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The preparation and characterisation of certified reference materials of four selenium-rich rocks (GBW07397 to GBW07400) are described in this paper. The raw materials were derived from selenium-rich rocks in two famous seleniferous regions, Enshi Prefecture, Hubei Province and Ziyang County, Shaanxi Province, China. Sample homogeneity and stability were tested by inductively coupled plasma-mass spectrometry and atomic fluorescence spectrometry. The determined element mass fractions included selenium, arsenic, copper, zinc, molybdenum, cadmium, lead, vanadium and silver. Except for silver, the results of analysis of variance (ANOVA) and the relative standard deviations of the element mass fractions showed that the four materials exhibited good homogeneity and stability. Ten laboratories were involved in an interlaboratory comparison scheme for certification. Eight element mass fractions in the selenium-rich rocks were assigned as certified values, while only indicative values were obtained for Ag mass fractions. The certified values and expanded uncertainties for the selenium mass fractions in GBW07397-GBW07400 are 0.96 ± 0.05, 1.03 ± 0.05, 49 ± 4 and 38.5 ± 1.9 lg g -1 , respectively.

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Selenium (Se) enrichments or deficiency in maize (Zea mays L.), one of the world’s most important staple foods and livestock feeds, can significantly affect many people’s diets, as Se is essential though harmful in excess. In particular, Se-rich maize seems to have been one of the factors that led to an outbreak of selenosis in the 1980s in Naore Valley in Ziyang County, China. Thus, this region’s geological and pedological enrichment offers some insight into the behavior of Se in naturally Se-rich crops. This study examined total Se and Se species in the grains, leaves, stalks, and roots of 11 maize plant samples, Se fractions of soils around the rhizosphere, and representative parent rock materials from Naore Valley. The results showed that total Se concentrations in the collected samples were observed in descending order of soil > leaf > root > grain > stalk. The predominant Se species detected in maize plants was SeMet. Inorganic Se forms, mainly Se(VI), decreased from root to grain, and were possibly assimilated into organic forms. Se(IV) was barely present. The natural increases of Se concentration in soils mainly affected leaf and root dry-weight biomasses of maize. In addition, Se distribution in soils markedly correlated with the weathered Se-rich bedrocks. The analyzed soils had lower Se bioavailability than rocks, with Se accumulated predominantly as recalcitrant residual Se. Thus, the maize plants grown in these natural Se-rich soils may uptake Se mainly from the oxidation and leaching of the remaining organic-sulfide-bound Se fractions. A viewpoint shift from natural Se-rich soils as menaces to possibilities for growing Se-rich agricultural products is also discussed in this study.