Negative Ce anomalies in Mn oxides: The role of Ce4+ mobility during water-mineral interaction

A. Loges, Thomas Wagner, M. Barth, M. Bau, S. Göb, G. Markl

Forskningsoutput: TidskriftsbidragArtikelVetenskapligPeer review

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We present one of the very rare natural examples of extremely negative Ce anomalies (up to 4 orders of magnitude) in manganese oxides, caused by higher mobility of Ce4+ compared to REE3+ in an aquatic environment. The young secondary Mn oxides formed together with fluorites and goethites during water-mineral interaction in a hydrothermal fluorite vein. Our findings are in contrast to the oxidative scavenging of Ce, which is commonly observed in Mn oxides. Comparison of REE patterns from modern mine waters with primary and secondary minerals demonstrates that this cannot be solely explained as a source-related feature or by immobilization of Ce, but must at least partially be the result of preferential mobilization of Ce4+ compared to REE3+. We propose that this very unusual behavior is due to strong complexation of Ce4+, most likely by siderophores or similar organic molecules, based on published complex formation constants. The presence of dissolved organic carbon (DOC) even in water samples outflowing at the deepest mine level lends support to this model. Recent experimental studies have also demonstrated that negative Ce anomalies develop in biogenic Mn oxides, but this effect has not yet been reported from a natural environment. Our findings emphasize the relevance of experimental results for natural systems and have considerable implications for the assessment of the mobility of tetravalent actinide elements (especially Pu4+) in earth surface environments or potential high-level permanent repositories.

Originalspråkengelska
TidskriftGeochimica et Cosmochimica Acta
Volym86
Sidor (från-till)296-317
ISSN0016-7037
DOI
StatusPublicerad - 2012
Externt publiceradJa
MoE-publikationstypA1 Tidskriftsartikel-refererad

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title = "Negative Ce anomalies in Mn oxides: The role of Ce4+ mobility during water-mineral interaction",
abstract = "We present one of the very rare natural examples of extremely negative Ce anomalies (up to 4 orders of magnitude) in manganese oxides, caused by higher mobility of Ce4+ compared to REE3+ in an aquatic environment. The young secondary Mn oxides formed together with fluorites and goethites during water-mineral interaction in a hydrothermal fluorite vein. Our findings are in contrast to the oxidative scavenging of Ce, which is commonly observed in Mn oxides. Comparison of REE patterns from modern mine waters with primary and secondary minerals demonstrates that this cannot be solely explained as a source-related feature or by immobilization of Ce, but must at least partially be the result of preferential mobilization of Ce4+ compared to REE3+. We propose that this very unusual behavior is due to strong complexation of Ce4+, most likely by siderophores or similar organic molecules, based on published complex formation constants. The presence of dissolved organic carbon (DOC) even in water samples outflowing at the deepest mine level lends support to this model. Recent experimental studies have also demonstrated that negative Ce anomalies develop in biogenic Mn oxides, but this effect has not yet been reported from a natural environment. Our findings emphasize the relevance of experimental results for natural systems and have considerable implications for the assessment of the mobility of tetravalent actinide elements (especially Pu4+) in earth surface environments or potential high-level permanent repositories.",
author = "A. Loges and Thomas Wagner and M. Barth and M. Bau and S. G{\"o}b and G. Markl",
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Negative Ce anomalies in Mn oxides: The role of Ce4+ mobility during water-mineral interaction. / Loges, A.; Wagner, Thomas; Barth, M.; Bau, M.; Göb, S.; Markl, G.

I: Geochimica et Cosmochimica Acta, Vol. 86, 2012, s. 296-317.

Forskningsoutput: TidskriftsbidragArtikelVetenskapligPeer review

TY - JOUR

T1 - Negative Ce anomalies in Mn oxides: The role of Ce4+ mobility during water-mineral interaction

AU - Loges, A.

AU - Wagner, Thomas

AU - Barth, M.

AU - Bau, M.

AU - Göb, S.

AU - Markl, G.

PY - 2012

Y1 - 2012

N2 - We present one of the very rare natural examples of extremely negative Ce anomalies (up to 4 orders of magnitude) in manganese oxides, caused by higher mobility of Ce4+ compared to REE3+ in an aquatic environment. The young secondary Mn oxides formed together with fluorites and goethites during water-mineral interaction in a hydrothermal fluorite vein. Our findings are in contrast to the oxidative scavenging of Ce, which is commonly observed in Mn oxides. Comparison of REE patterns from modern mine waters with primary and secondary minerals demonstrates that this cannot be solely explained as a source-related feature or by immobilization of Ce, but must at least partially be the result of preferential mobilization of Ce4+ compared to REE3+. We propose that this very unusual behavior is due to strong complexation of Ce4+, most likely by siderophores or similar organic molecules, based on published complex formation constants. The presence of dissolved organic carbon (DOC) even in water samples outflowing at the deepest mine level lends support to this model. Recent experimental studies have also demonstrated that negative Ce anomalies develop in biogenic Mn oxides, but this effect has not yet been reported from a natural environment. Our findings emphasize the relevance of experimental results for natural systems and have considerable implications for the assessment of the mobility of tetravalent actinide elements (especially Pu4+) in earth surface environments or potential high-level permanent repositories.

AB - We present one of the very rare natural examples of extremely negative Ce anomalies (up to 4 orders of magnitude) in manganese oxides, caused by higher mobility of Ce4+ compared to REE3+ in an aquatic environment. The young secondary Mn oxides formed together with fluorites and goethites during water-mineral interaction in a hydrothermal fluorite vein. Our findings are in contrast to the oxidative scavenging of Ce, which is commonly observed in Mn oxides. Comparison of REE patterns from modern mine waters with primary and secondary minerals demonstrates that this cannot be solely explained as a source-related feature or by immobilization of Ce, but must at least partially be the result of preferential mobilization of Ce4+ compared to REE3+. We propose that this very unusual behavior is due to strong complexation of Ce4+, most likely by siderophores or similar organic molecules, based on published complex formation constants. The presence of dissolved organic carbon (DOC) even in water samples outflowing at the deepest mine level lends support to this model. Recent experimental studies have also demonstrated that negative Ce anomalies develop in biogenic Mn oxides, but this effect has not yet been reported from a natural environment. Our findings emphasize the relevance of experimental results for natural systems and have considerable implications for the assessment of the mobility of tetravalent actinide elements (especially Pu4+) in earth surface environments or potential high-level permanent repositories.

U2 - 10.1016/j.gca.2012.03.017

DO - 10.1016/j.gca.2012.03.017

M3 - Article

VL - 86

SP - 296

EP - 317

JO - Geochimica et Cosmochimica Acta

JF - Geochimica et Cosmochimica Acta

SN - 0016-7037

ER -