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Rare-earth-element enrichment in post-Variscan polymetallic vein systems of the Harz Mountains, Germany

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Abstract

Carbonate gangue in historically important post-Variscan polymetallic Pb-Zn-Cu-Ag vein systems in the Upper Harz Mountains has elevated rare earth element contents (ΣREE+Y, 1500 ± 340 ppm; n = 16) in bulk samples. This enrichment is due to the occurrence of abundant micrometer-sized synchysite inclusions in calcite, identified via Raman spectroscopy. Calcite bulk analyses have roof-shaped PAAS-normalized REE patterns with a Eu peak but without Ce or Y anomalies and with a steeply dipping HREE pattern. Microbeam analysis (electron microprobe and LA-ICPMS) identifies these patterns as dominated by synchysite-(Ce–Nd) with strong Eu enrichment in the weight percent range and LREE/HREE fractionation (La/Lu ~ 100, PAAS-normalized). The synchysite component in calcite gangue is detected in polymetallic veins all over the Harz Mountains, which seems to be a diagnostic feature of the region and suggests a large-scale Mesozoic fluid system. However, the Upper (western) Harz systems with no fluorite have more elevated REE content, compared with the Lower (eastern) Harz fluorite-rich systems with less REE content. Carbonate gangue in the Upper Harz systems has homogeneous 87Sr/86Sri around 0.714 and εNdi of ~ − 9, while carbonate gangue in the Lower Harz systems has 87Sr/86Sri around 0.716 and εNdi of − 2 to − 5. Fluorite in the Lower Harz Mountains has strong positive Y anomalies and variable Eu anomalies at generally low REE abundances and no REE-mineral inclusions. Both Sr and Nd isotope compositions in the fluorite are very variable and indicate an open system (87Sr/86Sri, 0.710–0.718; εNdi, − 3 to − 17). The synchysite MREE enrichment in calcite gangue in the Upper Harz Mountains compares favorably with carbonatite-related LREE-dominated bastnäsite from China and elsewhere and allows an interesting perspective as a by-product of Pb–Zn mining.

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Acknowledgements

This study is funded by the German Ministry of Education and Research (BMBF) in the r4-initiative, project ResErVar (Ressourcenpotential hydrothermaler Lagerstätten der Varisziden: Harz). We are grateful to Alfons van den Kerkhof, Göttingen, for his support with cathodoluminescence microscopy, Klaus Simon, Göttingen, for his assistance in LA-ICP-MS analysis, Burkhard C. Schmidt, Göttingen, for Raman spectroscopy, and to Johannes Heider, Sangerhausen, for the photomicrographs with a special water immersion technique. We also want to thank Ulf Hemmerling and Fred Türck, Clausthal, for sample preparation and technical support. The manuscript benefited from discussions with Klaus Stedingk, critical review by Thomas Wagner and Volker Lüders, and editorial comments by Gregor Markl and Georges Beaudoin.

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  1. Mineralogy/Mineral Resources, Technische Universität Clausthal, Adolph-Roemer-Str. 2A, 38678, Clausthal-Zellerfeld, Germany

    Jonas Alles, Alexander-Maria Ploch, Thomas Schirmer, Wilfried Liessmann & Bernd Lehmann

  2. Geoscience Centre Göttingen, Universität Göttingen, Isotope Geology, Goldschmidtstrasse 3, 37077, Göttingen, Germany

    Nicole Nolte

  3. MAS-Analytics UG, Goldschmidtstrasse 3, 37077, Göttingen, Germany

    Nicole Nolte

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  1. Jonas Alles
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  2. Alexander-Maria Ploch
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Correspondence to Bernd Lehmann.

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Editorial handling: G. Markl

Electronic supplementary material

ESM Table 1

List of all samples analyzed and their location. (XLS 21 kb)

ESM Table 2

Complete trace element data from solution-based ICP-MS analysis of all samples. f, fluorite; c, calcite; n.a., not analyzed. REE are highlighted. (XLS 53 kb)

ESM Table 3

Conditions for EPMA measurements. (XLS 8 kb)

ESM Table 4-8

LA-ICPMS analytical settings and data. (XLS 679 kb)

ESM Table 9

Sr and Nd isotope data. (XLS 37 kb)

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Alles, J., Ploch, AM., Schirmer, T. et al. Rare-earth-element enrichment in post-Variscan polymetallic vein systems of the Harz Mountains, Germany. Miner Deposita 54, 307–328 (2019). https://doi.org/10.1007/s00126-018-0847-8

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