wAbstract
@The redox-sensitive geochemical behavior of uranium permits the
use of Th/U ratios as a geochemical proxy for the oxidation state
of the atmosphere during deposition. Due to the effects of post-depositional
uranium mobility on Th/U ratios during events involving oxygenated
fluids, direct measurements of Th/U ratios are often misleading
even for drill core samples. Because both of these elements radioactively
decay and produce lead isotopes, the Pb isotope composition may
reflect the depositional Th/U ratio, although the Th/U ratios
induced by changes shortly after deposition may not be distinguished
from the true depositional Th/U ratios. In order to effectively
evaluate the time-integrated Th/U ratio (Θa), values for the initial
depositional Pb isotope composition must be determined or accepted
from the models for the whole Earth.
@While the timing for the rise of atmospheric oxygen is reasonably
well constrained now, its effect on continental weathering and
ocean redox state remains poorly constrained and debated. The
ca. 2.15 Ga Sengoma Argillite Formation of Botswana contains organic-rich
shales deposited during the Great Oxidation Event. The slope of
the 207Pb/204Pb-206Pb/204Pb
array of shales from the Sengoma Argillite Formation corresponds
to a Pb-Pb age that is within analytical error of the depositional
age and is, therefore, inferred to be the time by which the time-integrated
thorogenic and uranogenic lead growth started. The time-integrated
lead growth corresponds to an average Θa of 2.63 (}0.62, 1Π) for
the organic-rich shales of the Sengoma Argillite Formation . This
is lower than Th/U ratios measured in Archean shale suites or
estimated for the Archean-Proterozoic average upper continental
crust [Taylor,S.R. and McLennan,S.M., 1985. The Continental Crust:
Its Composition and Evolution. Blackwell, Oxford, 312pp.], which
indicates that these samples were enriched in uranium with respect
to thorium (and perhaps lead) at the time of deposition. In the
modern ocean, sediments are enriched in uranium under reducing
conditions by reduction of the water-soluble uranyl ion, which
is delivered to the ocean by oxidative weathering of continental
crust. To evaluate the potential mobility of Th, U, and Pb during
post-depositional processes, the concentrations of the rare earth
elements (REE) were also determined. Interelement ratios of the
largely immobile REE (in this study, La/Nd and Gd/Er) can be used
as a proxy for the Th/U ratio, as the geochemical behavior of
the lanthanide and actinide elements is similar under a variety
of conditions. Furthermore, close similarity in the chondrite-normalized
REE patterns and small range in La/Nd and Gd/Er ratios in studied
samples indicate that variations in Θa values are not likely to
have been controlled by mixing of one or more REE-, Th-, and U-rich
heavy minerals from the multiple detrital sources. Our study of
shales from the ca. 2.15 Ga Sengoma Argillite Formation indicates
that decoupling of U from Th, most likely related to the oxidative
continental weathering, began by 2.15 Ga, at the latest.
Keywords: Pb isotopes; Atmospheric oxygen; Great Oxidation Event;
Oxidative continental weathering; Rare earth elements; U-Th decouplingx
1. Introduction
2. Geochemical background
@2.1. U-Th-Pb geochemistry
@2.2. Rare earth element geochemistry
@2.3. Th-U-REE compatibility
3. Application of Pb isotopes and REE systematics to resolve between
redox decoupling of U from Th and multiple provenance sources
@3.1. Pb isotope ratio interpretations
@3.2. REE pattern interpretation
4. Regional geology and stratigraphy of the Sengoma Argillite
Formation
5. Analytical methods
@5.1. Whole-rock Pb isotope analysis
@5.2. Sequential acid Pb leaching
@5.3. Whole-rock REE analysis
6. Results
@6.1. Whole-rock Pb isotope ratios
@6.2. Leach step Pb isotope compositions
@6.3. REE data
7. Discussion
@7.1. Implications from U-Th-REE data
@7.2. Comparison to Archean and Paleoproterozoic record
8. Conclusions
Acknowledgements
References