RESUMEN
Vessel-inside-vessel microwave-assisted acid digestion was developed for the analysis of samples with high-unsaturated fat content. For the first time, thermal decomposition of (NH4)2S2O8 solutions was evidenced for SO3 generation in situ and gas-phase modification in pressurized digestion flasks. NMR analysis demonstrated the oxidative effect of SO3 on olefin double bonds despite incomplete mineralization of oil samples. In this context, (NH4)2S2O8 decomposition was used in association with HNO3 solutions for sample digestion and mineral determination in edible oils (safflower, coconut, flaxseed, and chia). For all oils, dissolved organic carbon (DOC) contents lower than 5% m m-1 were obtained under optimum conditions: 210 °C with an irradiation time of 40 min, 7.0 mol L-1 HNO3 and 2.0 mol L-1 (NH4)2S2O8 in 0.9 mol L-1 H2SO4. Thus, a DOC reduction of about 70% was reached compared to digestions using only HNO3 at the same conditions. Additionally, a time reduction of up to three-fold was achieved compared to typically demanding edible oil digestions. The proposed method allowed the determination of As, Cd, Cr, Mn, Ni, and Pb in edible vegetable oil samples by ICP-MS. Accuracy was evaluated against the reference method, and no significant difference was observed (p = 0.05), with wide linear ranges and good linearity (r ≥ 0.999) and LOD ranging from 0.48 (As) to 2.41 (Cd) µg L-1.
RESUMEN
A new chemiluminescence (CL) flow method for persulfate determination was developed based on luminol oxidation by in-line generated radicals. Reactive oxygen species (ROS) generated by CdTe quantum dots (QDs) under a low energetic radiation (visible light emitted by LEDs) promoted the decomposition of persulfate ion (S2O8(2-)) into sulfate radical (SO4(â-)), leading to subsequent radical chain reactions that yield the emission of light. Due to the inherent radical short lifetimes and the transient behavior of CL phenomena an automated multi-pumping flow system (MPFS) was proposed to improve sample manipulation and reaction zone implementation ensuring reproducible analysis time and high sampling rate. The developed approach allowed up to 60 determinations per hour and determine S2O8(2-) concentrations between 0.1 and 1 mmol with good linearity (R=0.9999). The method has shown good repeatability with relative standard deviations below 2.5% (n=3) for different persulfate concentrations (0.1 and 0.625 mmol L(-1)). Limits of detection (3σ) and quantification (10σ) were 2.7 and 9.1 µmol L(-1), respectively. The MPFS system was applied to persulfate determination in bench scale UV/S2O8(2-) drug degradation processes of model samples showing good versatility and providing real time information on the persulfate consumption in photo-chemical degradation methodologies.
