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Geochemical diagenetic trends during phosphorite formation – economic implications: The case of the Negev Campanian phosphorites, Southern Israel



Research on the Upper Campanian (Upper Cretaceous) Negev phosphorites (Mishash Formation), based on microprobe analyses, Fourier Transform Infrared spectroscopy, wet chemistry, microtextural (Scanning Electron Microscopy) studies and mineralogical analyses, together with quantified rates of sedimentation and P accumulation, enables the chemistry of these rocks to be better constrained across the Negev area and allows their suitability for the manufacture of P fertilizers to be better determined. Two phosphorite facies are differentiated: (i) a pristine phosphorite facies of low P content, more typical of basinal sections and (ii) a reworked, granular phosphorite facies commonly enriched in P, found predominantly near palaeo-highs and forming most of the economic phosphates. The distribution of F/P2O5, CO2/F, U(IV), Cd, Zn and other trace metals (Mo, Ni, Cr, Cu, V and Y), rare-earth elements concentration, Ce and Eu anomalies and heavy rare earth elements enrichment, are controlled by these two facies. F/P2O5 in carbonate-fluorapatite is much lower (0·090 to 0·107) in the pristine than in the reworked facies (0·107 to 0·120); in addition, the lower F/P2O5 in the pristine facies is coupled with: (i) higher Cd, Zn, Mo, Ni, Cr, Cu and V concentrations; (ii) a considerably reduced (< 10%) U(IV) fraction of total U; (iii) lower rare earth elements/P2O5 and Y/P2O5 ratios; (iv) less negative Ce and Eu anomalies and lower heavy rare earth elements (Lu/La) enrichment; (v) an increase in Fe-rich smectites in the clay fraction; and (vi) presence of OH in the carbonate-fluorapatite structure. Sedimentary reworking of previously formed pristine phosphate, together with its redeposition near structural highs in more oxic bottom conditions, results in considerable diagenetic changes in the chemistry of the phosphorites, making them more suitable for economic exploitation. The results presented here provide geochemical criteria for identifying pristine phosphate in other phosphorite sequences and may help to better locate phosphate strata chemically suitable for the phosphate industry elsewhere.