Change search
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf
Rare earth element enriched birnessite in water-bearing fractures, the Ytterby mine, Sweden
Stockholm University, Faculty of Science, Department of Geological Sciences.
Stockholm University, Faculty of Science, Department of Geological Sciences.
Stockholm University, Faculty of Science, Department of Geological Sciences.ORCID iD: 0000-0002-7578-3455
Show others and affiliations
Number of Authors: 102017 (English)In: Applied Geochemistry, ISSN 0883-2927, E-ISSN 1872-9134, Vol. 78, p. 158-171Article in journal (Refereed) Published
Abstract [en]

Characterization of a black substance exuding from fractured bedrock in a subterranean tunnel revealed a secondary manganese oxide mineralisation exceptionally enriched in rare earth elements (REE). Concentrations are among the highest observed in secondary ferromanganese precipitates in nature. The tunnel is located in the unsaturated zone at shallow depth in the former Ytterby mine, known for the discovery of yttrium, scandium, tantalum and five rare earth elements.

Elemental analysis and X-ray diffraction of the black substance establish that the main component is a manganese oxide of the birnessite type. Minor fractions of calcite, other manganese oxides, feldspars, quartz and about 1% organic matter were also found, but no iron oxides were identified. The Ytterby birnessite contains REE, as well as calcium, magnesium and traces of other metals. The REE, which constitute 1% of the dry mass and 2% of the metal content, are firmly included in the mineral structure and are not released by leaching at pH 1.5 or higher. A strong preference for the trivalent REE over divalent and monovalent metals is indicated by concentration ratios of the substance to fracture water. The REE-enriched birnessite has the general formula Mx(Mn3+,Mn4+)(2)O-4 center dot(H2O)(n) with M = (0.37-0.41) Ca + 0.02 (REE + Y), 0.04 Mg and (0.02-0.03) other metals, and with [Mn3+]/[Mn4+] = 0.86-1.00.

The influence of microorganisms on the accumulation of this REE enriched substance is demonstrated by electron paramagnetic resonance spectroscopy. Results show that it is composed of two or more manganese phases, one of which has a biogenic signature. In addition, the occurrence of C-31 to C-35 extended side chain hopanoids among the identified lipid biomarkers combined with the absence of ergosterol, a fungal lipid biomarker, indicate that the in-situ microbial community is bacterial rather than fungal.

Place, publisher, year, edition, pages
2017. Vol. 78, p. 158-171
Keywords [en]
Ytterby mine, Manganese oxides, Birnessite, Rare earth elements, Microbial mediation
National Category
Earth and Related Environmental Sciences
Research subject
Geochemistry
Identifiers
URN: urn:nbn:se:su:diva-142464DOI: 10.1016/j.apgeochem.2016.12.021ISI: 000395599500015OAI: oai:DiVA.org:su-142464DiVA, id: diva2:1096421
Available from: 2017-05-17 Created: 2017-05-17 Last updated: 2019-12-17Bibliographically approved
In thesis
1. Microbially mediated manganese oxides enriched in yttrium and rare earth elements in the Ytterby mine, Sweden
Open this publication in new window or tab >>Microbially mediated manganese oxides enriched in yttrium and rare earth elements in the Ytterby mine, Sweden
2019 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Microorganisms are able to manipulate redox reactions and thus exert extensive control on chemical speciation and element partitioning in nature, affecting the formation and dissolution of certain minerals. One of these redox active elements is manganese (Mn), which in its oxidized states (III/IV), commonly forms Mn oxide-hydroxide minerals. A microbially mediated birnessite-type Mn oxide enriched in yttrium (Y) and rare earth elements (REE) has been studied in our research. The YREE-enriched birnessite was found in a tunnel to the main shaft of the former Ytterby mine in Sweden, well known as the place of discovery of scandium, yttrium, tantalum and five of the REEs. The thesis aims to define preconditions and processes leading to the formation of this Ytterby birnessite, with particular focus on microbial involvement and the potentially promoting role of biofilms. Dynamics and mineral products of the natural system are studied in combination with analyses of Mn phases produced in vitro by microbes isolated from this system. In addition, the nature of the YREE association with the birnessite-type Mn oxides is investigated.

Natural birnessite has the composition Mx(Mn3+, Mn4+)2O4•(H2O)n  with M ususally being (Na,Ca) and x=0.5. An empirical formula based on element analyses for the Ytterby birnessite has been assessed as M = (Ca0,37-0,41YREE0.02Mg0.04Other metals0.02-0.03), with [Mn3+]/[Mn4+] = 0.86-1.00 to achieve charge balance. We find that there is a preference for the trivalent YREEs over divalent and monovalent metals. There is also a preferential uptake of light rare earth elements (LREE) relative to heavy rare earth elements (HREE), likely due to mineralogical preferences for charge and ionic radius. The YREEs are strongly bound to the mineral structure and not merely adsorbed on the surface. The Mn deposit subsystems (fracture water, Mn oxide precipitating biofilm and bubble biofilm) are phylogenetically significantly different and the microbial community composition of the feeding water has little impact on the derived biofilms. The signature microbial groups of the Mn oxide producing biofilm Rhizobiales (e.g., Pedomicrobium), PLTA13 Gammaproteobacteria, Pirellulaceae, Blastocatellia and Nitrospira are adapted to the specific characteristics of the biofilm: an emerging extreme environment (low temperature, no light, high metal concentration) which is in part generated by the biofilm components themselves. Known Mn oxidizers are identified among these niched microbial groups and four of the isolated bacterial species (Hydrogenophaga sp., Pedobacter sp., Rhizobium sp. and Nevskia sp.) as well as one fungal species (Cladosporium sp.) are involved in Mn oxide production. Hydrogenophaga sp. and Pedobacter sp. produce Mn oxides independently while results imply a synergistic relationship between Rhizobium sp. and selected species. Members of the Pedobacter and Nevskia genera are previously not known to oxidize Mn. Microstructural characterizaton show that the growth pattern of the birnessite-type Mn oxides is either dendritic/shrublike or spherulitic/botryoidal. Nucleation takes place in close association to the biofilm and initial Mn precipitates are observed at different locations depending on the mediating species. Encrustations of cells and other organic structures by Mn precipitates serve as stable nuclei for further growth. The close relationship appears to decrease in importance as the aggregates of poorly crystalline precipitates grow. In the more developed crystals, a repetitive pattern, Liesegang-type of rings, suggests that abiotic factors take over.

Place, publisher, year, edition, pages
Stockholm: Department of Geological Sciences, Stockholm University, 2019. p. 63
Series
Meddelanden från Stockholms universitets institution för geologiska vetenskaper ; 378
Keywords
manganese oxidizers, birnessite, yttrium and rare earth elements (YREE), biofilms, shallow subsurface, Ytterby mine, geomicrobiology, microbial geochemistry, manganoxiderare, birnessit, yttrium och sällsynta jordartsmetaller (YREE), underjordisk, Ytterby mine, geomikrobiologi, mikrobiell kemi
National Category
Earth and Related Environmental Sciences
Research subject
Geochemistry
Identifiers
urn:nbn:se:su:diva-175390 (URN)978-91-7797-841-1 (ISBN)978-91-7797-842-8 (ISBN)
Public defence
2019-12-11, Nordenskiöldsalen, Geovetenskapens hus, Svante Arrhenius väg 12, 10:00 (English)
Opponent
Supervisors
Note

At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 3: Manuscript. Paper 4: Manuscript.

Available from: 2019-11-18 Created: 2019-10-23 Last updated: 2019-11-07Bibliographically approved

Open Access in DiVA

No full text in DiVA

Other links

Publisher's full text

Search in DiVA

By author/editor
Sjöberg, SusanneRattray, Jayne E.Callac, NolwennSkelton, AlasdairDupraz, Christophe
By organisation
Department of Geological Sciences
In the same journal
Applied Geochemistry
Earth and Related Environmental Sciences

Search outside of DiVA

GoogleGoogle Scholar

doi
urn-nbn

Altmetric score

doi
urn-nbn
Total: 23 hits
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf