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Iron mobilization during continental weathering was pervasive before the Great Oxidation Event (GOE) that started at around 2.43 billion years (Ga) ago, due to the soluble nature of reduced iron. However, various geochemical proxies indicate transient oxygenation during deposition of the Mesoarchean (∼2.95 Ga) Pongola Supergroup, South Africa, which suggests that continental weathering could have also occurred under transiently oxic conditions before the GOE. We analyzed trace elemental and Fe, Ti, and Cr isotopic compositions of the ca. 2.95 Ga Denny Dalton paleosol in the Pongola Supergroup to better understand continental weathering and redox conditions in the ancient critical zone, and the nature of geochemical fluxes from the continents to the oceans and marine sediments. Iron isotope systematics are consistent with a model where Fe was released during intense leaching from the paleosol to concentrate in Fe-rich groundwaters in the deeper part of the soil horizon. We show for the first time that Fe isotopic fractionation during Mesoarchean continental weathering was limited, and Fe enrichments and depletions are coupled with those of divalent transition metals, Co, Ni, and particularly Zn. This suggests that Fe redox cycling was not involved in paleosol formation, and Fe2+ was mobilized under anoxic conditions. Chromium isotopes are also unfractionated relative to the parent igneous rock in this paleosol, which precludes removal of isotopically heavy Cr6+ and thus supports anoxic continental weathering. We show that previously reported Cr isotopic fractionation in another Denny Dalton paleosol profile does not follow a Cr6+ leaching trend, but instead scales with Cr enrichment and may reveal Cr enrichment from post-burial fluids. Thus, there is no clear evidence for an oxidative continental weathering during deposition of the Pongola Supergroup. Titanium isotopes are not significantly fractionated in the paleosol, suggesting that continental weathering and erosion in the Archean did not fractionate Ti isotopes. Similarly, Ni/Co and Th/Sc ratios are reasonably conserved, which validates their use as a robust proxy for upper continental crust composition in shales, whereas La/Sc, Cr/Zn and Cr/U ratios are highly variable relative to the provenance composition, which suggests that caution should be used when applying these ratios in shale studies of the ancient upper continental crust composition.

Recent work has demonstrated that titanium (Ti) isotopes undergo mass-dependent isotope fractionation during magmatic differentiation, leaving evolved silicic melts preferentially enriched in heavy Ti isotopes. Preferential incorporation of light Ti isotopes in crystallizing Fe-Ti oxides is thought to be the mechanism responsible for this fractionation in magmatic rocks. To test this hypothesis, we present Ti isotope measurements of Fe-Ti oxide mineral separates of Kilauea Iki lava lake samples. We find that the Ti in Fe-Ti oxides is isotopically light while Ti in the residual melt and minerals is isotopically heavy. This result is consistent with the results of density functional theory (DFT) calculations in other studies, which show progressive heavy isotope enrichment for Ti from 6-fold, 5-fold, through 4-fold coordinated minerals. We therefore conclude that Ti isotopes in silicate melts undergo isotope fractionation during the crystallization of Fe-Ti oxides because Ti in oxides is primarily in 6-fold coordination whereas Ti in silicate melts is in 5- or 4-fold coordination (Ti in more evolved magmas tends to be in lower coordination). Based on our mineral separate results, we estimate the fractionation factor at 1000 °C between silicate and oxide Δ49Tisilicate-oxide to be 0.39 ± 0.06‰. This result is consistent with the fractionation factors inferred in previous studies based on Ti isotopic analyses and modeling of bulk rock measurements. We use this fractionation factor and the fractionation factors proposed by previous workers in Rhyolite MELTS to model the δ49Ti evolution of plume lavas. We find the model to generally predict the fractionations observed in Kilauea Iki, as well as the fractionations previously observed in volcanics from Hekla, Iceland and Afar, East Africa.

Titanium isotopes reveal a shift toward convergent arc magmatism in some of Earth’s oldest known rocks., Plate subduction greatly influences the physical and chemical characteristics of Earth’s surface and deep interior, yet the timing of its initiation is debated because of the paucity of exposed rocks from Earth’s early history. We show that the titanium isotopic composition of orthogneisses from the Acasta Gneiss Complex spanning the Hadean to Eoarchean transition falls on two distinct magmatic differentiation trends. Hadean tonalitic gneisses show titanium isotopic compositions comparable to modern evolved tholeiitic magmas, formed by differentiation of dry parental magmas in plume settings. Younger Eoarchean granitoid gneisses have titanium isotopic compositions comparable to modern calc-alkaline magmas produced in convergent arcs. Our data therefore document a shift from tholeiitic- to calc-alkaline–style magmatism between 4.02 and 3.75 billion years (Ga) in the Slave craton.

Changes in the composition of dust trapped in ice provide evidence of past atmospheric circulation and earth surface conditions. Investigations of dust provenance in Antarctic ice during glacial and interglacial periods indicate that South America is the primary dust source during both climate regimes. Here, we present results from a new ice core dust archive extracted from the Taylor Glacier in coastal East Antarctica during the deglacial transition from Marine Isotope Stage 6 to 5e. Radiogenic strontium and neodymium isotopes indicate that last interglacial dust is young and volcanic, in contrast to the observed preindustrial and Holocene (Marine Isotope Stage 1) dust composition. The dust composition differences from the last interglacial and current interglacial period at the site require a profound difference in atmospheric transport and environmental conditions. We consider several potential causes for enhanced transport of volcanic material to the site, including increased availability of volcanic material and large-scale atmospheric circulation changes.

The generation, transport, and deposition of mineral dust are detectable in paleoclimate records from land, ocean, and ice, providing valuable insight into earth surface conditions and cycles on a range of timescales. Dust deposited in marine and terrestrial ecosystems can provide critical nutrients to nutrient-limited ecosystems, and variations in dust provenance can indicate changes in dust production, sources and transport pathways as a function of climate variability and land use change. Thus, temporal changes in locations of dust source areas and transport pathways have implications for understanding interactions between mineral dust, global climate, and biogeochemical cycles. This work characterizes dust from areas in the American West known for dust events and/or affected by increasing human settlement and livestock grazing during the last 150 years. Dust generation and uplift from these dust source areas depends on climate and land use practices, and the relative contribution of dust has likely changed since the expansion of industrialization and agriculture into the western United States. We present elemental and isotopic analysis of 28 potential dust source area samples analyzed using Thermal Ionization Mass Spectrometry (TIMS) for 87Sr/86Sr and 143Nd/144Nd composition and Multi-Collector Inductively Coupled Plasma Mass Spectrometer (MC-ICPMS) for 176Hf/177Hf composition, and ICPMS for major and trace element concentrations. We find significant variability in the Sr, Nd, and Hf isotope compositions of potential source areas of dust throughout western North America, ranging from 87Sr/86Sr = 0.703699 to 0.740236, eNd = −26.6 to 2.4, and eHf = −21.7 to −0.1. We also report differences in the trace metal and phosphorus concentrations in the geologic provinces sampled. This research provides an important resource for the geochemical tracing of dust sources and sinks in western North America, and will aid in modeling the biogeochemical impacts of increased dust generation and deposition caused by higher drought frequency and human activity.

Isotopic characterization of aerosol mineral particles (atmospheric dust) of varying sizes is essential in classifying source areas, and for determining the source of dust deposited over oceans and icesheets. However, the effect of atmospheric transport on radiogenic isotopic compositions is not well constrained, making provenance interpretation difficult. In order to investigate the isotopic variability of 176Hf/177Hf, 87Sr/86Sr and 143Nd/144Nd we analyzed eight airborne dust samples in two size fractions collected along a cross-Atlantic transect through a dust storm originating in the Sahara in late 2002. Past measurements of 176Hf/177Hf, 87Sr/86Sr and 143Nd/144Nd of dust have focused primarily on coarse sized particles (< 30 μm), whereas far field deposition is primarily finer particles (< 2 μm). Strontium or neodymium isotopic sorting based on distance is not evident in our dataset; however, the combined isotopic ratios of the dust collected suggest a Saharan origin. Hafnium isotopic compositions show an east to west trend towards more radiogenic compositions across the Atlantic, suggesting grain and mineral sorting during dust transport along the ~ 4000 km transect. Transport models with variable dust particle diameter and wind speed demonstrate the preferential depletion of the high-density mineral zircon during transport of dust from the source area. The transport model combined with a simple two component mixing model show that the Hf isotopic composition changes can be explained by the loss of the mineral zircon during transport. Modeling of this “zircon effect” with distance from the dust source in the Hf isotopic composition of marine, terrestrial and glacial dust deposits may reveal additional information concerning dust transport and sources in the geologic past.