Screening of volatile compounds in honey using a new sampling strategy combining multiple extraction temperatures in a single assay by HS-SPME-GC-MS.

This paper proposes a new optimization strategy for the extraction of volatile compounds from honey samples using headspace solid-phase microextraction (HS-SPME) and separation/detection by gas chromatography-mass spectrometry (GC-MS). The new optimization strategy was based on the use of three different extraction temperatures in a single assay, aiming at extracting a high number of compounds with wide range of volatilities. As an analytical tool, experimental designs were used for the optimization. The variables extraction time (10-80 min), extraction temperature (0-60 °C), water volume (0.5-5 mL) and percentage of sodium chloride saturation in water (0-100%) were optimised using a five-level fractional central composite design with CAR/DVB/PDMS fibre. The final optimised combination of extraction times at each temperature was 60 min with the sample temperature being held at 60 °C for 36 min, 40 °C for 18 min and 0 °C for 6 min. The proposed method was compared to conventional methods which employ one or two extraction temperatures. It was found that the proposed method presented better results considering the response in terms of the arithmetic means of the peak areas. The use of multiple extraction temperatures for the HS-SPME procedure proved to be an excellent alternative for the screening of compounds present in honey with a wide range of volatilities.

Use of two different coating temperatures for a cold fiber headspace solid-phase microextraction system to determine the volatile profile of Brazilian medicinal herbs.

In this study, the experimental extraction conditions on applying headspace solid-phase microextraction and cold fiber headspace solid-phase microextraction (CF-HS-SPME) procedures to samples of six medicinal herbs commonly found in southern Brazil were optimized. The optimized conditions for headspace solid-phase microextraction were found to be an extraction temperature of 60°C and extraction time of 40 min. For CF-HS-SPME, the corresponding values were 60°C and 15 min. In the case of the coating temperature for the CF-HS-SPME system, two approaches were investigated: (i) Temperature of 5°C applied during the whole extraction procedure; and (ii) the use of two fiber temperatures in the same extraction procedure with the aim of extracting the volatile and semivolatile compounds, the ideal condition being 60°C for the first 7.5 min and 5°C for the final 7.5 min. The three extraction procedures were compared. The CF-HS-SPME procedure had good performance only for the more volatile compounds whereas the strategy using two coating temperatures in the same procedure showed good performance for all compounds studied. It was also possible to determine the profile for the volatile fraction of each herb studied applying this technique followed by GC-MS.

Simultaneous determination of polycyclic aromatic hydrocarbons and benzene, toluene, ethylbenzene and xylene in water samples using a new sampling strategy combining different extraction modes and temperatures in a single extraction solid-phase microextraction-gas chromatography-mass spectrometry procedure.

This study proposes a new optimization approach for the simultaneous determination of polycyclic aromatic hydrocarbons (PAHs) and benzene, toluene, ethylbenzene and xylene isomers (BTEX) from water samples using the solid-phase microextraction technique followed by gas chromatography-mass spectrometry (GC-MS) separation and detection. The objective of the study was to achieve compromise extraction conditions, suitable for all semi-volatile and volatile compounds, under which the amount extracted is maximized for all analytes. This was achieved by careful optimization of the fiber coating, salting-out effect, extraction time and temperature and extraction mode (headspace or direct immersion). With the optimized fiber coating - PDMS/DVB 65 µm - the other selected factors were optimized using a response surface methodology through central composite designs. As expected, the optimized results for each class of analytes varied significantly, probably due to the differences in their volatility and the equilibrium constants for the analyte/fiber coating. In order to overcome this issue, a new optimization approach was proposed based on a combination of extraction modes and extraction temperatures in a single extraction procedure. The final optimized procedure was: 48 min of extraction in direct immersion mode with the sample maintained at 80 °C followed by a further 32 min of headspace extraction with the sample temperature kept at 10 °C. The proposed procedure was compared with conventional methods based on the use of a single extraction mode and temperature (80 min of headspace extraction at 60 °C or 80 min of direct immersion extraction at 50 °C). The newly proposed method was shown to be more attractive as it extracted higher amounts of both semi-volatile and volatile compounds in a single extraction procedure compared to the conventional approaches. The optimized method was validated and excellent results were obtained.

Determination of trace silver in water samples by online column preconcentration flame atomic absorption spectrometry using termite digestion product.

A new method for Ag determination in water samples using solid phase extraction (SPE) coupled to a flow injection system and flame atomic absorption spectrometry was developed. The sorbent used for Ag preconcentration and extraction was the termite digestion product. Flow and chemical variables of the system were optimized through a multivariate procedure. The factors selected were adsorbent mass, buffer type and concentration, sample pH, and sample flow rate. The detection limit and precision were 3.4 µg L(-1) and 3.8% (n = 6, 15 µg L(-1)), respectively. The enrichment factor and the linear working range were, respectively, 21 and 10-50 µg L(-1). Results for recovery tests using different water samples were between 96 and 107%. The proposed methodology was applied with success for the determination of Ag in water used to wash clothes impregnated with silver nanoparticles, supplied by a factory located in Santa Catarina, Brazil.

Determination of cadmium in alcohol fuel using Moringa oleifera seeds as a biosorbent in an on-line system coupled to FAAS.

In this study a new method for determination of cadmium in alcohol fuel using Moringa oleifera seeds as a biosorbent in an on-line preconcentration system coupled to flame atomic absorption spectrometry (FAAS) was developed. Flow and chemical variables of the proposed system were optimized through multivariate designs. The limit of detection for cadmium was 5.50microg L(-1) and the precision was below 2.3% (35.0microg L(-1), n=9). The analytical curve was linear from 5 to 150microg L(-1), with a correlation coefficient of 0.9993. The developed method was successfully applied to spiked alcohol fuel, and accuracy was assessed through recovery tests, with recovery ranging from 97.50 to 100%.

Development of a flow system for the determination of cadmium in fuel alcohol using vermicompost as biosorbent and flame atomic absorption spectrometry.

In this study a method for the determination of cadmium in fuel alcohol using solid-phase extraction with a flow injection analysis system and detection by flame atomic absorption spectrometry was developed. The sorbent material used was a vermicompost commonly used as a garden fertilizer. The chemical and flow variables of the on-line preconcentration system were optimized by means of a full factorial design. The selected factors were: sorbent mass, sample pH, buffer concentration and sample flow rate. The optimum extraction conditions were obtained using sample pH in the range of 7.3-8.3 buffered with tris(hydroxymethyl)aminomethane at 50 mmol L(-1), a sample flow rate of 4.5 mL min(-1) and 160 mg of sorbent mass. With the optimized conditions, the preconcentration factor, limit of detection and sample throughput were estimated as 32 (for preconcentration of 10 mL sample), 1.7 microg L(-1) and 20 samples per hour, respectively. The analytical curve was linear from 5 up to at least 50 microg L(-1), with a correlation coefficient of 0.998 and a relative standard deviation of 2.4% (35 microg L(-1), n=7). The developed method was successfully applied to spiked fuel alcohol, and accuracy was assessed through recovery tests, with recovery ranging from 94% to 100%.