Analysis of polycyclic aromatic hydrocarbons in atmospheric particulate samples by microwaveassisted extraction and liquid chromatography

A methodology based on microwave-assisted extraction (MAE) and LC with fluorescence detection (FLD) was investigated for the efficient determination of 15 polycyclic aromatic hydrocarbons (PAHs) regarded as priority pollutants by the US Environmental Protection Agency and dibenzo(a,l)pyrene in atmospheric particulate samples. PAHs were successfully extracted from real outdoor particulate matter (PM) samples with recoveries ranging from 81.4±8.8 to 112.0±1.1%, for all the compounds except for naphthalene (62.3±18.0%) and anthracene (67.3±5.7%), under the optimum MAE conditions (30.0 mL of ACN for 20 min at 110ºC). No clean-up steps were necessary prior to LC analysis. LOQs ranging from 0.0054 ng/m3 for benzo( a)anthracene to 0.089 ng/m3 for naphthalene were reached. The validated MAE methodology was applied to the determination of PAHs from a set of real world PM samples collected in Oporto (north of Portugal). The sum of particulate-bound PAHs in outdoor PM ranged from 2.5 and 28 ng/m3.

Anodic adsorptive stripping voltammetric determination of atrazine in spiked soil samples with a gold microelectrode

Microwave-assisted solvent extraction was combined with anodic adsorptive stripping voltammetry at a gold microelectrode to extract and quantify the herbicide atrazine in spiked soil samples. A systematic study of the experimental parameters affecting the stripping response was carried out by square-wave voltammetry. The voltammetric procedure is based on controlled adsorptive accumulation of atrazine at the potential of 0.35V (versus Ag/AgCl) in the presence of Britton–Robinson buffer pH (2.0). The limit of detection obtained for a 30 sec collection time was 4.3x10-7 mol L-1. Recovery experiments, at the 1µgg-1 level of spiking, gave good results for the global procedure, and the values found were comparable to those obtained by HPLC.

Development of a SPME-GC-ECD methodology for selected pesticides in must and wine samples

A method for the determination of some pesticide residues in must and wine samples was developed using solid-phase microextraction (SPME) and gas chromatography – electron capture detection (GC/ECD). The procedure only needs dilution as sample pre-treatment and is therefore simple, fast and solvent-free. Eight fungicides (vinclozolin, procymidone, iprodione, penconazole, fenarimol, folpet, nuarimol and hexaconazole), one insecticide (chlorpyriphos) and two acaricides (bromopropylate and tetradifon) can be quantified. Good linearity was observed for all the compounds in the range 5–100 µg/L. The reproducibility of the measurements was found acceptable (with RSD’s below 20%). Detection limits of 11 µg/L, on average, are sufficiently below the proposed maximum residue limits (MRL’s) for these compounds in wine. The analytical method was applied to the determination of these compounds in Portuguese must and wine samples from the Demarcated Region of Alentejo, where any residues could be detected.

Optimization of HS-SPME analytical conditions using factorial design for trihalomethanes determination in swimming pool water samples

Trihalomethanes (THMs) are widely referred and studied as disinfection by-products (DBPs). The THMs that are most commonly detected are chloroform (TCM), bromodichloromethane (BDCM), chlorodibromomethane (CDBM), and bromoform (TBM). Several studies regarding the determination of THMs in swimming pool water and air samples have been published. This paper reviews the most recent work in this field, with a special focus on water and air sampling, sample preparation and analytical determination methods. An experimental study has been developed in order to optimize the headspace solid-phasemicroextraction (HS-SPME) conditions of TCM, BDCM, CDBM and TBM from water samples using a 23 factorial design. An extraction temperature of 45 °C, for 25min, and a desorption time of 5 min were found to be the best conditions. Analysis was performed by gas chromatography with an electron capture detector (GC-ECD). The method was successfully applied to a set of 27 swimming pool water samples collected in the Oporto area (Portugal). TCM was the only THM detected with levels between 4.5 and 406.5 μg L−1. Four of the samples exceeded the guideline value for total THMs in swimming pool water (100 μgL−1) indicated by the Portuguese Health Authority.

Sarcosine oxidase composite screen-printed electrode for sarcosine determination in biological samples

As the prostate cancer (PCa) progresses, sarcosine levels increase both in tumor cells and urine samples, suggesting that this metabolite measurements can help in the creation of non-invasive diagnostic methods for this disease. In this work, a biosensor device was developed for the quantification of sarcosine via electrochemical detection of H2O2 (at 0.6 V) generated from the catalyzed oxidation of sarcosine. The detection was carried out after the modification of carbon screen printed electrodes (SPEs) by immobilization of sarcosine oxidase (SOX) on the electrode surface. The strategies used herein included the activation of the carbon films by an electrochemical step and the formation of an NHS/EDAC layer to bond the enzyme to the electrode, the use of metallic or semiconductor nanoparticles layer previously or during the enzyme immobilization. In order to improve the sensor stability and selectivity a polymeric layer with extra enzyme content was further added. The proposed methodology for the detection of sarcosine allowed obtaining a limit of detection (LOD) of 16 nM, using a linear concentration range between 10 and 100 nM. The biosensor was successfully applied to the analysis of sarcosine in urine samples.

Sarcosine oxidase composite screen-printed electrode for sarcosine determination in biological samples

XIX Meeting of the Portuguese Electrochemical Society - XVI Iberic Meeting of Electrochemistry