creatinine and lysine, respectively, and accuracy of the method was evaluated in terms of apparent recoveries and values were found to be between 80 and 127%. Matrix effects were evaluated and it was found that the analytical outcome was influenced by the matrix of the sample. Thus, a one-point standard addition method was used for quantification. The optimized two-step procedure was applied to saliva samples from apparent healthy volunteers. Overall, satisfactory results were obtained in both steps, demonstrating its applicability for quantitative analysis of polar endogenous compounds in this kind of matrices.

Non-separative mass spectrometry methods for non-invasive medical diagnostics based on volatile organic compounds: A review.

In this review, an assessment of non-separative methods based on mass spectrometry used to analyse volatile organic compounds in the field of bioanalysis is performed. The use of non-separative methods based on mass spectrometry has been established as an attractive option for analysing compounds. These instrumental configurations are suitable for biomedical applications because of their versatility, rapid output of results, and the wide range of volatile organic compounds that can be determined. Here, techniques such as headspace sampling coupled to mass spectrometry, membrane introduction mass spectrometry, selected ion flow tube mass spectrometry, proton transfer reaction mass spectrometry, secondary electrospray ionization mass spectrometry and ion mobility mass spectrometry, are evaluated. Samples involving non-invasive methods of collection, such as urine, saliva, breath and sweat, are mainly considered. To the best of our knowledge, a comprehensive review of all the non-separative instrumental configurations applied to the analysis of gaseous samples from all matrices non-invasively collected has not yet been carried out. The assessment of non-separative techniques for the analysis of these type of samples can be considered a key issue for future clinical applications, as they allow real-time sample analysis, without patient suffering. Any contribution to the early diagnosis of disease can be considered a priority for the scientific community. Therefore, the identification and determination of volatile organic compounds related to particular diseases has become an important field or research.

Quantitative and qualitative analysis of polycyclic aromatic hydrocarbons in urine samples using a non-separative method based on mass spectrometry.

In this work, a method for the quantitative and qualitative analysis of 11 polycyclic aromatic hydrocarbons (PAHs) in urine samples is reported. The method is based on the coupling of a programmed temperature vaporizer (PTV) with a quadrupole mass spectrometer (qMS), via a deactivated fused silica tubing. Before the PTV-qMS analysis, the samples were subjected to a liquid-liquid extraction (LLE). The method was rapid since no chromatographic separation was performed. The samples were introduced directly into the PTV, and the analytes were trapped in the Tenax-TA® packed liner while the solvent was purged. After that, all the compounds reached the mass spectrometer, obtaining the fingerprint of the analysed samples. Urine samples free of PAHs and the same samples spiked with the compounds were analysed. The resulting profile signals were used to quantify the analytes using multivariate calibration, and to classify the samples according to the presence or absence of the PAHs. In the latter task, non-supervised and supervised pattern recognition techniques were employed. The calibration models worked satisfactorily and errors lower or equal to 15% were obtained, in most cases, when an external validation set was analysed. Regarding the classification of the samples, most of the supervised pattern recognition techniques provided excellent results (100% success), where all of the samples were classified correctly.

Use of microextraction by packed sorbent directly coupled to an electron ionization single quadrupole mass spectrometer as an alternative for non-separative determinations.

Sometimes it is not necessary to separate the individual compounds of a sample to resolve an analytical problem, it is enough to obtain a signal profile of the sample formed by all the components integrating it. Within this strategy, electronic noses based on the direct coupling of a headspace sampler with a mass spectrometer (HS-MS) have been proposed. Nevertheless, this coupling is not suitable for the analysis of non-volatile compounds. In order to propose an alternative to HS-MS determinations for non-volatile compounds, here we present the first 'proof of concept' use of the direct coupling of microextraction by packed sorbents (MEPS) to a mass spectrometer device using an electron ionization (EI) and a single quadrupole as ionization source and analyzer, respectively. As target compounds, a set of analytes with different physic-chemical properties were evaluated (2-ethyl-1-hexanol, styrene, 2-heptanone, among others). The use of MEPS extraction present many advantages, such as it is fast, simple, easy to automate and requires small volumes of sample and organic solvents. Moreover, MEPS cartridges are re-usable as samples can be extracted more than 100 times using the same syringe. In order to introduce into the system all the elution volume from the MEPS extraction, a programmable temperature vaporizer (PTV) is proposed as the injector device. Results obtained with the proposed methodology (MEPS-PTV/MS) were compared with the ones obtained based on the separative scheme, i.e. using gas chromatography separation (MEPS-PTV-GC/MS), and both methods provided similar results. Limits of detection were found to be between 3.26 and 146.6µgL-1 in the non-separative scheme and between 0.02 and 1.72µgL-1 when the separative methodology was used. Repeatability and reproducibility were evaluated with values below 17% in all cases.

Headspace-programmed temperature vaporizer-mass spectrometry and pattern recognition techniques for the analysis of volatiles in saliva samples.

A rapid method for the analysis of volatiles in saliva samples is proposed. The method is based on direct coupling of three components: a headspace sampler (HS), a programmable temperature vaporizer (PTV) and a quadrupole mass spectrometer (qMS). Several applications in the biomedical field have been proposed with electronic noses based on different sensors. However, few contributions have been developed using a mass spectrometry-based electronic nose in this field up to date. Samples of 23 patients with some type of cancer and 32 healthy volunteers were analyzed with HS-PTV-MS and the profile signals obtained were subjected to pattern recognition techniques with the aim of studying the possibilities of the methodology to differentiate patients with cancer from healthy controls. An initial inspection of the contained information in the data by means of principal components analysis (PCA) revealed a complex situation were an overlapped distribution of samples in the score plot was visualized instead of two groups of separated samples. Models using K-nearest neighbors (KNN) and Soft Independent Modeling of Class Analogy (SIMCA) showed poor discrimination, specially using SIMCA where a small distance between classes was obtained and no satisfactory results in the classification of the external validation samples were achieved. Good results were obtained when Mahalanobis discriminant analysis (DA) and support vector machines (SVM) were used obtaining 2 (false positives) and 0 samples misclassified in the external validation set, respectively. No false negatives were found using these techniques.

Derivatization coupled to headspace programmed-temperature vaporizer gas chromatography with mass spectrometry for the determination of amino acids: Application to urine samples.

A new method based on headspace programmed-temperature vaporizer gas chromatography with mass spectrometry has been developed and validated for the determination of amino acids (alanine, sarcosine, ethylglycine, valine, leucine, and proline) in human urine samples. Derivatization with ethyl chloroformate was employed successfully to determine the amino acids. The derivatization reaction conditions as well as the variables of the headspace sampling were optimized. The existence of a matrix effect was checked and the analytical characteristics of the method were determined. The limits of detection were 0.15-2.89 mg/L, and the limits of quantification were 0.46-8.67 mg/L. The instrumental repeatability was 1.6-11.5%. The quantification of the amino acids in six urine samples from healthy subjects was performed with the method developed with the one-point standard additions protocol, with norleucine as the internal standard.

Use of microextraction by packed sorbents and gas chromatography-mass spectrometry for the determination of polyamines and related compounds in urine.

A novel methodology for the determination of ornithine, putrescine, cadaverine, spermidine and gamma-amino butyric acid in urine samples has been developed. The method uses in situ aqueous derivatization followed by automated microextraction by packed sorbent coupled to a gas chromatography-mass spectrometry system equipped with a programmed temperature vaporizer. This instrumental configuration minimizes sample manipulation due to from the mixing of the reagents, the process is completely automated. The analytes were derivatized using ethyl chloroformate as derivatization reagent. The reaction occurred in aqueous medium and was carried out in 1min in the vial of an autosampler used to perform microextraction by packed sorbent. The parameters affecting derivatization, extraction and separation were optimized in order to obtain maximum sensitivity. Calibration curves were obtained for five calibration levels in three different matrices. All the calibration models displayed good linearity, with R(2) values higher than 0.95. The validity of the models was checked using ANOVA, and it was observed that they did not exhibit any lack of fit. Repeatability and reproducibility was evaluated, with values below 15% in both cases. LOD and LOQ values were found to be in the low µg/L level. Influence of the matrix was confirmed, thus quantification was performed using the standard additions method and normalization to IS. The method developed was applied to the analysis of these compounds in urine samples from healthy individuals and cancer diagnosed patients (Internal Medicine Unit of the Virgen de la Vega Hospital, Salamanca, Spain). Significant differences (Mann-Whitney U test) were observed for putrescine and ornithine concentrations.

In situ derivatization combined to automated microextraction by packed sorbents for the determination of chlorophenols in soil samples by gas chromatography mass spectrometry.

A method based on the coupling of in situ extraction and derivatization of chlorophenols (CPs) (2-chlorophenol, 4-chloro-3-methylphenol, 2,4-dichlorophenol, and 2,4,6-trichlorophenol) from soils, accomplishing their preconcentration by means of automated microextraction by packed sorbent (MEPS), is proposed. After extraction and acylation of the chlorophenols in aqueous medium, the liquid phase obtained is subjected to the MEPS procedure. The QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) and MEPS techniques were compared and the results confirmed the preconcentration carried out with MEPS. The existence of a matrix effect was checked and the analytical characteristics of the method were determined in a soil sample. The method provided good linearity (from 1 to 12µgkg(-1)), together with good repeatability and reproducibility values (RSD equal to or less than 10%). The limits of detection were in the 0.118-0.894µgkg(-1) range. A certified reference material was applied to validate the proposed methodology.

Sensitivity enhancement in the determination of volatile biomarkers in saliva using a mass spectrometry-based electronic nose with a programmed temperature vaporizer.

With a view to improving the sensitivity of direct coupling of a headspace sampler (HS) with a mass spectrometer (MS), here we propose the use of a programmed temperature vaporizer (PTV) in solvent-vent injection mode before the sample is introduced into the MS. This preconcentration scheme has been used for some time in many methods based on gas chromatography (GC), but to the best of our knowledge it has not yet been used in an electronic nose based on MS. The increase in the S/N ratio with the proposed instrumental configuration (HS-PTV/MS) lies between 6.9- and 22-fold. The main advantage of using this injector lies in the fact that it does not involve time-consuming steps. To check the possibilities of this methodology, saliva samples from healthy volunteers and patients with different types of illnesses (including some types of cancer) were analyzed. None of the compounds studied was detected in the samples corresponding to the healthy volunteers. One or more biomarkers, at levels ranging from 13 to 500 µg/L, were found in five of the samples from the patients. Additionally, separative analysis by HS-PTV-GC/MS was performed for confirmatory purposes and both methods provided similar results. The main advantage of the proposed methodology is that no prior chromatographic separation and no sample manipulation are required.

Ionic liquids as stationary phases in gas chromatography: determination of chlorobenzenes in soils.

The present research focuses on the evaluation of different ionic liquid (IL) stationary phases in gas chromatography. The different IL columns were evaluated in terms of peak resolution (Rs) and peak symmetry for the separation of the chlorobenzenes. The determination of chlorobenzenes in soil samples by means of the optimal IL stationary phase (SLB-IL82) is proposed as an application. Soil pretreatment was based on a simplified quick, easy, cheap, effective, rugged, and safe extraction procedure and a large injection volume via a programed temperature vaporizer working in solvent vent mode. The retention time of the chlorobenzenes increased as the polarity of the IL column decreased. SLB-IL82 is the stationary phase that provides the best values as regards Rs and asymmetry factor. Soil sample blanks were spiked with the analytes before subjecting the sample to the extraction process. The existence of a matrix effect was checked and the analytical characteristics of the method were determined in a fortified garden soil sample. The method provided good linearity, good repeatability and reproducibility values, and the LODs were in the 0.1-4.7 µg/kg range. Two fortified soil samples were applied to validate the proposed methodology.

Determination of chlorobenzenes in water samples based on fully automated microextraction by packed sorbent coupled with programmed temperature vaporization-gas chromatography-mass spectrometry.

A fully automated method consisting of microextraction by packed sorbent (MEPS) coupled directly to programmed temperature vaporizer-gas chromatography-mass spectrometry (PTV-GC-MS) has been developed to determine the 12 chlorobenzene congeners (chlorobenzene; 1,2-, 1,3-, and 1,4-dichlorobenzene; 1,2,3-, 1,2,4-, and 1,3,5-trichlorobenzene; 1,2,3,4-, 1,2,3,5-, and 1,2,4,5-tetrachlorobenzene; pentachlorobenzene; and hexachlorobenzene) in water samples. The effects of the variables on MEPS extraction, using a C18 sorbent, and the instrumental PTV conditions were studied. The internal standard 1,4-dichlorobenzene d4 was used as a surrogate. The proposed method afforded good reproducibility, with relative standard deviations (RSD %) lower than 12%. The limits of detection varied between 0.0003 µg L(-1) for 1,2,3,4-tetrachlorobenzene and 0.07 µg L(-1) for 1,3- and 1,4-dichlorobenzene, while those of quantification varied between 0.001 µg L(-1) and 0.2 µg L(-1) for the same compounds. Accuracy of the proposed method was confirmed by applying it to the determination of chlorobenzenes in different spiked water samples, including river, reservoir, and effluent wastewater.

Coupling of microextraction by packed sorbents with gas chromatography with ionic liquid stationary phases for the determination of haloanisoles in wines.

A new method based on the coupling of microextraction by packed sorbents (MEPS) and gas chromatography with ionic liquid stationary phases for the determination of four haloanisoles in wine matrices is proposed. The analytes were concentrated in a C18 barrel insert and needle (BIN), desorbed with a small volume of an organic solvent, and determined by gas chromatography with electron-capture detection (GC-µECD). The influence of several factors on the efficiency of extraction, washing and elution steps was investigated. Additionally, ionic liquid stationary phases of very different polarities were evaluated in terms of efficiency. Under optimized conditions, the analytes were first extracted in the sorbent material and, after an adequate washing step, eluted with 50 µL of ethanol. An aliquot of 5 µL of this extract was further injected, using a programmed temperature vaporizer (PTV), into the chromatographic system. The yield of the overall procedure ranged from 48 to 60%; the reproducibility of the method, calculated as the relative standard deviation (RSD), was below 10% for all compounds, and the limits of detection ranged from 1.2 to 4.8 ng L(-1). External calibration was used in the determination of the target compounds in wine samples.

A method based on microextraction by packed sorbent-programmed temperature vaporizer-fast gas chromatography-mass spectrometry for the determination of aromatic amines in environmental water samples.

We report a sensitive method for the determination of 15 aromatic amines in environmental water samples. They have been included in the list of priority pollutants in surface water by the European Union. The method is based on analyte enrichment using microextraction by packed sorbent (MEPS) and later analysis using programmed temperature vaporizer-gas chromatography-mass spectrometry (PTV-GC-MS). All MEPS steps were carried out manually. The detection limits were of the order of nanograms per liter for most of the compounds. The results were compared with those obtained without MEPS using the method exclusively based on direct injection of the sample into the PTV-GC-MS. External calibration in ultrapure water was used in the determination of the compounds studied in five types of water samples (sea, river, tap, influent, and effluent waste water) since no significant matrix effect was found. The results obtained can be considered highly satisfactory and they revealed the presence of aniline in the sea and the influent and effluent waste water samples.

A simplified Quick, Easy, Cheap, Effective, Rugged and Safe approach for the determination of trihalomethanes and benzene, toluene, ethylbenzene and xylenes in soil matrices by fast gas chromatography with mass spectrometry detection.

A method based on simplified QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) extraction followed by large-injection volume-fast gas chromatography and mass spectrometry detection has been developed for the determination of trihalomethanes (chloroform, bromodichloromethane, dibromochloromethane and bromoform) and BTEX (benzene, toluene, ethylbenzene and xylenes) in soil samples. The simplified version of QuEChERS used meets the requirements of the "green chemistry" and provides reliable results with high sample throughput, low solvent consumption, little labour and the use of materials commonly employed in laboratories. The GC device used is equipped with a programmable temperature vaporizer (PTV), with a liner packed with Tenax-TA(®). Using the solvent-vent mode, the PTV allows the injection of large volumes of sample, affording an improvement in the sensitivity of the method. The chromatographic conditions used here allowed the separation of the compounds in less than 5.50 min. Good linearity was obtained for all the target compounds, with highly satisfactory repeatability and reproducibility values. The limits of detection were in the 0.2 to 15 µg kg(-1) range. The method was validated by the analysis of two certified reference materials.

Determination of antioxidants in new and used lubricant oils by headspace-programmed temperature vaporization-gas chromatography-mass spectrometry.

A sensitive method is presented to determine antioxidants (2-, 3-, and 4-tert-butylphenol, 2,6-di-tert-butylphenol, 3-tert-butyl-4-hydroxyanisol, 2,6-di-tert-butyl-4-methylphenol, 1-naphthol, and diphenylamine) in new and used lubricant oil samples. Research was carried out on a GC device equipped with a headspace sampler, a programmed temperature vaporizer, and an MS detector unit. The proposed method does not require sample treatment prior to analyses, hence eliminating possible errors occurring in this step. Sample preparation is reduced when placing the oil sample (2.0 g) in the vial and adding propyl acetate (20 µL). Solvent vent injection mode permits a pre-concentration of the compounds of interest in the liner filled with Tenax-TA®, while venting other species present in the headspace. Thereby, both the life of the liner and the capillary column is prolonged, and unnecessary contamination of the detector unit is avoided. Calibration was performed by adding different concentrations of analytes to a new oil which did not contain any of the studied compounds. Limits of detection as low as 0.57 µg/L (2-tert-butylphenol) with a precision lower or equal to 5.3% were achieved. Prediction of the antioxidants in new oil samples of different viscosities (5W40, 10W40, and 15W40) was accomplished with the previous calibration, and the results were highly satisfactory. To determine antioxidants in used engine oils, standard addition method was used due to the matrix effect.

Determination of trihalomethanes in soil matrices by simplified quick, easy, cheap, effective, rugged and safe extraction and fast gas chromatography with electron capture detection.

A method based on QuEChERS extraction is proposed for the determination of trihalomethanes (chloroform, bromodichloromethane, dibromocloromethane and bromoform) in soil samples. The new version of QuEChERS adapted to soil samples consists of liquid extraction with ethyl acetate, the addition of water to moisten the samples, salting-out partitioning of the water with anhydrous MgSO4, and direct injection of the organic extract, obtained after the centrifugation step, into the gas chromatograph. This simplified extraction procedure maintains the advantages of the original method and avoids some steps, making the final procedure simpler, faster, and cheaper, with the consequent reduction in errors associated with sample manipulation. The experimental conditions of the analytical method, based on fast gas chromatography (FGC) and micro-electron capture detection (microECD), were optimized. The column and oven program used allowed fast separation of the compounds in less than 4 min and the total analysis cycle time was as short as 10 min. The existence of a matrix effect was checked and the analytical conditions of the method were studied in a fortified garden soil sample. The highly sensitive and selective detector used afforded to detection limits in the order of ng/kg for the target compounds. To validate the proposed method two certified reference materials (CRMs) were analyzed.