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Geochemical and isotopic (Sm–Nd and Sr) studies of deposits of the Baikal and Oselok Groups in the southern Siberian Craton and LA-ICP-MS U–Pb dating of detrital zircons show that they accumulated in passive continental-margin settings in the Vendian. The time limits of sedimentation were assessed on the basis of Sr chemostratigraphy of carbonate deposits of the Baikal Group and LA-ICP-MS U–Pb dating of detrital zircons in first-cycle terrigenous deposits of the Oselok Group. The main provenances for rocks of these groups were constant. These were rocks of the cover and basement of the Siberian Craton. Tuffite horizons in upper portions of the groups are the only sign of Late Vendian activation of this block, which is reflected in changes of geochemical indices of terrigenous rocks and their younger Sm–Nd model ages.

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The aim of the present work is to demonstrate the application of the x‐ray fluorescence (XRF) technique to the determination of Rb, Sr, Y, Zr, and Nb contents in phosphorites. The effect of a chemical sample composition on fluorescence intensities of analytical lines has been taken into account using the background standard method. A novelty of the work is the detailed study of a background to choose the background position, free from the spectral line overlaps of the elements presented in the sample. The most suitable background position is the position at the angle 2θ = 29° when using the analyzing crystal LiF(200). During our investigation we faced a problem of choice of Certified Reference Materials (CRMs) for the calibration of the phosphorites. To estimate interelement effects and to choose CRMs for the calibration the intensities were theoretically calculated. The statistical processing of analytical results of the technique is carried out. This technique may be applied to the determination of Rb, Sr, Y, Zr, and Nb contents in the phosphorites. Also, the possibility has been demonstrated to use the XRF technique for geochemical investigations of rocks. Phosphorites of Bokson‐Khubsugul Basin were selected as an example. As a result of the investigation the genetic type of phosphorites was established, which corresponded to the present geodynamical depositional environment. The character of the distribution of Rb, Sr, Y, Zr, and Nb contents in the phosphorites was also studied. Copyright © 2008 John Wiley & Sons, Ltd.