ICP-MS and ESI orbitrap MS/MS for plant elemental speciation. The need for accurate mass measurements

Complete text of publication follows. Metallomics approaches based on the combined use of elemental and molecular mass spectrometry have been developed to gain a better understanding of the factors involved in the uptake and distribution of selenium (Se) and arsenic (As) in a well-known hyperaccumulator, Arabidopsis thaliana. Plants, individually and simultaneously supplemented with As and Se (1, 3, 5 μg g-1), were grown hydroponically for 7 weeks in a controlled environment. The effect of the presence of Se on the As uptake by the plant leaves was investigated here for the first time; Se in the growing media was found not to affect As concentrations of the leaves in comparison with individual exposure to As. The use of 1% formic acid (1 deg C, 1 h), compared with buffer extraction (2, 5, 12 h) by sonication, was found to be the choice as a compromise between extraction efficiency and preservation of the compound entity. Using size-exclusion HPLC-ICP-MS, the coelution of the main As peak (70% of the total chromatogram area) with sulphur was observed, suggesting the presence of biomolecules containing S and As in the leaves. A deeper insight into the As species distribution in the leaves was achieved using reversed phase HPLC in combination with ICP-MS and ESI Orbitrap MS/MS. The need for accurate mass measurements (using ESI Orbitrap MS/MS) to minimize ambiguity in species identification will be demonstrated.