Application of tandem column solid phase extraction and flame atomic absorption spectrometry for the determination of inorganic and organically bound forms of iron in wine

A tandem column solid phase extraction (SPE) procedure has been devised to examine the fractionation of Fe in wine. Wine was filtered through a 0.45 μm filter and then, the filtrate was driven through an adsorbing Amberlite XAD-7HP column followed by a cation exchange Dowex 50W-x8-200 column. Three different Fe groupings are discriminated and assessed, including hydrophobic species of Fe bound to phenolic substances and related species (phenolic fraction), cationic species comprising simple Fe ions and labile Fe forms (cationic fraction), in addition to anionic and/or neutral Fe complexes with organic acids (residual fraction). The suitability of the procedure has been evaluated analyzing four bottled red wines. The results obtained were verified using another tandem column assemblage in which an adsorbing Amberlite XAD-16 column was exchanged by the Amberlite XAD-7HP column. The fractionation pattern ascertained for Fe in analyzed wines is discussed in reference to previously published works. In addition, a conditioning treatment and preparation of Amberlite XAD resins have been revised.     

Determination of terpenoids in wines by solid phase extraction and gas chromatography

A new method for determination of volatile terpenoids in wine is proposed. An off-line solid phase extraction—gas chromatographic method has been used for the determination. The influence of several extraction variables was studied, including the solid phase employed (C-18 versus divinylbenzene-based), eluting solvent (n-pentane, dichloromethane, ethanol and methanol), volume of eluting solvent (1-4 ml) and drying time (0-20 min). Complete recovery of volatile terpenoids from several kinds of wines was obtained under the optimized conditions.     

Volatile compounds responsible for aroma of Jutrzenka liquer wine

Jutrzenka is a sweet liquer wine produced in Poland from the grape variety of the same name, developed in Poland to withstand the harsh climate of winery regions. Jutrzenka wine has a characteristic aroma with strong fruity and flowery notes, which make it unique among other liquer wines as demonstrated in sensory profile analysis. The work was aimed at characterization of volatile compounds in this wine, with the emphasis on characterization of compounds responsible for its unique aroma. Gas chromatography-olfactometry (GC-O) was applied to identify the key odorants using aroma extract dilution analysis (AEDA) approach. To facilitate free and bound terpenes and C(13)-norisoprenoids identification solid phase extraction (SPE) was used followed by GC/MS. Among identified key odorants β-damascenone was the compound having the highest FD (4096), followed by isoamyl alcohol, 4-mercapto-4-methyl-2-pentanone (FD=2048), methional, linalool, ethyl decanoate (FD=1024) and ethyl hexanoate, furaneol (FD=512). Other significant compounds were ethyl 2-methyl propanoate, ethyl 2-methylbutanoate and phenyl ethyl alcohol. Determination of odor activity values (OAV) showed the highest values for β-damascenone (566), 4-mercapto-4-methyl-2-pentanone (288) ethyl hexanoate (32) and linalool (7). Jutrzenka exhibited also a rich profile of free, and to lesser extent bound terpenes.     

Analytical performance of three commonly used extraction methods for the gas chromatography–mass spectrometry analysis of wine volatile compounds

The analytical performance of three extraction procedures based on cold liquid–liquid extraction using dicloromethane (LLE), solid phase extraction (SPE) using a styrene–divinylbenzene copolymer and headspace solid phase microextraction (SPME) using a carboxen–polydimethylsiloxane coated fibre has been evaluated based on the analysis of 30 representative wine volatile compounds. From the comparison of the three procedures, LLE and SPE showed very good linearity covering a wide range of concentrations of wine volatile compounds, low detection limits, high recovery for most of the volatile compounds under study and higher sensitivity compared to the headspace-SPME procedure. The latter showed in general, poor recovery for polar volatile compounds. Despite some drawbacks associated with the LLE and SPE procedures such as the more tedious sampling treatment and the use of organic solvents, the analytical performance of both procedures showed that they are more adequate for the analysis of wine volatiles.     

Monoterpenes in grape juice and wines

The importance of monoterpenes on varietal flavour of wines has been reviewed. These compounds were mainly found linked to sugar moieties in the grape juice and wines, showing no olfactive characteristics. In this way, mechanisms to liberate terpenes were studied, making a comparative study between acidic and enzymic hydrolysis of terpene glycosides. Finally, analytical techniques developed to study these compounds, in both free or glycosidically forms, and also to fractionate glycosidic precursors, have been discussed.     

Impurities Released from Extractive Phases Used in the Analysis of Pesticides

Abstract

Elution fractions relative to solid phase extraction (SPE) procedures using C-18 bonded silica and Carbopack B columns plus C-18 membranes have been analyzed by gas chromatography-mass spectrometry (GC-MS) for the characterization of interfering compounds from the phases. Alkanes, alkenes, phthalates and some silyl compounds (silanols, siloxanes) have been tentatively identified. Experiments on commercial C-18 phases prepacked in plastic tubes show that the increased interference compared to the phases alone comes from the polymer container. N-butylbenzensulfonamide (NBBSA) was identified as causing interference when the extraction device used for SPE involved plastic components. Increasing amounts of silanol interferences released from the C-18 phases were observed after passage of the water sample, depending on the acidic pH, as evidence of the hydrolysis of the bonded silica.     

Hyphenated gas chromatography-mass spectrometry analysis of 3-mercaptohexan-1-ol and 3-mercaptohexyl acetate in wine: Comparison with results of other sampling procedures via a robust regression

This work describes a new purge and trap gas chromatography electron impact mass spectrometry (PT-GC-EIMS) method for quantifying 3-mercaptohexan-1-ol (3-MH) and 3-mercaptohexyl acetate (3-MHA), two molecules able to characterize some wines with their tropical scents. Firstly the experimental conditions of the purge and trap extraction (sample temperature, extraction time, trap temperature, flow rate) following a multivariate approach were optimized. Then the method through the construction of the calibration curves and the establishment of the detection limits was validated. The purge and trap procedure appears faster and more sensitive than both the headspace solid phase microextraction (HS-SPME) and the solid phase extraction (SPE) procedures, reaching detection limits for the two thiols closer to their sensory thresholds. Evidence of similar performances of the three sampling methods considered was gained comparing the results relevant to same wine samples. The Theil's regression method was used for purpose of comparison.     

Gas chromatography-mass spectrometry determination of 3-mercaptohexan-1-ol and 3-mercaptohexyl acetate in wine: a comparison of headspace solid phase microextraction and solid phase extraction methods

A gas chromatography-mass spectrometry method was established using headspace solid phase microextraction (HS-SPME) as the sampling procedure to analyse 3-mercaptohexan-1-ol (3-MH) and 3-mercaptohexyl acetate (3-MHA), two molecules with a tropical fruit aroma, in wine at trace level. This method offers important advantages, as it neither requires time-consuming sample preparation nor uses dangerous organic compounds, thus making control of wine aroma easier and suitable for routine analysis. As a comparison, a solid phase extraction (SPE) method, already described elsewhere for aroma analysis, was applied to quantify these analytes, extending this exhaustive enrichment to two important thiols. Detection limits for both the approaches were close to the sensory threshold value, resulting lower for the HS-SPME procedure and suitable for requirements in the oenological field. The application of the two proposed methods to 52 wines of different varieties gave similar results.     

Identification of free disaccharides and other glycosides in wine

Free soluble carbohydrates of different wine samples were analyzed by GC–MS as their trimethylsilyloximes using a methylsilicone column. Besides α,α-trehalose, several β-glucosylglucoses such as cellobiose, sophorose, laminaribiose and gentiobiose were the main disaccharides identified. With the exception of gentiobiose, these disaccharides are now reported for the first time in wine. Lactose (4-O-β-d-galactopyranosyl-d-glucose), previously described in this product, was also tentatively identified. Several free glycosides: β-ethyl-glucoside and seven glyceryl-glycosides (including glucosides and galactosides) were also identified for the first time in wine. On the contrary, disaccharides in grape juice were mainly constituted of fructose derivatives, including sucrose, and no glycosides were detected. Although the total amount of disaccharides was different in white wines (<50 mg/L) from those in rosé and red wines (80–130 mg/L), the chromatographic profile was noticeably similar in all wine samples. The method here reported allows the identification of several carbohydrates which have not been previously detected in wines and could contribute to increase the understanding of enzymatic activity during winemaking.     

固相微萃取与色谱联用方法分析水中12种有机氯化合物

运用顶空固相微萃取与色谱闻用方法（ＨＳ－ＳＰＭＥ－ＧＣ）对水中的残留有机氯化合物进行了分析。对影响ＨＳ－ＳＰＭＥ－ＧＣ分析灵敏度的各种实验因素如涂层种类,萃取温度、平衡时间,离子浓度等进行了讨论并将该方法与固相萃取法（ＳＰＥ）,液液萃取法（ＬＬＥ）作了对比,同时考察了常见环境共存污染物直链烷基苯磺酸钠（ＬＡＳ）对几种方法的影响。     

Sampling free and particle‐bound chemicals using solid‐phase microextraction and needle trap device simultaneously

The possibility of sampling the free and particle‐bound concentrations of organic compounds was studied using two different sampling techniques at the same time: needle trap device (NTD) and solid‐phase microextraction (SPME). In this study, a mosquito coil was used to produce gaseous (free) and particle‐bound compounds. Allethrin, the active ingredient in mosquito coils, was chosen as the target analyte. Under the same sampling conditions, the amount of allethrin extracted from the mosquito‐coil smoke was higher for the NTD compared to the SPME fiber, while the extracted amounts were almost the same for both devices when sampling gaseous samples of allethrin. These results can be explained by the fact that the SPME fiber can only extract free molecules (based on diffusion), whereas the NTD, an exhaustive sampling device, collects both free and particle‐bound allethrin. Breakthrough for NTD and carryover for both NTD and SPME were negligible under the given sampling and desorption conditions.     

A reliable and simple method for the assay of neuroendocrine tumor markers in human urine by solid-phase microextraction–gas chromatography-triple quadrupole mass spectrometry

Homovanillic acid (HVA), vanylmandelic acid (VMA), and 5-hydroxyindoleacetic acid (5-HIAA) are the metabolites of some catecholamines such as epinephrine, nor-epinephrine, dopamine and serotonin and their quantification is used in the diagnosis and management of patients with neurocrine tumors. A novel approach in the assay of these biomarkers in human urine samples by solid phase microextraction (SPME) combined with gas chromatography-triple quadrupole mass spectrometry (GC–QqQ-MS) is presented. A preliminary derivatization with ethyl chloroformate/ethanol was used and the corresponding derivatives were then extracted by SPME in immersion mode. The performance of five SPME fibers and three chloroformates were evaluated in univariate mode and the best results were obtained using the polyacrylate fiber and ethyl chloroformate. The variables affecting the efficiency of SPME analysis were optimized by the multivariate approach of “Experimental design” and, in particular, a central composite design (CCD) was applied. The optimum working conditions in terms of response values were achieved by performing analysis at room temperature with addition of NaCl (9.5%) and with an extraction time of 25.8 min. Identification and quantification of analytes were carried out by using a gas chromatography-triple quadrupole mass spectrometry (GC–QqQ MS) system in multiple reaction monitoring (MRM) acquisition. An evaluation of all analytical parameters shows that the proposed method provides satisfactory results. Very good linearities were, in fact, achieved in the tested calibration ranges with correlation coefficient values >0.99 for all the analytes and accuracies and RSDs calculated for between-run and tested at concentrations of 1, 10, and 80 mg L⁻¹ were ranging from 91.3% to 106.6%, and from 0.5 to 8.9%, respectively. Moreover, the LOD values obtained can be considered very satisfactory (1.3, 0.046 and 24.3 μg L⁻¹ for HVA, VMA and 5-HIAA, respectively). The developed protocol represents, therefore, a simple, rapid and selective tool for assaying these acidic biomarkers in urine samples for neuroendocrine cancer diagnosis.     

Development of a simple and rapid solid phase microextraction-gas chromatography–triple quadrupole mass spectrometry method for the analysis of dopamine,serotonin and norepinephrine in human urine

The work aims at developing a simple and rapid method for the quantification of dopamine (DA), serotonin (5-HT) and norepinephrine (NE) in human urine. The urinary levels of these biogenic amines can be correlated with several pathological conditions concerning heart disease, stress, neurological disorders and cancerous tumors. The proposed analytical approach is based on the use of solid phase microextraction (SPME) combined with gas chromatography–triple quadrupole mass spectrometry (GC–QqQ-MS) after a fast derivatization of both aliphatic amino and phenolic moieties by propyl chloroformate. The variables influencing the derivatization reaction were reliably optimized by the multivariate approach of “Experimental design”. The optimal conditions were obtained by performing derivatization with 100 μL of propyl chloroformate and 100 μL of pyridine. The extraction ability of five commercially available SPME fibers was evaluated in univariate mode and the best results were obtained using the polyacrylate fiber. The variables affecting the efficiency of SPME analysis were again optimized by the multivariate approach of “Experimental design” and, in particular, a central composite design (CCD) was applied. The optimal values were extraction in 45 min at room temperature, desorption temperature at 300 °C, no addition of NaCl. Assay of derivatized analytes was performed by using a gas chromatography–triple quadrupole mass spectrometry (GC–QqQ-MS) system in selected reaction monitoring (SRM) acquisition. An evaluation of all analytical parameters demonstrates that the developed method provides satisfactory results. Indeed, very good linearities were achieved in the tested calibration range with correlation coefficient values of 0.9995, 0.9999 and 0.9997 for DA, 5-HT and NE, respectively. Accuracies and RSDs calculated for between-run and tested at concentrations of 30, 200, and 800 μg L⁻¹ were in the range from 92.8% to 103.0%, and from 0.67 to 4.5%, respectively. Finally, the LOD values obtained can be considered very good (0.587, 0.381 and 1.23 μg L⁻¹ for DA, 5-HT and NE, respectively).     

A useful approach for the differentiation of wines according to geographical origin based on global volatile patterns

In this study, the feasibility of solid‐phase extraction combined with gas chromatography and mass spectrometry in tandem with partial least squares discriminant analysis was evaluated as a useful strategy to differentiate wines according to geographical origin (Azores, Canary and Madeira Islands) and types (white, red and fortified wine) based on their global volatile patterns. For this purpose, 34 monovarietal wines from these three wine grape‐growing regions were investigated, combining the high throughput extraction efficiency of the solid‐phase extraction procedure with the separation and identification ability. The partial least squares discriminant analysis results suggested that Madeira wines could be clearly discriminated from Azores and Canary wines. Madeira wines are mainly characterized by 2‐ethylhexan‐1‐ol, 3,5,5‐trimethylhexan‐1‐ol, ethyl 2‐methylbutanoate, ethyl dl ‐2‐hydroxycaproate, decanoic acid, 3‐methylbutanoic acid, and (E)‐whiskey lactone, whereas 3‐ethoxypropan‐1‐ol, 1‐octen‐3‐ol, (Z)‐3‐hexenyl butanoate, 4‐(methylthio)‐1‐butanol, ethyl 3‐hydroxybutanoate, isoamyl lactate, 4‐methylphenol, γ‐octalactone and 4‐(methylthio)‐1‐butanol, are mainly associated with Azores and Canary wines. The data obtained in this study revealed that solid‐phase extraction combined with gas chromatography and quadrupole mass spectrometry data and partial least squares discriminant analysis provides a suitable tool to discriminate wines, both in terms of geographical origin as well as wine type and vintage.     

Headspace solid-phase microextraction–gas chromatography–mass spectrometry for profiling free volatile compounds in Cabernet Sauvignon grapes and wines

The complex aroma of wine is derived from many sources, with grape-derived components being responsible for the varietal character. The ability to monitor grape aroma compounds would allow for better understanding of how vineyard practices and winemaking processes influence the final volatile composition of the wine. Here, we describe a procedure using GC–MS combined with headspace solid-phase microextraction (HS-SPME) for profiling the free volatile compounds in Cabernet Sauvignon grapes. Different sample preparation (SPME fiber type, extraction time, extraction temperature and dilution solvent) and GC–MS conditions were evaluated to optimize the method. For the final method, grape skins were homogenized with water and 8 ml of sample were placed in a 20 ml headspace vial with addition of NaCl; a polydimethylsiloxane SPME fiber was used for extraction at 40 °C for 30 min with continuous stirring. Using this method, 27 flavor compounds were monitored and used to profile the free volatile components in Cabernet Sauvignon grapes at different maturity levels. Ten compounds from the grapes, including 2-phenylethanol and β-damascenone, were also identified in the corresponding wines. Using this procedure it is possible to follow selected volatiles through the winemaking process.     

Solid-phase extraction followed by dispersive liquid–liquid microextraction for the sensitive determination of selected fungicides in wine

A novel approach for the determination of seven fungicides (metalaxyl-M, penconazole, folpet, diniconazole, propiconazole, difenoconazole and azoxystrobin) in wine samples is presented. Analytes were extracted from the matrix and transferred to a small volume of a high density, water insoluble solvent using solid-phase extraction (SPE) followed by dispersive liquid–liquid microextraction (DLLME). Variables affecting the performance of both steps were thoroughly investigated (metalaxyl-M was not included in some optimisation studies) and their effects on the selectivity and efficiency of the whole sample preparation process are discussed. Under optimised conditions, 20 mL of wine were first concentrated using a reversed-phase sorbent and then target compounds were eluted with 1 mL of acetone. This extract was mixed with 0.1 mL of 1,1,1-trichloroethane (CH₃CCl₃) and the blend added to 10 mL of ultrapure water. After centrifugation, an aliquot (1–2 μL) of the settled organic phase was analyzed by gas chromatography (GC) with electron capture (ECD) and mass spectrometry (MS) detection. The method provided enrichment factors (EFs) around 200 times and an improved selectivity in comparison to use of SPE as single sample preparation technique. Moreover, the yield of the global process was similar for red and white wine samples and the achieved limits of quantification (LOQs) (from 30 to 120 ng L⁻¹ and from 40 to 250 ng L⁻¹, for GC–ECD and GC–MS, respectively) were low enough for the determination of target species in commercial wines. Among compounds considered in this work, metalaxyl-M and azoxystrobin were found in several wines at concentrations from 0.8 to 32 ng mL⁻¹.     

Using on-line solid phase extraction for flow-injection spectrophotometric determination of salbutamol

In the proposed procedure, the determination of salbutamol with Folin-Ciocalteau reagent (FC) using a flow injection analysis technique (FIA) with spectrophotometric detection at 750 nm is described. The lab-made FIA system consisted of a peristaltic pump Gilson Minipulse 3 equipped with Tygon tubes, double 6-port external Vici Valco sample injector and S 2000/SAD500 fiber optic spectrophotometer. It was controlled by a PC with use of originally compiled LabVIEW^®—supported software containing the mathematical library with various statistical functions for off-line data evaluation. Concentration, volume of reagents and flow rate were optimised by a simplex method. The proposed system was used for the direct determination of salbutamol sulphate in the tablets and the human urine without preliminary pre-treatment of the sample. The negative effect of interfering substances (excipients of the tablets and matrix of the urine) is overcome by a solid phase extraction (SPE), when salbutamol is adsorbed on the solid phase in the microcolumn, which is integrated directly into the flow system. Pre-treatment of the sample takes place directly in the flowing stream. The sample throughput without carryover of on-line SPE was 60-80 samples per hour. With the SPE column (Baker—carboxylic acid), salbutamol was determined in the linear range from 1 to 15 μg ml⁻¹ (R.S.D.=1.2%), with detection limit (3σ) 0.1 μg ml⁻¹ and a frequency of 40-60 samples per hour in the water solutions. The salbutamol was determined in the linear range from 2 to 20 μg ml⁻¹ (R.S.D.=1.7%), with detection limit (3σ) 1 μg ml⁻¹ and a frequency of 30 samples per hour in the samples of the human urine.     

Solid phase extraction of amines

The objective of this paper is to provide information about solid phase extraction (SPE) as an alternative to liquid-liquid extraction of amines from several matrices. Different sorbents ranging from non-polar phases, such as C₁₈ silica to more polar such as cyanopropylsilica (CN) have been tested for analysis of aliphatic amines as monoamines, diamines and polyamines. Phenylalkylamines such as amphetamine or methamphetamine and heterocyclic amines such as histamine or cephalosporins (which also contain a carboxylic group), have also been studied. The different steps involved in the extraction procedure have been tested (conditioning, retention, pre-concentration, washing and elution) in order to obtain extracts free of interferences and enough sensitivity. C₁₈ silica (100 mg) was selected as optimal phase with recoveries nearly of 100%. The elution of more polar amines was performed in acidic conditions while less polar amines required organic solvents. Cephalosporin retention was performed in acid condition by using disk cartridges EM C_18, which gave better selectivity. The optimised clean-up procedures have been discussed to the quantification of the corresponding amines in real samples (urine, water and beer). The accuracy and precision were outlined.