Investigation of the conditions for selenium determination by photochemical vapor generation coupled to graphite furnace atomic absorption spectrometry

Abstract

In this study instrumental parameters and sample preparation methods for Se determination using photochemical vapor generation (PVG) coupled to graphite furnace atomic absorption spectrometry (GF AAS) were investigated. Coconut water was selected as sample due to its nutritional importance and matrix complexity. The PVG was performed in a flow injection mode. The Se volatile species, generated in the UV reactor, were separated from the condensed phase in a gas-liquid separator and introduced automatically in the graphite furnace. These species were trapped on the integrated graphite platform surface coated with Ir as permanent modifier. The PVG conditions such as concentration of low molecular weight organic compound (LMWC), sample and carrier gas flow rate, effect of reagents frequently used in sample preparation (HNO3 and H2O2) were investigated. Formic acid 0.44 mol L−1 was selected as LMWC. The addition of HNO3 (14 mmol L−1) and H2O2 (145 mmol L−1) increased the sensitivity. Pre-reduction of Se (VI) to Se (IV) was performed on-line in a quartz spiral tube coated with a thin film of TiO2. The insertion of Ar flow rate (115 mL min−1) before the reactor inlet has improved the sensitivity, comparing with the introduction of Ar after the reactor. UV-assisted photo-oxidation of coconut water samples was employed as an alternative sample preparation to avoid the NO3−/NO2−, and H2O2 interference. The figures of merit were: sensitivity 0.0680 s ng−1, limits of detection and quantification 0.65 μg L−1 and 2.2 μg L−1, respectively, and characteristic mass of 62 pg. The PVG efficiency was estimated as 79% when comparing with conventional hydride generation. Furthermore, a mass balance study was accomplished in order to identify possible analyte losses in the PVG system, which the overall recovery was up to 85%. The results of recovery tests accomplished with real samples of coconut waters varied between 80 and 103% for Se (IV), Se (VI), and selenomethionine.