Development of a method for the determination of polyamines including N-acetylated forms in human saliva via benzoylation and gas chromatography-mass spectrometry.

A simple method for the determination of polyamines and their N-acetylated forms was developed using benzoyl chloride as derivatization reagent, and 1,6-diaminohexane as internal standard, followed by liquid-liquid extraction with ethyl acetate. The organic extract was injected in a gas chromatograph using a programmed temperature vaporizer and the determination and quantification was performed with a quadrupole mass spectrometer. There was no matrix effect with the proposed method, so internal calibration was used to quantify the corresponding derivatives.

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.

In situ derivatization coupled to microextraction by packed sorbentand gas chromatography for the automated determination ofhaloacetic acids in chlorinated water.

A novel analytical method is reported for the determination of monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, monobromoacetic acid, and dibromoacetic acid. These are the five haloacetic acids (HAAs) for which the U.S.

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.

In situ aqueous derivatization as sample preparation technique for gas chromatographic determinations.

The use of derivatization reactions is a common practice in analytical laboratories. Although in many cases it is tedious and time-consuming, it does offer a good alternative for the determination of analytes not compatible to gas chromatography. Many of the reactions reported in the literature occur in organic medium.

Microextraction by packed sorbent for the analysis of pharmaceutical residues in environmental water samples by in situ derivatization-programmed temperature vaporizer-gas chromatography-mass spectrometry.

The present work describes the development and validation of a method for the determination of five non-steroidal anti-inflammatory drugs (NSAIDs: clofibric acid, ibuprofen, naproxen, diclofenac and ketoprofen) in water samples. The fully automated method includes in situ aqueous derivatization followed by analyte enrichment by microextraction by packed sorbent (MEPS) coupled directly to programmed temperature vaporizer-gas chromatography-mass spectrometry (PTV-GC-MS). The MEPS variables, such as sample volume, elution solvent, elution volume, fill and injection speed and washing steps were optimized.

In situ aqueous derivatization and determination of non-steroidal anti-inflammatory drugs by salting-out-assisted liquid-liquid extraction and gas chromatography-mass spectrometry.

A new analytical method for the determination of trace levels of five non-steroidal anti-inflammatory drugs (NSAIDs: clofibric acid, ibuprofen, naproxen, diclofenac and ketoprofen) in water samples is described. The analytical procedure involves in situ aqueous derivatization with N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride (EDC) and 2,2,2-trifluoroethylamine hydrochloride (TFEA) and salting-out liquid-liquid extraction (SALLE), followed by gas chromatography-programmed temperature vaporizer-mass spectrometry (GC-PTV-MS). The influence of several parameters on the efficiency of the derivatization (stirring time, reaction time, reagent concentration and pH), and the extraction (solvent, volume, salts and stirring time) and injection steps (liner, injection volume, liner temperature, injection time, venting time and venting flow) was investigated.

Headspace sampling with in situ carbodiimide-mediated derivatization for the determination of ibuprofen in water samples.

A method using headspace generation and in situ derivatization with water soluble EDC (1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide) and TFEA (2,2,2-trifluoroethylamine) has been optimized for the determination of ibuprofen (2-(p-isobutylphenyl)propionic acid), one of the most common non-steroid anti-inflammatory drug (NSAIDs) residues in surface and wastewater samples. Derivatization was carried out in the vial of the headspace sampler (HS) in only 15 min, after which instrumental measurements were made with gas chromatography-mass spectrometry (GC-MS). As the injection system, a programmed temperature vaporizer (PTV) in the solvent-vent injection mode is proposed in order to increase the sensitivity of the measurements.

GC-MS determination of parabens, triclosan and methyl triclosan in water by in situ derivatisation and stir-bar sorptive extraction.

Stir-bar sorptive extraction in combination with an in situ derivatisation reaction and thermal desorption-gas chromatography-mass spectrometry was successfully applied to determine parabens (methylparaben, isopropylparaben, n-propylparaben, butylparaben and benzylparaben), triclosan and methyltriclosan in water samples. This approach improves both the extraction efficiency and the sensitivity in the GC in a simple way since the derivatisation reaction occurs at the same time as the extraction procedure. The in situ derivatisation reaction was carried out with acetic anhydride under alkaline conditions.

Simplified QuEChERS approach for the extraction of chlorinated compounds from soil samples.

A simplified version of the QuEChERS method for the extraction of chlorinated pollutant compounds from soil samples is proposed. The procedure involves simple liquid extraction of the soil sample with ethyl acetate, followed by the addition of anhydrous MgSO(4). Gas chromatography/electron capture detection (ECD) is then used to analyse the extracts without any other sample pretreatment.

In situ derivatization reaction and determination of ibuprofen in water samples using headspace generation-programmed temperature vaporization-gas chromatography-mass spectrometry.

The aim of the present work is to propose a method for the determination of ibuprofen, as a typical representative of pharmaceutical compounds, in aqueous samples. To do so, an in situ derivatization reaction in aqueous medium was employed in the vial of a headspace sampler (HS), after which instrumental measurements were made with gas chromatography-mass spectrometry (GC-MS). As the injection system we propose a programmed temperature vaporizer (PTV) where, in solvent vent mode, better results can be obtained than with the conventional split and splitless injection modes.

Determination of filbertone in spiked olive oil samples using headspace-programmed temperature vaporization-gas chromatography-mass spectrometry.

A sensitive method for the fast analysis of filbertone in spiked olive oil samples is presented. The applicability of a headspace (HS) autosampler in combination with a gas chromatograph (GC) equipped with a programmable temperature vaporizer (PTV) and a mass spectrometric (MS) detector is explored. A modular accelerated column heater (MACH) was used to control the temperature of the capillary gas chromatography column.

Use of a programmed temperature vaporizer and an in situ derivatization reaction to improve sensitivity in headspace-gas chromatography. Application to the analysis of chlorophenols in water.

In the present work we propose the combined use of a derivatization reaction within the vial of a headspace sampler with a programmed temperature vaporizer (PTV) inlet in the solvent vent mode as a new methodology for obtaining an increase in sensitivity in headspace-gas chromatography (HS-GC) for the analysis of sparingly volatile compounds. As test analytes the following chlorophenols were used: 2-chlorophenol (2CP), 2,4-dichlorophenol (24DCP), 4-chloro-3-methylphenol (4C3MP) and 2,4,6-trichlorophenol (246TCP). The derivatization reaction was carried out with acetic anhydride because it can be carried out in situ in aqueous medium.

Determination of aromatic and polycyclic aromatic hydrocarbons in gasoline using programmed temperature vaporization-gas chromatography-mass spectrometry.

A sensitive method is presented for the fast analysis of three aromatic and six polycyclic aromatic hydrocarbons (biphenyl, 3-methylbiphenyl, 4-methylbiphenyl, fluorene, phenanthrene, fluoranthene, pyrene, 1,2-benz(a)anthracene and chrysene) in gasoline samples. The applicability of a GC device equipped with a programmable temperature vaporizer (PTV) and an MS detector is explored. Additionally, a modular accelerated column heater (MACH) was used to control the temperature of the capillary gas chromatography column.

Simultaneous determination of gasoline oxygenates and benzene, toluene, ethylbenzene and xylene in water samples using headspace-programmed temperature vaporization-fast gas chromatography-mass spectrometry.

A sensitive method is presented for the fast analysis of seven fuel oxygenates (methanol, ethanol, tert-butyl alcohol (TBA), methyl tert-butyl ether (MTBE), ethyl tert-butyl ether (ETBE), tert-amyl methyl ether (TAME) and diisopropyl ether (DIPE)) and benzene, toluene, ethylbenzene and p-xylene (BTEX) in water samples. The applicability of a headspace (HS) autosampler in combination with a GC device equipped with a programmable temperature vaporizer (PTV) and a MS detector is explored. The proposed method achieves a clear improvement in sensitivity with respect to conventional headspace methods due to the use of the PTV.

Determination of benzene in gasoline using direct injection-mass spectrometry.

A high-speed determination of benzene in gasoline samples using a non-separative method based on direct injection into the mass spectrometer is proposed. The results obtained are very similar to those provided with fast GC-MS. The calibration set was made up of gasoline samples in which the benzene was determined chromatographically and samples of gasoline subjected to a process of evaporation--until the complete disappearance of the original benzene--to which known concentrations of this compound had been added.

Use of mass spectrometry methods as a strategy for detection and determination of residual solvents in pharmaceutical products.

In the present work a strategy for the qualitative and quantitative analysis of residual solvents in pharmaceutical products is reported. First, a low-resolution chromatogram is generated for the identification of the solvents present in the samples by means of headspace generation-fast gas chromatography-mass spectrometry (HS-fast GC/MS). From the plotting of this information by means of contour plots with time and mass/charge axes, it is decided whether quantification of such compounds can be accomplished without chromatographic separation or whether it should be done by fast gas chromatography.

Factors affecting signal intensity in headspace mass spectrometry for the determination of hydrocarbon pollution in beach sands.

One of the main limitations to the use of direct coupling of headspace mass spectrometry (HS-MS) for the quantitative determination of analytes in a sample is related to factors affecting the signal intensity. The importance of strategies aimed at compensating this problem is considerable in the case of classification, and is indeed critical as regards the problems involved in quantification. This paper reports the effects of the different factors affecting HS-MS signal intensity in the quantification of the pollution of beach sands by hydrocarbons--the matrix effect, signal instability over time and nature of the different pollutants present in the polluted sands--and proposes possible solutions.

Determination of methyl tert-butyl ether in gasoline: a comparison of three fast methods based on mass spectrometry.

A high-speed quantitative analysis of methyl tert-butyl ether (MTBE) using three different methods with mass spectrometry detection has been performed. The first method is based on fast chromatography and required an analysis time of 5.23 min per sample, although a certain period (6 min) was necessary for the initial measurement conditions to be regained prior to analysing the next sample.

Calibration transfer for solving the signal instability in quantitative headspace-mass spectrometry.

It is reported that calibration transfer is able to compensate the variations in sensitivity in direct coupling of a headspace sampler to a mass spectrometer when used for quantification purposes using multivariate calibration techniques. This strategy of signal stability compensation allows the use of models constructed from large calibration standard sets without having to repeat their measurement even though variations occur in sensitivity, which may or may not be constant along the mass range. This technique offers advantages over the use of internal standards in this methodology and only requires the measurement of a small number of transfer samples with each set of unknown samples.

A method for the detection of hydrocarbon pollution in soils by headspace mass spectrometry and pattern recognition techniques.

In the present work, we report a methodology for the rapid detection of soil pollution by hydrocarbons that is based on direct coupling of a headspace sampler with a mass spectrometer. With no prior treatment, the samples are subjected to the headspace generation process and the volatiles generated are introduced directly into the mass spectrometer, thereby obtaining a fingerprint of the sample analyzed. The mass spectrum corresponding to the mass/charge ratios (m/z) ranging between 49 and 160 atomic mass units (amu) contains the information related to the composition of the headspace and is used as the analytical signal for the characterization of the samples.

Evolution over time of the agricultural pollution of waters in an area of Salamanca and Zamora (Spain).

A survey of the herbicides present in surface and groundwaters was conducted in 1999 in an area of the provinces of Salamanca and Zamora (Central-Western Spain) to assess the degree of pollution of the agricultural land and seasonal changes in the presence of herbicide residues. Ten sites were sampled and screened for 17 herbicides commonly used in the area; the compounds were ureas, triazines, amides, and others. A previously optimised method involving solid-phase extraction with polymeric cartridges, followed by HPLC with diode array detection, was used to monitor the herbicides.

Detection of adulterants in olive oil by headspace-mass spectrometry.

In the present work, we propose the use of direct coupling of a headspace sampler to a mass spectrometer for the detection of adulterants in olive oil. Samples of olive oils were mixed with different proportions of sunflower oil and olive-pomace oil, respectively, and patterns of the volatile compounds in the original and mixed samples were generated. Application of the linear discriminant analysis technique to the data from the signals was sufficient to differentiate the adulterated from the non-adulterated oils and to discriminate the type of adulteration.