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The geochemistry of phosphate rocks can provide valuable information on their depositional environment and the redox condition of global oceans through time. Here we examine trace metal concentrations and uranium (δ238U, δ234U) and strontium (87Sr/86Sr) isotope variations of marine sedimentary phosphate rocks and the phosphate-bearing carbonate fluorapatite (CFA) mineral phase, originating from Precambrian to mid-Miocene aged major global phosphate deposits. We find elevated concentrations of several trace elements (Al, V, Cr, Cd, U, Mn, Co, Cu, As, and Rb) in the CFA mineral phase of young phosphate rocks (Miocene to Late Cretaceous) relative to those of older (Devonian to Precambrian) rocks. The δ238U of phosphate rocks of Mid-Miocene to Permian age range from −0.311‰ to 0.070‰, exhibiting a positive fractionation relative to modern seawater (−0.38‰). This is similar to the isotope fractionation reported for carbonate and shale sediments, likely resulting from the reduction of uranium in porewaters during CFA precipitation. Cambrian to Precambrian phosphate rocks have lower δ238U of −0.583‰ to −0.363‰, indicating different depositional redox conditions likely resulting from seafloor anoxia and/or diagenetic modification. The 87Sr/86Sr ratios of phosphate rocks of Cretaceous to Mid-Miocene age generally follow the secular 87Sr/86Sr seawater curve. Phosphate rocks with 87Sr/86Sr that deviate from this curve have characteristic trace metal trends, such as lower Sr/Ca and Sr concentrations, suggesting later diagenetic modification. Older phosphate rocks of Precambrian age are systematically more radiogenic than the expected secular Sr seawater composition at the time of deposition, possibly due to the greater influence of terrestrial input in peritidal zones and/or more pervasive diagenetic modification. Overall, our study reveals connections between U and Sr isotope variations for reconstructing the depositional and diagenetic conditions of global phosphate rock formation through Earth history and the transition to an oxic ocean following the Paleozoic Oxygenation Event. 

Phosphate fertilizers may contain elevated concentrations of toxic metals and metalloids and therefore, their excessive application can result in the accumulation of both phosphorus (P) and metal(loid)s in agricultural soils. This study aims to investigate the occurrence, distribution, and potential plant-availability of metal(loid)s originating from phosphate fertilizer in a long-term experimental field at the Tidewater Research Station in North Carolina, where topsoil (10-20 cm deep) and subsoil (up to 150 cm deep) samples were collected from five plots with consistent and individually different application rates of P-fertilizer since 1966. We conducted systematic analyses of P and metal(loid)s in bulk soils, in the plant available fraction, and in four sequentially extracted soil fractions (exchangeable, reducible, oxidizable, and residual). The results show that P content in topsoils were directly associated with the rate of P-fertilizer application (=1, p<0.05). Furthermore, P concentrations were highly correlated with concentrations of Cd, U, Cr, V, and As in the bulk topsoil (>0.58, p<0.05), as well as the potential plant-available fraction (>0.67, p<0.01), indicating the accumulation of the fertilizer-derived toxic metal(loid)s in the topsoil. Significant correlations (p<0.001) of metal(loid)s concentrations between the bulk soil and the potential plant-available fraction raises the possibility that P-fertilizer application could increase the accumulation of toxic metal(loid)s in plants, which could increase human exposure. Results from sequential leaching experiments revealed that large portions of the trace elements, in particular Cd, occur in the soluble (exchangeable and reducing) fractions of topsoil with higher P-fertilizer input, whereas the levels of redox-sensitive elements (As, V, U, Cr) were higher in the reducible and oxidizable fractions of the soils. Overall, the data presented in this study demonstrate the effect of long-term P-fertilizer application on the occurrence and accumulation of a wide range of toxic metal(loid)s in agricultural topsoil.