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The evolution of early life is intimately related to environmental changes on Earth, and in particular, the accumulation of oxygen in the atmosphere and oceans. However, the record of environmental O2 abundance in the middle to late Proterozoic Eon, during which many new eukaryotic lineages emerged, is sparse and controversial. Here we present a uranium (U) isotope record from late Proterozoic shales from northwestern Canada, Arctic Canada (Baffin Island), Svalbard, and Greenland, coupled with a novel approach for inferring authigenic U isotope values (δ238Uauthigenic). A compilation comprising our new data and available literature data (854 δ238Uauthigenic values) through geologic time indicates a consistent rise in δ238Uauthigenic values following the Great Oxidation Event. This gradual increase in δ238U can be interpreted as an increase in the frequency of transient oxygenation events and also as a variation of U isotope fractionation factors between authigenic uptake and seawater (Δ238U) associated with different redox conditions occurring over the Earth's history. In conjunction with the U isotopic signature, we used previously published Fe speciation data from our samples to infer local controls on U incorporation and isotopic fractionation. The results suggest that late Proterozoic oceans were dominantly ferruginous, punctuated by periods of transient oxygenation. During these transient oxic conditions, high U isotope fractionation resulted in Δ238U values as high as ~1.2‰ relative to the δ238Ucrust. However, under ferruginous conditions, smaller isotopic fractionation led to Δ238U values

This study reports U-series activity ratios from river waters and six soil profiles across a soil chronosequence formed since the last glacial retreat, in Glen Feshie, Scotland. The overall aim is to examine the geochemical behaviour of the U-series nuclides in a boreal climate setting. The U-series data show that U is being both added to and leached out of the soils, to varying degrees. The U addition elevates the (234U/238U) of the bulk soils (up to 1.25), which is most pronounced in the youngest and the upper organic-rich soil horizons. The U addition appears to be linked to U adsorption, controlled by the degree of flooding by the Feshie River. The Feshie River has a high (234U/238U) ratio (~ 1.7), a feature shared with most high-latitude Northern Hemisphere rivers. For the soil profiles with no significant U addition, U-series nuclide modelling suggests U leaching rates on the order of 0.5–2 × 10− 5 y− 1, a similar range to other Northern Hemisphere high-latitude areas affected by the last glaciation, e.g. Mackenzie Basin, Canada. These two observations suggest a link between weathering rates and riverine (234U/238U) for areas that have been glaciated recently. A global compilation of major rivers shows that high-latitude Northern Hemisphere rivers comprise a significant U flux to the ocean with high (234U/238U). Thus, past changes in this Northern Hemisphere high-latitude U flux may have played a major role in oceanic (234U/238U) variation over glacial–interglacial cycles.

This study investigates U-series, Sr isotopes, major and trace elements in a chalk aquifer system located in Eastern France. Soil and rock samples were collected along depth profiles down to 45 m in four localities as an attempt to investigate the weathering processes in the soil, the unsaturated zone and the saturated zone of the aquifer. Interstitial water was extracted from soils and rocks by a centrifugation technique. U-series offer a powerful tool to calculate weathering rates because the relative mobility of the U- and Th-isotopes can be precisely measured and it does not require the determination of a reference state as in other approaches. As expected, the data show very large mobile element depletion in the soil with large 230Th excess relative to 238U, while the rocks show more limited but not insignificant mobile element depletion. The U-series data have been used to constrain weathering rates based on a 1-D reactive transport model. Weathering rates in the near surface are about 10–100 times faster than at depth. However, when integrated over the depth of the cores, including the unsaturated and the saturated zones, this underground weathering represents more than 30% of the total weathering flux, assuming congruent dissolution of carbonates. The (234U/238U) ratios in interstitial water are consistent with solid samples showing 234U depletion near the surface and an excess 234U at depth. A leaching experiment performed on chalk shows that the excess 234U in natural waters percolating through carbonate rocks results both from preferential 234U leaching and direct recoil in the interstitial water. A new approach was used to derive the recoil ejection factor based on BET measurements and the fractal dimension of chalk surface. Consideration of preferential leaching and recoil allows a more accurate modeling of weathering rates.

Novel metal isotope systematics are increasingly used to understand environmental change in geological history. On a global scale, the isotopic budgets of these metals respond to a range of environmental processes, allowing them to trace complex changes in the global climate system and carbon cycle. In particular, uranium (U) and molybdenum (Mo) isotopes are useful tools for quantifying the global extent of oceanic anoxia and euxinia respectively. The oceanic signature of these metals is recorded in contemporaneous marine sediments. Whilst, traditionally, organic-rich anoxic ‘black shales’ have provided a useful archive of these metals, carbonate sediments are increasingly being used as a passive recorder of ocean chemistry. The majority of published U and Mo isotope studies come from shallow water platform environments. By contrast, pelagic carbonate sediments are an under-explored archive for these metals, yet are widely available for important periods of Earth history. Despite their advantages, carbonates are a complex archive, containing multiple ‘contaminant’ components such as Mn-oxides, organic matter and detrital minerals. Each of these phases can have different metal concentrations and isotopic signatures, giving the potential to distort or bias the true oceanic signature recorded by the carbonate. Reductive cleaning procedures and selective leaching protocols can be used to avoid these contaminant phases, and are tested here on modern and ancient samples to judge their efficacy in isolating a ‘carbonate-bound fraction’. To this end, leaching experiments were performed using different concentration acetic acid, HCl and HNO3, on reductively cleaned and uncleaned sample pairs. The data demonstrate that Mn-oxide coatings and exchangeable phases have a large impact on the Mo isotopic signature (98Mo) of carbonates, even when weak leaching techniques are used to preferentially dissolve them. Furthermore, detrital sources of Mo are also easy to liberate with different leaching protocols, and exert a significant control on leachate isotopic composition. The leaching studies identify that the pelagic carbonate end-member has a relatively high 98Mo, but the precise relationship to seawater compositions remains unclear. For U, significant contributions from non-carbonate phases can clearly be identified in higher concentration leaching acids using U/Ca ratios. However, U isotopes (238U) show no resolvable difference with different leaching procedures and are not affected by reductive cleaning. This result probably reflects (a) the low potential for leaching refractory residual detrital U phases (e.g., zircon) that contain the majority of U in the sample and (b) the low U inventories of Mn oxides versus those of Mo. Instead, leaching likely extracts U that is mineralogically bound in carbonates and authigenic clays, which share a common isotopic signature. These new data suggest that U incorporation into pelagic carbonates may be dominated by adsorption, and be offset from seawater by ~ -0.15 ‰, in a similar manner to that seen for clays. ISSN:0009-2541 ISSN:1872-6836