Citation: Syczewski, M.D.; Siuda, R.;
Parafiniuk, J. REE Concentrations in
Secondary Uranium Minerals from
the Izera Metamorphic Complex (SW
Poland). Minerals 2023, 13, 945.
https://doi.org/10.3390/
min13070945
Received: 14 May 2023
Revised: 10 July 2023
Accepted: 12 July 2023
Published: 14 July 2023
Copyright: © 2023 by the authors.
Licensee MDPI, Basel, Switzerland.
This article is an open access article
distributed under the terms and
conditions of the Creative Commons
Attribution (CC BY) license (https://
creativecommons.org/licenses/by/
4.0/).
minerals
Article
REE Concentrations in Secondary Uranium Minerals from the
Izera Metamorphic Complex (SW Poland)
Marcin Daniel Syczewski
1,2,
* , Rafal Siuda
1
and Jan Parafiniuk
1
1
Faculty of Geology, University of Warsaw,
˙
Zwirki i Wigury 93, 02-089 Warsaw, Poland
2
Helmholtz Centre Potsdam, GFZ German Research Centre for Geosciences, Telegrafenberg,
D-14473 Potsdam, Germany
* Correspondence: marcinsyczewski@uw.edu.pl or marcin.syczewski@gfz-potsdam.de
Abstract: The subject of this work was supergene uranium mineralization and the YREE concen-
trations within. YREE differentiation patterns were used to recreate the prevailing crystallization
conditions of abandoned mine dumps in Kromnów, Kopaniec, and Radoniów, located in the Iz-
era Metamorphic Complex, Sudetes Mts. The collected samples were investigated using PXRD,
SEM-EDS, and EPMA. YREE concentrations were measured using LA-ICP-MS. The secondary ura-
nium mineralization from these locations consists of phosphates (meta-autunite, meta-torbernite,
metauranocircite-I, saleéite, bassetite, phosphuranylite), arsenates (zeunerite), silicates (uranophane,
sklodowskite), and uranyl hydroxides (likely becquerelite). Moreover, in Radoniów, phosphuranylite
was found; it had not been found in Poland previously. Uranyl mineral assemblages indicate the
diversity of chemistry of their mother solutions and suggest their weakly acidic character. The YREE
content in secondary uranium minerals also reflects the pore solutions’ chemistry variation. The
negative Y anomaly is observed in all uranyl phases. Similar behavior of Sm is also noted, exclud-
ing metatorbernite and torbernite. Among the uranyl minerals studied, only metatorbernite from
Kromnów showed a positive Nb anomaly, which was probably related to proximity to weathering in
YREE-breeding phases. Nevertheless, the YREE and chemical results suggest that this mineralization
originated from the oxidizing solutions generated during the weathering of primary hydrothermal
mineralization. In order to better understand the weathering zones in these locations, more detailed
studies on pore solution chemistry are needed.
Keywords: REY; uranyl phosphates; uranyl silicates; physicochemical conditions; Sudetes Mountains
1. Introduction
In the natural environment, uranium occurs in two oxidation states, reduced U
4+
and
oxidized U
6+
. Generally, uranium primary mineralization is represented by urani-nite
and sometimes by brannerite, coffinite, or davidite. The oxidation of these minerals starts
right after the decomposition of less stable phases in such an environment, e.g., ferric
sulfide. This process usually causes sharp and rapid decreases in pH values. Due to this,
barren minerals and more stable ones in oxidative conditions start to decay and release
many different ions into the weathering zone environment. These processes are further
accelerated by microbial activity. Under these conditions, uranium changes its oxidation
state from U
4+
to U
6+
, forming the highly soluble uranyl ion UO
2
2+
, which is the most
stable speciation in an aquatic environment. Uranium complexes with fluorides, sulfates,
phosphates, and carbonates exhibit high solubility and may migrate over long distances.
This paper presents a mineralogical study of uranyl mineralization in weathering
zones developed in uranium mine waste dumps in Kromnów, Kopaniec, and Radoniów
(SW Poland, central Europe). Due to the impossibility of collecting pore solutions in these
mine dumps, the differentiation patterns of rare earth elements and yttrium (YREE) were
used to reconstruct the prevailing physicochemical conditions during their crystallization.
Minerals 2023, 13, 945. https://doi.org/10.3390/min13070945 https://www.mdpi.com/journal/minerals