Optimization of an analytical methodology for the determination of alkyl- and methoxy-phenolic compounds by HS-SPME in biomass smoke.

A sampling and analysis method for the determination of 21 phenolic compounds in smoke samples from biomass combustion has been developed. The smoke is used to make smoked foods, following an artisanal procedure used in some parts of the Canary Islands. The sampling system consists of a Bravo H air sampler, two impingers, each one containing an aqueous solution of sodium hydroxide 0.1 mol L(-1), followed by a silica gel trap. The variables optimized to reach the best sampling conditions were volume of absorbent solution and sampling flow. Under the optimum conditions, 100 mL of absorbent solution of NaOH 0.10 mol L(-1) and 2 L min(-1) for the sampling flow, sampling efficiencies are higher than 80%. Analysis of phenolic compounds was carried out by headspace solid-phase microextraction (HS-SPME) coupled to gas chromatography-mass spectrometry (GC-MS). Five different fiber coatings were employed in this study. By means of a central composite design, extraction time, salt concentration, and pH of the solution were optimized: 65-microm carbowax-divinylbenzene, extraction time 90 min, concentration in NaCl of 35% (m/v), and pH 2 yielded the highest response. Detection limits of phenol and their alkyl derivatives, guaiacol and eugenol, are between 1.13 and 4.60 ng mL(-1). 3-Methoxyphenol, 2,6-dimethoxyphenol, and vanillin have detection limits considerably higher. Good linearity (R2 > or = 0.98) was observed for all calibration curves in the established ranges. The reproducibility of the method (RSD, relative standard deviation) was found to oscillate between 7 and 18% (generally close or lower than 10%).

Study of the interactions between phenolic compounds and micellar media using micellar solid-phase microextraction/gas chromatography.

Solid-phase microextraction coupled to gas-chromatography with mass-spectrometry detection has been employed to establish the sensitivity indexes as well as to study the partition coefficients of phenols into ionic and nonionic micelles. The sensitivity indexes values can be used to estimate qualitatively the affinity between phenols and micelles. The studied phenols, some of them with high environmental interest, include chloro-, alkyl-, and methoxy-phenols. The results obtained in this work, using 85 microm polyacrylate fiber and anionic (sodium dodecyl sulphate), cationic (cetyltrimethylammonium bromide), and nonionic (Triton X-100 and polyoxyethylene-10-lauryl ether) surfactants, indicate that SPME is a viable method for estimating the micelle partition coefficients.

Polycyclic aromatic hydrocarbons in smoke used to smoke cheese produced by the combustion of rock rose (Cistus monspeliensis) and tree heather (Erica arborea) wood.

In this work, the polycyclic aromatic hydrocarbons (PAHs) and their methyl derivatives concentrations have been determined in smoke from the rock rose and tree heather wood combustion. The combustion is done in two types of smokers, kiln and drum, commonly used in the Canary Islands (Spain) to smoke cheese. The low control of the operational conditions justify the great variability of the PAHs concentration in the emissions, with values between 251.8 and 2547 microg/m3N. In general, the lowest concentrations correspond to the tree heather wood combustion in the drum, while the highest concentrations are usually reached in the rock rose wood combustion in the kiln. However, the relative contributions of each PAH to the total concentration are independently similar to the type of smoker and wood used. In the combustion conditions, the equilibrium is not reached during the PAHs distribution process between the gas and aerosol phases. Therefore, while naphthalene and their 1- and 2-methyl derivatives remain in the gas phase, phenanthrene and PAHs with higher molecular weight remain mainly in the aerosol phase. In this phase, the PAHs concentration represents 39.9% of the total PAHs produced by burning rock rose wood and 29.1% of the total PAHs when tree heather wood is used. To establish the carcinogenic potential in both phases, the percentages of some PAHs were calculated. These values are significantly higher in the aerosol phase and, at the same time, higher when rock rose wood is used.