Selenium speciation in soils using flow injection hydride generation atomic absorption spectrometry with on-line removal of organic matter interferences

A method based on flow injection hydride generation atomic absorption spectrometry (FI-HGAAS) with an on-line pre-reduction of Se(VI) to Se(IV) was developed and optimized to determine phosphate-extractable Se (0.1 M phosphate buffer KH2PO4/K2HPO4 at pH 7). The extracted fraction involves water-soluble Se (i.e. the most mobile Se fraction) and exchangeable Se (i.e. sorbed onto soil component surface). Kinetic discrimination mechanisms allowed the complete removal of interferences caused by organic matter due to the formation of humic substances (HS)–Se(IV) complexes observed when batch pre-reduction processes were used. Se(IV) and Se(VI) recoveries ranged 95–105% at a fortification level of 150 μg kg−1. The pre-reduction was efficiently carried out in 20 s in a 6 M HCl medium at 100 °C. Results from phosphate-extractable fractions were comparable to those obtained by ICP-MS. Se bound to organic matter was released digesting the remaining material from the phosphate buffer extraction with 0.1 M K2S2O8. Detection and quantification limits were 15 μg kg−1 Se and 50 μg kg−1 Se, respectively, in each fraction. The methodology was applied to 10 agricultural soils from Argentina with total Se concentration levels between 130 μg kg−1 and 419 μg kg−1. [Display omitted] •Se distribution in Argentinean agricultural soils is studied using FI-HGAAS.•Interferences in HG process caused by Se4+ organic complexes are overcome.•Results for Se in the bioavailable fraction are verified by ICP-MS.•A low Se bioavailability in agricultural soils is found.