Selenium (Se) is a necessary micronutrient for humans, and its supplementation from crop grains is important to address the ubiquitous Se deficiency in people worldwide. Se uptake by crops largely depend on soil bioavailable Se rather than soil total Se content, which provides possibilities to explore the Se-rich crops in Se-poor area. Here, the possibility of cultivating Se-rich maize grains in Se-poor farmland was tested based on intensive field sampling and mathematical modelling. Sampling was conducted at county scale, and a total of 7779 topsoil samples and 109 maize samples with paired rhizosphere soils samples were collected. Results showed that although the soil Se content in the study county from southwestern China was at a low level (0.01–2.75 mg kg−1), 54.1% of the maize grain samples satisfied the standard for Se-rich products (0.02–0.30 mg kg−1). Soil organic matter, iron oxide, and phosphorus levels were correlated negatively with Se bioconcentration factor (BCF) of maize grain. Compared with the multivariate linear regression model, the artificial neural network (ANN) model was more accurate and reliable in predicting maize Se BCF. Prediction using the ANN model showed that 22.7% of the county's farmland was suitable for cultivating naturally Se-rich maize, which increased 21.3% growing areas than that from cultivation based on simply soil total Se. This study provided a new methodological framework for natural Se-rich maize production and verified the probability of cultivating naturally Se-rich maize in Se-poor farmland.
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