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The Early Jurassic Butcher Ridge Igneous Complex (BRIC) in the Transantarctic Mountains contains abundant and variably hydrated silicic glass which has the potential to preserve a rich paleoclimate record. Here we present Fourier Transform Infrared Spectroscopic data that indicates BRIC glasses contain up to ~8 wt.% molecular water (H₂O_m), and low (<0.8 wt.%) hydroxyl (OH) component, interpreted as evidence for secondary hydration by meteoric water. BRIC glasses contain the most depleted hydrogen isotopes yet measured in terrestrial rocks, down to δD = −325 ‰. In situ⁴⁰Ar/³⁹Ar geochronology of hydrated glasses with ultra-depleted δD values yield ages from 105 Ma to 72 Ma with a peak at c. 91.4 Ma. Combined, these data suggest hydration of BRIC glasses by polar glacial ice and melt water during the Late Cretaceous, contradicting paleoclimate reconstructions of this period that suggest Antarctica was ice-free and part of a global hot greenhouse.

Oxygen isotopic ratios are largely homogenous in the bulk of Earth’s mantle but are strongly fractionated near the Earth’s surface, thus these are robust indicators of recycling of surface materials to the mantle. Here we document a subtle but significant ~0.2‰ temporal decrease in δ¹⁸O in the shallowest continental lithospheric mantle since the Archean, no change in Δ′¹⁷O is observed. Younger samples document a decrease and greater heterogeneity of δ¹⁸O due to the development and progression of plate tectonics and subduction. We posit that δ¹⁸O in the oldest Archean samples provides the best δ¹⁸O estimate for the Earth of 5.37‰ for olivine and 5.57‰ for bulk peridotite, values that are comparable to lunar rocks as the moon did not have plate tectonics. Given the large volume of the continental lithospheric mantle, even small decreases in its δ¹⁸O may explain the increasing δ¹⁸O of the continental crust since oxygen is progressively redistributed by fluids between these reservoirs via high-δ¹⁸O sediment accretion and low-δ¹⁸O mantle in subduction zones.

There is abundant evidence for significant H2O in evolved melts from the platinum-rich UG2 chromitite and the Merensky Reef of the Bushveld Complex (South Africa), but there is no consensus about the source of H2O. We report triple-oxygen and hydrogen isotope ratios of interstitial, late-magmatic phlogopite from three localities of the UG2 layer. The phlogopite yielded δD values of –43‰ to –23‰, which is >30‰ higher than previously known from Bushveld rocks and far above the mantle values of ~–75‰. The phlogopite triple-oxygen isotope ratios are the first to be reported for Bushveld rocks, with values of Δ′17O0.5305 (17O excess relative to the reference line 0.5305) from –0.069‰ to –0.044‰ (δ18O 5.2‰–6.2‰). The oxygen data support existing models of as much as 30%–40% contamination of mantle-derived magmas in the lower to middle crust. However, the high δD values require a second step of contamination, which we attribute to brines from the marine sediments in the Transvaal Basin at the emplacement level.

This Chapter considers triple oxygen isotope variations and their 4 Gyr temporal evolution in bulk siliciclastic sedimentary rocks and in granites. The d18O and D'17O values provide new insights into weathering in the modern and ancient hydrosphere and coeval crustal petrogenesis. We make use of the known geological events and processes that affect the rock cycle: supercontinent assembly and breakup that influence continent-scale and global climate, the fraction of the exposed crust undergoing weathering, and isotopic values of precipitation. New data from a 5000 m Texas drillhole into the Oligocene Frio Formation demonstrate minimal isotopic shifts from mudrocks to shales during diagenesis, mostly related to expulsion of water from smectite-rich loosely cemented sediment and its conversion to illite-rich shale. Inversion of triple oxygen isotope fractionations return isotopic values and temperatures along the hole depth that are more consistent with weathering conditions in the Oligocene and modern North America (d18O = -7 to -15‰, and T of +15 to +45°C) rather than d18O from 8 to 10‰ diagenetic water in the drill hole at 175-195°C. More precise T and d18Owater are obtained where the chemical index of alteration (CIA) based detrital contribution is subtracted from these sediments. Triple oxygen isotopes frommore »suspended sediments in major world rivers record conditions (T and d18Ow) of their watersheds, and not the composition of bedrock because weathering is water-dominated. In parallel, the Chapter presents new analyses of 100 granites, orthogneisses, migmatites, tonalite-trondhjemite-granodiorite (TTG), and large-volume ignimbrites from around the world that range in age from 4 Ga to modern. Most studied granites are orogenic and anatectic in origin and represent large volume remelting/assimilation of shales and other metasediments; the most crustal and high-d18O of these are thus reflect and record the average composition of evolving continental crust. Granites also develop a significant progressive increase in d18O values from 6-7‰ (4-2.5 Ga) to 10-13‰ (~1.8-1.2 Ga) after which d18O stays constant or even decreases. More importantly, we observe a moderate -0.03‰ step-wise decrease in D'17O between 2.1 and 2.5 Ga, which is about half of the step-wise decrease observed in shales over this time interval. We suggest that granites, as well as shales, record the significant advent and greater volumetric appearance of low-D'17O, high-d18O weathering products (shales) altered by meteoric waters upon rapid emergence of large land masses at ~2.4 Ga, although consider alternative interpretations. These weathering products were incorporated into abundant 2.0-1.8 Ga orogens around the world, where upon remelting, they passed their isotopic signature to the granites. We further observe the dichotomy of high-D'17O Archean shales, and unusually low-D'17O Archean granites. We attribute this to greater contribution from shallow crustal hydrothermal contribution to shales in greenstone belts, while granites in the earliest 3.0-4.0 Ga crust and TTGs require involvement of hydrothermal products with lower-D'17O signatures at moderately high-d18O, which we attribute to secondary silicification of their protoliths before partial melting. The Chapter further discusses evolution of the shale record through geologic history and discusses the step-wise change in d18O and D'17O values at Archean/Proterozoic transition. Denser coverage for shales in the past 1 billion years permits investigation of the rocks and their weathering in the last supercontinent cycle, with observed lighter d18O values, characteristic for the mid-Phanerozoic at the initiation of Gondwana breakup. The continuing increase in d18O values of the shales since 4 Ga is interpreted to reflect accumulation of weathering products via shale accretion to continents, as low-density and buoyant shales tend to not subduct back into the mantle. The rock cycle passes triple oxygen isotopic signatures from precipitation to sedimentary, metasedimentary, and finally to anatectic igneous rocks. Continental crust became progressively heavier in d18O, lighter in D'17O due to incremental accumulation of high-d18O sediments in accretionary wedges. Second-order trends in d18O and D'17O are due to supercontinent cycles and glacial episodes.« less