Coordination chemistry applied to anti-doping analysis: Cobalt quantification as its diethyldithiocarbamate complex by liquid chromatography coupled to high resolution tandem mass spectrometry.

Cobalt was included on the World Anti-Doping Agency Prohibited List in 2015 due to its effect on stimulus of erythropoiesis via stabilization of hypoxia-inducible factor. Although it has proven benefits for performance enhancement, the unavailability of inductively coupled plasma-mass spectrometry on routine of the accredited laboratories is a factor that reduces its applicability in anti-doping analysis. Therefore, an analytical method for quantification of urinary cobalt as its diethyldithiocarbamate complex by liquid chromatography coupled with high-resolution tandem mass spectrometry was developed and validated. Palladium was proposed as internal standard and rhodium as a complexation control. A microwave-assisted acid digestion of the urine samples was essential, not only to eliminate the matrix effect but mainly to avoid the non-specific bond of cobalt to endogenous molecules. A linear method was obtained over the studied range from a negative urine control to a spiked concentration of 25 ng/mL, with an estimated limit of quantification of 2.5 ng/mL, and an adequate combined standard uncertainty of 11.4%. Considering that all reagents are commercially available, the proposed strategy is feasible to be included on routine sample preparation. Monitoring urinary cobalt concentrations globally opens the perspective to support the anti-doping system to define a suitable threshold value and to understand its potential misuse by athletes seeking for performance improvement.

Essential and Potentially Toxic Elements from Brazilian Geopropolis Produced by the Stingless Bee Melipona quadrifasciata anthidioides Using ICP OES.

Melipona quadrifasciata anthidioides is a species of stingless bee popularly known in Brazil as "mandaçaia". Products derived from bees for food and therapeutic uses, have stimulated the evaluation of the chemical composition of geopropolis. Concentrations of 24 essential and potentially toxic elements were determined in geopropolis samples, using a sequential optical emission spectrometer with inductively coupled plasma (ICP OES) after microwave-assisted acid digestion. Principal component analysis (PCA) and Hierarchical cluster analysis (HCA) were used to carry out an exploratory analysis of the samples. The following elements were quantified (in mg Kg-1): Al (320,414.40-36,911.1), As (

Optimization of a Digestion Method to Determine Total Mercury in Fish Tissue by Cold Vapor Atomic Fluorescence Spectrophotometry.

Several microwave-assisted digestion methods were tested at the Centro de Estudios Aplicados en Química laboratory in Quito, Ecuador, to determine the accuracy and performance efficiency of the mineralization process for the determination of total mercury in fish tissue by cold vapor atomic fluorescence spectrophotometry. The use of MARSEasyPrep high-pressure vessels, low amounts of reagents (1 cm3 HNO3, 1 cm3 H2O2, and 1 cm3 HClO4), an irradiation temperature of 210 °C, and 35 min of mineralization time resulted in accurate performance, with recoveries of certified reference material DORM-4 between 90.1% and 105.8%. This is better than the Association of Official Analytical Chemists 2015.01 method, which has a reported accuracy of 81%. The repeatability precision and intermediate precision were established at three concentration levels (0.167, 0.500, and 0.833 mg·kg-1) and expressed as the percentage of the relative standard deviation ranging from 1.5% to 3.0% and 1.7% to 4.2%, respectively. Further, the method was satisfactorily applied to analyze fortified samples of tilapia (Oreochromis niloticus), with recoveries ranging from 98.3% to 104.3%. The instrumental limits of detection and quantification were 0.118 µg·dm-3 and 0.394 µg·dm-3, respectively.

Determination of elemental impurities in poly(vinyl chloride) by inductively coupled plasma optical emission spectrometry.

In this work, a method for poly(vinyl chloride) (PVC) analysis by inductively coupled plasma optical emission spectrometry (ICP-OES) was developed. Samples were digested by microwave-induced combustion (MIC) and thirteen elements (Ba, Cd, Co, Cu, Fe, Mg, Mn, Mo, Ni, Pb, Sr, V and Zn) were determined by ICP-OES. Operational conditions of MIC were investigated allowing quantitative determination of all the analytes and suitable results were achieved using a 3 mol L(-1) HNO3 solution. Microwave-assisted wet digestion (MAWD) using closed quartz vessels and a single reaction chamber microwave digestion system (MAWD-SRC), were also evaluated for PVC digestion for results comparison. All the evaluated sample preparation methods were considered suitable for PVC digestion but MIC was preferable due to the possibility of using diluted HNO3 instead of concentrated reagents and due to the better digestion efficiency. The residual carbon content (RCC) in digests obtained by MIC was significantly lower in comparison with the values obtained after MAWD and by MAWD-SRC. Accuracy for the proposed method was better than 94% for all analytes by comparison of results with those obtained by neutron activation analysis (NAA). Using MIC, it was possible to digest a relatively high sample mass (500 mg) and up to 8 samples in less time (25 min) in comparison with MAWD and MAWD-SRC (about 60 min for both methods). The efficiency of digestion by MIC was higher 99% and lower limits of detection (as low as 0.1 µg g(-1)) were obtained avoiding the use of concentrated acids that is of great concern according to the current green chemistry recommendations.