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Background and Aims Rice accounts for around 20% of the calories consumed by humans. Essential nutrients like zinc (Zn) are crucial for rice growth and for populations relying on rice as a staple food. No well-established study method exists. As a result, we a lack a clear picture of the chemical forms of zinc in rice grain. Furthermore, we do not understand the effects of widespread and variable zinc deficiency in soils on the Zn speciation, and to a lesser extent, its concentration, in grain. Methods The composition and Zn speciation of Cambodian rice grain is analyzed using synchrotron-based microprobe X-ray fluorescence (µ-XRF) and extended X-ray absorption fine-structure spectroscopy (EXAFS). We developed a method to quantify Zn species in different complexes based on the coordination numbers of Zn to oxygen and sulfur at characteristic bond lengths. Results Zn levels in brown rice grain ranged between 15-30 mg kg-1 and were not correlated to Zn availability in soils. 72%-90% of Zn in rice grains is present as Zn-phytate, generally not bioavailable, while smaller quantities of Zn are bound as labile nicotianamine complexes, Zn minerals like ZnCO3¬ or thiols. Conclusion Zn speciation in rice grain is affected by Zn deficiency more than previously recognized. A majority of Zn was bound in phytate complexes in rice grain. Zinc phytate complexes were found in higher concentrations and also in higher proportions, in Zn-deficient soils, consistent with increased phytate production under Zn deficiency. Phytates are generally not bioavailable to humans, so low soil Zn fertility may not only impact grain yields, but also decrease the fraction of grain Zn bioavailable to human consumers. The potential impact of abundant Zn-phytate in environments deficient in Zn on human bioavailability and Zn deficiency requires additional research. 

We have measured the absolute doubly differential angular sputtering yield for 20 keV Kr+ impacting a polycrystalline Cu slab at an incidence angle of θi = 45° relative to the surface normal. Sputtered Cu atoms were captured using collectors mounted on a half dome above the sample, and the sputtering distribution was measured as a function of the sputtering polar, θs, and azimuthal, ϕs, angles. Absolute results of the sputtering yield were determined from the mass gain of each collector, the ion dose, and the solid angle subtended, after irradiation to a total fluence of ∼1 × 1018 ions/cm2. Our approach overcomes shortcomings of commonly used methods that only provide relative yields as a function of θs in the incidence plane (defined by the ion velocity and the surface normal). Our experimental results display an azimuthal variation that increases with increasing θs and is clearly discrepant with simulations using binary collision theory. We attribute the observed azimuthal anisotropy to ion-induced formation of micro- and nano-scale surface features that suppress the sputtering yield through shadowing and redeposition effects, neither of which are accounted for in the simulations. Our experimental results demonstrate the importance of doubly differential angular sputtering studies to probe ion sputtering processes at a fundamental level and to explore the effect of ion-beam-generated surface roughness.