Frei,R. and Polat,A.(2013): Chromium isotope fractionation during oxidative weathering - Implications from the study of a Paleoproterozoic (ca. 1.9 Ga) paleosol, Schreiber Beach, Ontario, Canada. Precambrian Research, 224, 434-453.

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wAbstract
@This study reports detailed stable Cr, Sm-Nd and Rb-Sr isotope data for a ca. 1.9 Ga old subaerial weathering profile at Schreiber Beach, Ontario, Canada, from which detailed major and trace element signatures and ƒΒ18O values were previously reported. The weathering profile developed on Neoarchean (`2.7 Ga) pillow basalts and is unconformably overlain by the Paleoproterozoic (`1.88 Ga) Gunflint Chert and basal conglomerates. This stratigraphy suggests that the basalts were uplifted and subaerially weathered prior to deposition of the Gunflint Formation.
@The aim was to investigate the behaviour of chromium during ancient weathering processes and to contribute to the question whether or not stable isotope fractionation accompanied the release of chromium from the weathering rocks at times when atmospheric oxygen was supposedly high enough (in a period following the Great Oxygenation Event (GOE) `2.45 Ga ago and prior to the deposition of the Gunflint cherts at `1.82 Ga). These iron-rich cherts belong to one of the last regionally extensive banded iron formations (BIFs) deposited before the `1 billion year-long Mesoproterozoic period during which a drastic change in ocean chemistry prevented deposition of BIFs.
@The gradual textural, mineralogical, and geochemical changes from unweathered basalts to strongly weathered hematite-bearing basalts with increasing stratigraphic height are associated with shifts in the chromium isotope compositions. The ƒΒ53Cr value of unweathered pillow basalt cores (-0.19}0.02ρ, 2ƒΠ) is within the range of mantle inventory values, whereas weathered brown to green basalts (soils), exhibiting up to 30% lower Cr concentrations compared to unweathered pillow cores, are isotopically lighter (ƒΒ53Cr = -0.35}0.11ρ). In contrast, red, hematite-rich basalts and hyaloclastites underlying the brown to green basaltic soils, with the highest ƒΒ18O enrichment in the profile, are isotopically heavier (ƒΒ53Cr = +0.05}0.15ρ). Rb-Sr isotope data of weathered basalts define a correlation line with a slope corresponding to an age of 1574}24 Ma (MSWD = 13) which we interpret to reflect a diagenetic event accompanied by alkaline metasomatism during subsidence/burial of the Gunflint basin. The non-correlation of K enrichment factors with ƒΒ53Cr, ƒΒ18O and other major and trace elements in the weathered rocks indicates that alkaline metasomatism did not affect the geochemical signatures produced during in situ subaerial weathering. Instead, correlations between ƒΒ53Cr and ƒΒ18O, and between ƒΒ53Cr, Ce/Ce*, U and V, indicate coupled mobilization of the redox sensitive elements during oxidative processes and their partial re-deposition at depth from high ƒΒ18O freshwaters. Partial re-precipitation of heavy Cr at depth can be explained on the basis of the weak positive correlation between ƒΒ53Cr and Fe enrichment factors; it is seen as a consequence of the reduction of mobile Cr(VI) and co-precipitation as mixed Fe(III)-Cr(III) oxhydroxides during contemporaneous oxidation of the Fe2+-bearing groundwaters at depth, a process similar to the one governing the deposition of most Precambrian BIFs. Redistribution of certain elements during the weathering process, in this case REEs, is furthermore indicated by a correlation line in a Sm-Nd isochron diagram defined by the Schreiber Beach data with a slope corresponding to an age of 1.93}0.19 Ga (MSWD = 26), an age which is compatible with the direct geological constraints for the timing of the paleosol formation at this locality.

Keywords: Chromium isotopes; Paleosol; Paleoproterozoic weathering profile; Red soil; Gunflint Formation; Trace elements; Oxygen isotopesx

1. Introduction
2. Geological relationships
@2.1. Regional geology
@2.2. The Schreiber Beach profile
3. Samples
4. Analytical methods
@4.1. Separation of Cr
@4.2. Separation of Sm-Nd and Rb-St isotopes
@4.3. TIMS measurements
@4.4. Major and trace elements, and oxygen isotopes
@4.5. SEM (scanning electron microscope)-BSE (backscatter electron) analyses
5. Results
@5.1. Cr isotopes and Cr concentrations
@5.2. Rb-Sr isotopes
@5.3. Sm-Nd isotopes
@5.4. Element enrichment/depletion and inter element/isotope relationships
6. Discussion
@6.1. Is the Schreiber Beach profile a weathering profile?
@6.2. Cr mobility recorded in the weathering profile
@6.3. Alkaline metasomatism versus in situ weathering
@6.4. Implications for the use of Cr isotopes as a tracer for oxidative weathering
7. Conclusions
Acknowledgements
References


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