TY - JOUR

T1 - Micro-scale tracing of Fe and Si isotope signatures in banded iron formation using femtosecond laser ablation

AU - Steinhoefel, Grit

AU - Horn, Ingo

AU - von Blanckenburg, Friedhelm

N1 - Funding Information: We acknowledge the support of this study by the DFG, BGR-Hochschulvergabeprogramm, and New Wave Research. T. Oberthuer (BGR) kindly provided sample material. O. Dietrich and W. Hurkuck are thanked for technical support. We thank K. Konhauser for helpful comments on an early version of the paper and three reviewers for their constructive suggestions.

PY - 2009/9/15

Y1 - 2009/9/15

N2 - We have detected micrometre-scale differences in Fe and Si stable isotope ratios between coexisting minerals and between layers of banded iron formation (BIF) using an UV femtosecond laser ablation system connected to a MC-ICP-MS. In the magnetite-carbonate-chert BIF from the Archean Old Wanderer Formation in the Shurugwi Greenstone Belt (Zimbabwe), magnetite shows neither intra- nor inter-layer trends giving overall uniform δ56Fe values of ∼0.9‰, but exhibits intra-crystal zonation. Bulk iron carbonates are also relatively uniform at near-zero values, however, their individual δ56Fe value is highly composition-dependent: both siderite and ankerite and mixtures between both are present, and δ56Fe end member values are 0.4‰ for siderite and -0.7‰ for ankerite. The data suggest either an early diagenetic origin of magnetite and iron carbonates by the reaction of organic matter with ferric oxyhydroxides catalysed by Fe(III)-reducing bacteria; or more likely an abiotic reaction of organic carbon and Fe(III) during low-grade metamorphism. Si isotope composition of the Old Wanderer BIF also shows significant variations with δ30Si values that range between -1.0‰ and -2.6‰ for bulk layers. These isotope compositions suggest rapid precipitation of the silicate phases from hydrothermal-rich waters. Interestingly, Fe and Si isotope compositions of bulk layers are covariant and are interpreted as largely primary signatures. Moreover, the changes of Fe and Si isotope signatures between bulk layers directly reflect the upwelling dynamics of hydrothermal-rich water which govern the rates of Fe and Si precipitation and therefore also the development of layering. During periods of low hydrothermal activity, precipitation of only small amounts of ferric oxyhydroxide was followed by complete reduction with organic carbon during diagenesis resulting in carbonate-chert layers. During periods of intensive hydrothermal activity, precipitation rates of ferric oxyhydroxide were high, and subsequent diagenesis triggered only partial reduction, forming magnetite-carbonate-chert layers. We are confident that our micro-analytical technique is able to detect both the solute flux history into the sedimentary BIF precursor, and the BIF's diagenetic history from the comparison between coexisting minerals and their predicted fractionation factors.

AB - We have detected micrometre-scale differences in Fe and Si stable isotope ratios between coexisting minerals and between layers of banded iron formation (BIF) using an UV femtosecond laser ablation system connected to a MC-ICP-MS. In the magnetite-carbonate-chert BIF from the Archean Old Wanderer Formation in the Shurugwi Greenstone Belt (Zimbabwe), magnetite shows neither intra- nor inter-layer trends giving overall uniform δ56Fe values of ∼0.9‰, but exhibits intra-crystal zonation. Bulk iron carbonates are also relatively uniform at near-zero values, however, their individual δ56Fe value is highly composition-dependent: both siderite and ankerite and mixtures between both are present, and δ56Fe end member values are 0.4‰ for siderite and -0.7‰ for ankerite. The data suggest either an early diagenetic origin of magnetite and iron carbonates by the reaction of organic matter with ferric oxyhydroxides catalysed by Fe(III)-reducing bacteria; or more likely an abiotic reaction of organic carbon and Fe(III) during low-grade metamorphism. Si isotope composition of the Old Wanderer BIF also shows significant variations with δ30Si values that range between -1.0‰ and -2.6‰ for bulk layers. These isotope compositions suggest rapid precipitation of the silicate phases from hydrothermal-rich waters. Interestingly, Fe and Si isotope compositions of bulk layers are covariant and are interpreted as largely primary signatures. Moreover, the changes of Fe and Si isotope signatures between bulk layers directly reflect the upwelling dynamics of hydrothermal-rich water which govern the rates of Fe and Si precipitation and therefore also the development of layering. During periods of low hydrothermal activity, precipitation of only small amounts of ferric oxyhydroxide was followed by complete reduction with organic carbon during diagenesis resulting in carbonate-chert layers. During periods of intensive hydrothermal activity, precipitation rates of ferric oxyhydroxide were high, and subsequent diagenesis triggered only partial reduction, forming magnetite-carbonate-chert layers. We are confident that our micro-analytical technique is able to detect both the solute flux history into the sedimentary BIF precursor, and the BIF's diagenetic history from the comparison between coexisting minerals and their predicted fractionation factors.

UR - http://www.scopus.com/inward/record.url?scp=68249144723&partnerID=8YFLogxK

U2 - 10.1016/j.gca.2009.05.037

DO - 10.1016/j.gca.2009.05.037

M3 - Article

AN - SCOPUS:68249144723

VL - 73

SP - 5343

EP - 5360

JO - Geochimica et cosmochimica acta

JF - Geochimica et cosmochimica acta

SN - 0016-7037

IS - 18

ER -