Josias Merib

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.

Cork as a new (green) coating for solid-phase microextraction: Determination of polycyclic aromatic hydrocarbons in water samples by gas chromatography–mass spectrometry

A new fiber for solid-phase microextraction (SPME) was prepared employing cork as a coating. The morphology and composition of the cork fiber was evaluated by scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR), respectively. The proposed fiber was used for the determination of polycyclic aromatic hydrocarbons (PAHs) in river water samples by gas chromatography-selected ion monitoring-mass spectrometry (GC-SIM-MS). A central composite design was used for optimization of the variables involved in the extraction of PAHs from water samples. The optimal extraction conditions were extraction time and temperature of 60 min and 80°C, respectively. The detection and quantification limits were 0.03 and 0.1 μg L(-1), respectively. The recovery values were between 70.2 and 103.2% and the RSD was ≤15.7 (n=3). The linear range was 0.1-10 μg L(-1) with r≥0.96 and the fiber-to-fiber reproducibility showed RSD≤18.6% (n=5). The efficiency of the cork fiber was compared with commercially available fibers and good results were achieved, demonstrating the applicability and great potential of cork as a coating for SPME.

Use of green coating (cork) in solid-phase microextraction for the determination of organochlorine pesticides in water by gas chromatography-electron capture detection

A novel method for the determination of organochlorine pesticides in water samples with extraction using cork fiber and analysis by gas chromatography with electron capture detector was developed. Also, the procedure to extract these pesticides with DVB/Car/PDMS fiber was optimized. The optimization of the variables involved in the extraction of organochlorine pesticides using the aforementioned fibers was carried out by multivariate design. The optimum extraction conditions were sample temperature 75 °C, extraction time 60 min and sodium chloride concentration 10% for the cork fiber and sample temperature 50 °C and extraction time 60 min (without salt) for the DVB/Car/PDMS fiber. The quantification limits for the two fibers varied between 1.0 and 10.0 ng L(-1). The linear correlation coefficients were >0.98 for both fibers. The method applied with the use of the cork fiber provided recovery values between 60.3 and 112.7 and RSD≤25.5 (n=3). The extraction efficiency values for the cork and DVB/Car/PDMS fibers were similar. The results show that cork is a promising alternative as a coating for SPME.

Simultaneous determination of trihalomethanes and organochlorine pesticides in water samples by direct immersion-headspace-solid phase microextraction.

In this study the extraction conditions for the simultaneous extraction of volatile (trihalomethanes - THM) and semi-volatile (organochlorine pesticides) compounds from water samples by direct immersion-headspace-solid phase microextraction (DI-HS-SPME) were optimized and compared. The extraction efficiencies of the proposed DI-HS-SPME and traditional SPME modes were also compared. The separation and detection were performed by gas chromatography-mass spectrometry in SIM mode (GC-MS-SIM). The variables evaluated were extraction time, extraction temperature and added volume of aqueous NaCl solution at 20% (m/v). Central composite designs were carried out to determine the optimal extraction conditions for each SPME mode. The optimal condition for the DI-HS-SPME mode was 80min of total extraction time (64min at 70°C in DI-SPME mode and 16min at 12°C in HS-SPME mode) with 5mL of 20% (m/v) NaCl solution. The SPME extraction modes were compared and the DI-HS-SPME produced excellent results for both volatile and semi-volatile compounds. This represents a promising alternative for the analysis of matrices that contain compounds with very different ranges of volatility. The analytical figures of merit were evaluated and good results were obtained using this procedure for both classes of compounds studied. The limit of quantitation ranged from 0.02 to 2.0μgL(-1) for organochlorine pesticides and from 0.30 to 0.77μgL(-1) for THM.

Novel analytical procedure using a combination of hollow fiber supported liquid membrane and dispersive liquid-liquid microextraction for the determination of aflatoxins in soybean juice by high performance liquid chromatography - Fluorescence detector.

This study describes a combination between hollow fiber membrane and dispersive liquid-liquid microextraction for determination of aflatoxins in soybean juice by HPLC. The main advantage of this approach is the use of non-chlorinated solvent and small amounts of organic solvents. The optimum extraction conditions were 1-octanol as immobilized solvent; toluene and acetone at 1:5 ratio as extraction and disperser solvents (100 μL), NaCl at 2% of the sample volume and extraction time of 60 min. The optimal condition for the liquid desorption was 150 μL acetonitrile:water (50:50 v/v) and desorption time of 20 min. The linear range varied from 0.03 to 21 μg L(-1), with R(2) coefficients ranging from 0.9940 to 0.9995. The limits of detection and quantification ranged from 0.01 μg L(-1) to 0.03 μg L(-1) and from 0.03 μg L(-1) to 0.1 μg L(-1), respectively. Recovery tests ranged from 72% to 117% and accuracy between 12% and 18%.

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.

A novel approach to bar adsorptive microextraction: Cork as extractor phase for determination of benzophenone, triclocarban and parabens in aqueous samples

This study describes the use of cork as a new coating for bar adsorptive microextraction (BAμE) and its application in determining benzophenone, triclocarban and parabens in aqueous samples by HPLC-DAD. In this study bars with 7.5 and 15 mm of length were used. The extraction and liquid desorption steps for BAμE were optimized employing multivariate and univariate procedures. The desorption time and solvent used for liquid desorption were optimized by univariate and multivariate studies, respectively. For the extraction step the sample pH was optimized by univariate experiments while the parameters extraction time and ionic strength were evaluated using the Doehlert design. The optimum extraction conditions were sample pH 5.5, NaCl concentration 25% and extraction time 90 min. Liquid desorption was carried out for 30 min with 250 μL (bar length of 15 mm) or 100 μL (bar length of 7.5 mm) of ACN:MeOH (50:50, v/v). The quantification limits varied between 1.6 and 20 μg L(-1) (bar length of 15 mm) and 0.64 and 8 μg L(-1) (bar length of 7.5 mm). The linear correlation coefficients were higher than 0.98 for both bars. The method with 7.5 mm bar length showed recovery values between 65 and 123%. The bar-to-bar reproducibility and the repeatability were lower than 13% (n = 2) and 14% (n = 3), respectively.

Use of Doehlert design in the optimization of extraction conditions in the determination of organochlorine pesticides in bovine milk samples by HS-SPME

In this study, the extraction of pesticides lindane, heptachlor, aldrin, dieldrin and endrin from milk samples by HS-SPME was investigated followed by separation/detection of these compounds by gas chromatography coupled to an electron capture detector (GC-ECD). Due to the high complexity of milk samples and the hydrophobicity of the studied organochlorine pesticides, the samples were diluted with saturated NaCl solution prior to optimization of the extraction conditions. Dilution tests indicated that a total sample volume of 2 mL (0.5 mL of milk and 1.5 mL of NaCl solution) provided the best chromatographic responses. The fiber coating DVB/Car/PDMS presented the best extraction efficiency towards the target compounds. Optimization was performed using a Doehlert design, and the best conditions were found to be an extraction temperature of 80 °C and an extraction time of 90 min. The HS-SPME mode was used for all extractions from the milk samples. A single fiber, selected during the optimization of fiber coating, was used throughout the study, and no damage on coating was observed. The analytical figures of merit were evaluated, and good results were obtained for the extraction of the target organochlorine pesticides. The percentages of recovery were higher than 75% and the limit of quantitation ranged from 0.5 to 1.2 μg L−1 (for heptachlor and dieldrin, respectively).

A hybrid material as a sorbent phase for the disposable pipette extraction technique enhances efficiency in the determination of phenolic endocrine-disrupting compounds

In this study, the hybrid material 3-n-propyl(3-methylpyridinium) silsesquioxane chloride (Si3Py+Cl-) was synthesized and investigated as a novel sorbent phase for the disposable pipette extraction (DPX) technique coupled to high-performance liquid chromatography-florescence detection. This sorbent phase was characterized by scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR). Aqueous samples containing the phenolic endocrine-disrupting compounds bisphenol A (BPA), 17α-ethynylestradiol (EE2), 4-tert-octylphenol (4-t-OP), 4-octylphenol (4-OP) and 4-nonylphenol (4-NP) were subjected to DPX procedures and a series of optimizations was performed to determine the ideal extraction conditions using this approach. The proposed sorbent phase exhibited higher extraction efficiency than DPX-RP (reversed phase tips containing styrene-divinylbenzene), commonly used for the determination of the phenolic endocrine- disrupting-compounds under study. Satisfactory analytical performance was achieved with linear ranges from 2 to 100μgL-1 for 4-t-OP and 1-100μgL-1 for the other analytes. Limits of detection of 0.60μgL-1 for 4-t-OP and 0.30μgL-1 for other analytes, RSDs ranging from 1 to 20% and relative recoveries of 83-116% were obtained. Based on these satisfactory results, this sorbent phase represents a valuable alternative for the extraction of compounds with polar moieties in their structure.