A green method for the determination of illicit drugs in wastewater and surface waters-based on a semi-automated liquid-liquid microextraction device.

Liquid-phase microextraction (LPME) is a simple, low-cost, and eco-friendly technique that enables the detection of trace concentrations of organic contaminants in water samples. In this work, a novel customized microextraction device was developed for the LPME extraction and preconcentration of nine illicit drugs in surface water and influent and effluent wastewater samples, followed by analysis by GC-MS without derivatization. The customized device was semi-automated by coupling it with a peristaltic pump to perform the collection of the upper layer of the organic phase. The extraction parameters affecting the LPME efficiency were optimized. The optimized conditions were: 100 µL of a toluene/DCM/EtAc mixture as extractor solvent; 30min of extraction time under vortex agitation (500rpm) and a solution pH of 11.6. The limits of detection and quantification ranged from 10.5ng L-1 (ethylone) to 22.0ng L-1 (methylone), and from 34.9ng L-1 to 73.3ng L-1 for these same compounds, respectively. The enrichment factors ranged from 39.7 (MDMA) to 117 (cocaethylene) and the relative recoveries ranged from 80.4% (N-ethylpentylone) to 120% (cocaine and cocaine-d3). The method was applied to real surface water, effluent, and influent wastewater samples collected in Salvador City, Bahia, Brazil. Cocaine was the main drug detected and quantified in wastewater samples, and its concentration ranged from 312ng L-1 to 1,847ng L-1. Finally, the AGREE metrics were applied to verify the greenness of the proposed method, and an overall score of 0.56 was achieved, which was considered environmentally friendly.

Influence of heating time and metal ions on the amount of free fatty acids and formation rates of selected carbonyl compounds during the thermal oxidation of canola oil.

Canola oil was heated continuously for 8 h at a typical frying temperature (180 °C) in the presence of various concentrations of the metal ions Fe(III), Cu(II), and Al(III) (9.2, 27.5, and 46.0 µg L(-1) of oil) to evaluate changes occurring in the amount of free fatty acids, expressed as acidity index, and in the formation rates of aldehydes. The aldehydes were collected and derivatized in silica cartridges functionalized with C18 and impregnated with an acid solution of 2,4-dinitrophenylhydrazine, after which they were eluted with acetonitrile and analyzed by LC-DAD-MS. Among the substances emitted, the following were identified and quantified: formaldehyde, acetaldehyde, acrolein, propanal, butanal, hexanal, (E)-2-heptenal, and octanal. During heating of the oil, the compounds presenting the highest mean formation rates were acrolein, hexanal, and acetaldehyde. In the study of the metal ions, the addition of ions to the samples generally led to a corresponding increase in the formation rates of the eight substances. The compounds showing the highest relative increases in formation rates were formaldehyde, acetaldehyde, propanal, and heptenal. In terms of catalytic effect, copper proved to be the most efficient in promoting increased formation rates, followed by iron and aluminum.

Development, validation and application of a methodology based on solid-phase micro extraction followed by gas chromatography coupled to mass spectrometry (SPME/GC-MS) for the determination of pesticide residues in mangoes.

A method was developed for the simultaneous analysis of 14 pesticide residues (clofentezine, carbofuran, diazinon, methyl parathion, malathion, fenthion, thiabendazole, imazalil, bifenthrin, permethrin, prochloraz, pyraclostrobin, difenoconazole and azoxystrobin) in mango fruit, based on solid-phase micro extraction (SPME) coupled to gas chromatography-mass spectrometry (GC-MS). Different parameters of the method were evaluated, such as fiber type, extraction mode (direct immersion and headspace), temperature, extraction and desorption times, stirring velocities and ionic strength. The best results were obtained using polyacrylate fiber and direct immersion mode at 50 degrees C for 30 min, along with stirring at 250 rpm and desorption for 5 min at 280 degrees C. The method was validated using mango samples spiked with pesticides at concentration levels ranging from 33.3 to 333.3 microg kg(-1). The average recoveries (n=3) for the lowest concentration level ranged from 71.6 to 117.5%, with relative standard deviations between 3.1 and 12.3%, respectively. Detection and quantification limits ranged from 1.0 to 3.3 microg kg(-1) and from 3.33 to 33.33 microg kg(-1), respectively. The optimized method was then applied to 16 locally purchased mango samples, all of them containing the pesticides bifenthrin and azoxystrobin in concentrations of 18.3-57.4 and 12.7-55.8 microg kg(-1), respectively, although these values were below the MRL established by Brazilian legislation. The method proved to be selective, sensitive, and with good precision and recovery rates, presenting LOQ below the MRL admitted by Brazilian legislation.

Influence of time, surface-to-volume ratio, and heating process (continuous or intermittent) on the emission rates of selected carbonyl compounds during thermal oxidation of palm and soybean oils.

The aim of this work was to compare the emission rates of selected carbonyl compounds (CC) produced by palm and soybean oils when heated at 180 degrees C in the presence of air, through different time intervals and at different surface-to-volume ratios ( S/ V), in continuous and intermittent processes. The CC were collected and derivatized onto silica C18 cartridges impregnated with an acid 2,4-dinitrophenylhidrazine solution, followed by extraction with acetonitrile and analysis by HPLC-UV and, in some cases, HPLC-MS with electrospray ionization. Among the CC quantified, namely, acetaldehyde, acrolein, propanal, butanal, hexanal, 2-heptenal, and 2-octenal, acrolein was the main emission in both oils and all S/ V ratios, followed by hexanal and 2-heptenal. The soybean oil has presented greater emission rates of acrolein than palm oil. When different S/ V ratios used during the heating process of the oil were compared, the emission rates, in general, were directly related to them, although saturated and nonsaturated CC have had different behaviors toward oxidation reactions. During intermittent heating, there was a trend of increasing emission rates of saturated aldehydes, whereas the opposite was observed with unsaturated aldehydes, probably due to the reactivity of the double bond present in these compounds.