Processes controlling rare earth element distribution in sedimentary apatite: Insights from spectroscopy, in situ geochemistry and O and Sr isotope composition
Apatite; Belgium; phosphogenesis; phosphorite; post-depositional processes; rare earth elements; Sr and O isotopes; Depositional process; Element distribution; Fluorapatites; Phosphogenesis; Phosphogenic event; Phosphorite; Post-depositional process; Process controlling; Sr and O isotope; Geology; Stratigraphy; General Engineering; Energy Engineering and Power Technology
Abstract :
[en] In phosphorites, the content and distribution of rare earth elements are linked to the environment of phosphogenesis. This paper focuses on the question of sources and processes controlling the rare earth element content of apatite from Belgian phosphorites formed during three major phosphogenic events in the Lower Palaeozoic, Late Cretaceous and Cenozoic. To constrain sources and processes, new data include petrological, mineralogical (including cathodoluminescence and Raman spectroscopy) and in situ trace element and Sr and O isotope analyses of apatite. Fluorapatite from Lower Palaeozoic P-rich conglomerates has the greatest rare earth element enrichment. It is affected by metamorphism that led to deformation of apatite nodules and formation of garnet porphyroblast inclusions. The role of Fe-oxyhydroxides in element scavenging is highlighted by some apatite nodules that maintain their primary middle rare earth element enrichment, while others are characterized by altered rare earth element patterns resulting from competition for these elements between co-crystallizing minerals during deformation. A systematic shift towards lower δ18O and radiogenic Sr isotopic composition compared to contemporaneous seawater indicate interaction with 18O-depleted meteoric fluids and a crustal component. By contrast, carbonate-rich fluorapatite from the Late Cretaceous phosphatic chalk mostly keeps its primary trace element and isotopic signatures (close to seawater), although an external rare earth element addition is noted, as well as rare earth element redistribution induced by diagenetic alteration. Cenozoic carbonate fluorapatite nodules mostly present flat rare earth element patterns that are indicative of a detrital influence. Slight changes in rare earth element distribution are assigned to post-depositional alteration, which also led to an increase in radiogenic Sr, with unchanged δ18O compared to seawater. The methodology followed here efficiently helps in deciphering the processes that modified the chemistry of apatite in the frame of major phosphogenic events.
Disciplines :
Earth sciences & physical geography
Author, co-author :
Decrée, Sophie ; Royal Belgian Institute of Natural Sciences-Geological Survey of Belgium, Brussels, Belgium ; The Mineral Resources Expert Group (MREG), EuroGeoSurveys, Brussels, Belgium
Deloule, Etienne; Université de Lorraine, CNRS, CRPG, Nancy, France
Barros, Renata; Royal Belgian Institute of Natural Sciences-Geological Survey of Belgium, Brussels, Belgium
Mercadier, Julien; GeoRessources Lab, Université de Lorraine, CNRS, Nancy, France
Höhn, Stefan; Department of Geodynamics and Geomaterials Research, Bavarian Georesources Centre, Institute of Geography and Geology, University of Würzburg, Würzburg, Germany
Peiffert, Chantal; GeoRessources Lab, Université de Lorraine, CNRS, Nancy, France
Baele, Jean-Marc ; Université de Mons - UMONS > Faculté Polytechniqu > Service de Géologie fondamentale et appliquée
Language :
English
Title :
Processes controlling rare earth element distribution in sedimentary apatite: Insights from spectroscopy, in situ geochemistry and O and Sr isotope composition
The authors would like to thank Alain Herbosch, Olivier Lambert and Etienne Steurbaut for having provided samples and crucial field information. Damien Jacquemin is thanked for his help in studying the phosphatic chalk of the Mons Basin. The authors are also grateful to Thommy D'heuvaert, Marleen DeCeukelaire and Thomas Goovaerts for the handling and preparation of samples from the collection of the RBINS. The GSB has received funding from the European Union's Horizon 2020 research and innovation program under grant agreement No 731166, through the project FRAME “Forecasting and assessing Europe's strategic raw materials needs”. This work is also part of the GSEU – Geological Service for Europe project (through its WP2: Critical Raw Materials, the International Centre of Excellence and the United Nations Framework Classification), which has received funding from the European Union's Horizon Europe research and innovation programme under Grant Agreement. This work was partly done at the LA‐ICP‐MS laboratory of GeoRessources in Nancy which is funded by the Labex Ressources 21 (ANR‐10‐LABX‐21‐RESSOURCES21), the Région Lorraine and the European Community through the FEDER (European Regional Development Fund) program. The Cameca IMS 1280 HR2 ion microprobe at CRPG Nancy is an instrument of the LG‐SIMS INSU CNRS national facility. The authors are grateful to Nathan Sheldon (Associate Editor), and an anonymous reviewer, for helpful remarks on the manuscript. Their comments have contributed to improve substantially the quality of this paper. Besides, they do thank Alex Brasier (Chief Editor) and Elaine Richardson (Journal Office Manager) for the handling of the manuscript.
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