RESUMEN
The simultaneous determination of chemical vapor-generating elements involving derivatization is difficult even by inductively coupled plasma optical emission spectrometry or mass spectrometry. This study proposes a new direct liquid microsampling method for the simultaneous determination of As, Bi, Se, Te, Hg, Pb, and Sn, using a fully miniaturized set-up based on electrothermal vaporization capacitively coupled plasma microtorch optical emission spectrometry. The method is cost-effective, free from non-spectral interference, and easy to run by avoiding derivatization. The method involves the vaporization of analytes from the 10 µL sample and recording of episodic spectra generated in low-power (15 W) and low-Ar consumption (150 mL min-1) plasma microtorch interfaced with low-resolution microspectrometers. Selective vaporization at 1300 °C ensured the avoidance of non-spectral effects and allowed the use of external calibration. Several spectral lines for each element even in the range 180-210 nm could be selected. Generally, this spectral range is examined with large-scale instrumentation. Even in the absence of derivatization, the obtained detection limits were low (0.02-0.75 mg kg-1) and allowed analysis of environmental samples, such as cave and river sediments. The recovery was in the range of 86-116%, and the accuracy was better than 10%. The method is of general interest and could be implemented on any miniaturized or classical laboratory spectrometric instrumentation.
RESUMEN
An analytical method for the quantification of total Hg and CH3Hg+ in biological tissues (fish, mushroom) and water sediment was developed based on small-sized electrothermal vaporization capacitively coupled plasma microtorch optical emission spectrometry using a low-resolution microspectrometer as detector. Sample preparation was carried out according to the procedure recommended by JRC Technical Report of European Commission for the determination of CH3Hg+ in seafood and adapted by us for lower consumption of reagents. Amounts of 0.1 - 0.5 g sample were subjected to extraction in 5 ml of 47% HBr then CH3Hg+ was extracted in 2 × 1 ml toluene and back-extracted in 2 ml aqueous solution of 1% l-cysteine. Total Hg/CH3Hg+ were quantified in 10 µl of acidic extract/l-cysteine solution after electrothermal vaporization and measurement of 253.652 nm Hg signal in the episodic emission spectra. Under the optimal working conditions of system (70 °C sample drying, 1300 °C sample vaporization, 10 W plasma power and 150 ml min-1 Ar flow) the limits of detection were 7.0 µg kg-1 total Hg and 3.5 µg kg-1 CH3Hg+. Comparison of slopes in external calibration and standard addition procedure revealed the lack of non-spectral interferences of multimineral matrix, so that the calibration against Hg2+ standards was adopted. Pooled recovery of total mercury/methylmercury was 101 ± 7%/100 ± 7%, while precision assessed from measurements of real samples was in the range 1.6-9.6%/2.7-12.8%. The proposed method validated according to Eurachem Guide 2014 is selective and complies with demands in European legislation (Decisions 657/2002; 333/2007; 836/2011) and Association of Official Analytical Chemists Guide in terms of performances for food control. The method displays a high degree of greenness by circumventing cold vapor generation, use of small amounts of reagents and full-miniaturized instrumentation resulting in low analytical costs without reducing results quality. Besides, the method is simple and rapid, since it uses external calibration curves prepared from Hg2+standard solutions both for total Hg and CH3Hg+ determination.