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Interpreting isotopic signatures documented in natural rocks requires knowledge of equilibrium isotopic fractionation factors. Here, we determine equilibrium Fe isotope fractionation factors between several common rock-forming minerals using a comparative approach involving three independent methods: (i) isotopic analyses of natural minerals from a metapelite from Mt. Moosilauke, New Hampshire, for which equilibration temperature and pressure are well constrained to be near the aluminosilicate triple point (T ≃ 500 °C, P ≃ 4 kbar), (ii) Nuclear Resonant Inelastic X-ray Scattering (NRIXS) measurements of Fe force constants of minerals, and (iii) Density Functional Theory (DFT) ab initio calculations of Fe force constants of minerals. The minerals studied for Fe isotopes include, in increasing order of their β-factors: garnet We show how the newly determined equilibrium fractionation factors can be used to address diverse problems in Earth and planetary sciences, notably (i) Fe and Mg isotopic fractionation during anatexis, (ii) Fe isotopic fractionation in lunar ilmenite, and (iii) Ti isotopic fractionation during fluvial transport of minerals.

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.

International audience; Magmatic differentiation produces positive correlations between δ49Ti and SiO2. The equilibrium Ti isotope fractionation factors of Ti-bearing minerals are essential for understanding the mechanisms driving this isotopic fractionation. We present ab initio-derived mean force constants of Ti-bearing minerals (barium orthotitanate, potassium titanium oxide, fresnoite, diopside, geikielite, karrooite, titanite, pseudobrookite, anatase, and titanium oxide) based on density functional theory (DFT) to calculate equilibrium isotopic fractionation factors. We find that the main driver for Ti isotopic fractionation is its coordination, with four-, five-, and sixfold-coordinated Ti characterized by mean force constants of 547, 462, and 310 N/m, respectively. The coordination number of Ti in silicate melts is thought to be lower than in minerals, driving magmas toward higher δ49Ti values by fractional crystallization. The mineral-melt fractionation factors allow modeling of the observed Ti isotope trends in tholeiitic and calc-alkaline rocks. Our model results indicate that to first order, the steeper δ49Ti trend observed in tholeiitic versus calc-alkaline magmas is most likely due to enhanced removal of Ti into sequestered minerals at low SiO2 concentration in tholeiitic series compared to calc-alkaline series. The δ49Ti–SiO2 differentiation trends, however, depend on Ti coordination in the melt and the strengths of Ti bonds in diverse Fe- and Ti-oxides, which are still uncertain. Our results show that Ti isotopes can be used to reconstruct the crystallization history and identify the magmatic series parentage of magmas that otherwise lack context, but further work is needed to identify the drivers behind Ti isotopic fractionation in igneous rocks.

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.

The residence time of subglacial meltwater impacts aquifer recharge, nutrient production, and chemical signals that reflect underlying bedrock/substrate, but is inaccessible to direct observation. Here we report the seasonal evolution of subglacial meltwater chemistry from the 2011 melt season at the terminus of the Athabasca Glacier, Canada. We measured major and trace analytes and U-series isotopes for twenty-nine bulk meltwater samples collected over the duration of the melt season. This dataset, which is the longest time-series record of ( 234 U/ 238 U) isotopes in a glacial meltwater system, provides insight into the hydrologic evolution of the subglacial system during active melting. Meltwater samples, measured from the outflow, were analyzed for ( 238 U), ( 222 Rn) and ( 234 U/ 238 U) activity , conductivity, alkalinity, pH and major cations. Subglacial meltwater varied in [ 238 U] and ( 222 Rn) from 23 to 832 ppt and 9 to 171 pCi/L, respectively. Activity ratios of ( 234 U/ 238 U) ranged from 1.003 to 1.040, with the highest ( 238 U), ( 222 Rn) and ( 234 U/ 238 U) activity values occurring in early May when delayed-flow basal meltwater composed a significant portion of the bulk melt. From the chemical evolution of the meltwater, we posit that the relative subglacial water residence times decrease over the course of the melt season. This decrease in qualitative residence time during active melt is consistent with prior field studies and model-predicted channel switching from a delayed, distributed network to a fast, channelized network flow. As such, our study provides support for linking U-series isotopes to storage lengths of meltwater beneath glacial systems as subglacial hydrologic networks evolve with increased melting and channel network efficiency.

The Upper Fremont Glacier (UFG), Wyoming, is one of the few continental glaciers in the contiguous United States known to preserve environmental and climate records spanning recent centuries. A pair of ice cores taken from UFG have been studied extensively to document changes in climate and industrial pollution (most notably, mid-19th century increases in mercury pollution). Fundamental to these studies is the chronology used to map ice-core depth to age. Here, we present a revised chronology for the UFG ice cores based on new measurements and using a novel dating approach of synchronizing continuous water isotope measurements to a nearby tree-ring chronology. While consistent with the few unambiguous age controls underpinning the previous UFG chronologies, the new interpretation suggests a very different time scale for the UFG cores with changes of up to 80 years. Mercury increases previously associated with the mid-19th century Gold Rush now coincide with early-20th century industrial emissions, aligning the UFG record with other North American mercury records from ice and lake sediment cores. Additionally, new UFG records of industrial pollutants parallel changes documented in ice cores from southern Greenland, further validating the new UFG chronologies while documenting the extent of late 19th and early 20th century pollution in remote North America.

The generation and transport of mineral dust is strongly related to climate on seasonal, year-to-year, and glacial-interglacial timescales. The modern dust cycle is influenced by soil moisture, which is partly a function of drought duration and severity. The production and transport of dust can therefore be amplified by global and regional droughts, thereby moderating ecosystem vulnerability to disturbance through the influence of dust on nutrient delivery to ecosystems. In this work, we use strontium and neodymium isotopes in combination with trace element concentrations in modern dust samples collected in 2015 to quantify the role of regionally versus globally supplied dust in nutrient delivery to a montane ecosystem. The study sites lie along an elevational transect in the southern Sierra Nevada, USA, with samples spanning the dry seasons of 2014 (Aciego et al., 2017) and 2015 (this study), when the region was experiencing a historic drought. The goal of our research was to quantify the spatial and temporal variability and sensitivity of the dust cycle to short term changes at nutrient-limited sites. We find that, during the dry season of 2015, Asian sources contributed between 10 and 40% of dust to sites located along this elevational transect, and importantly increased in importance during the summer growing season compared to regional dust sources. These changes are likely related to the prolonged drought in Asia in 2015, highlighting both the sensitivity of dust production and transport to drought and the teleconnections of dust transport in terrestrial ecosystems.

Over the past ~ 5000 years, amplified dust generation and deposition in the American West has been linked to human activity. In recent decades, intensified rates of agriculture and livestock grazing have been correlated with greater dust production detected on seasonal to annual timescales. The combination of land use intensification and climate change (i.e. increased drought frequency) in North America highlights the importance of characterizing the sources of dust both before and after the influence of anthropogenic activity. We apply high-precision geochemical and isotopic (Sr and Nd isotopes) techniques to an ice core from the Upper Fremont Glacier (Wyoming, USA) to produce the first glacial dataset from the American West. Our Sr-Nd isotopic composition data indicates the evolving dust provenance to the Upper Fremont Glacier (UFG) from a long-range transport of mineral dust to a local source. This increasing input of dust from a local source is supported by a rise in average dust particle diameter combined with greater average dust concentration throughout the record. The greater presence of dust particles smaller than 2.5 μm in the most recent samples from UFG ice core record support existing satellite and sediment core data regarding the effects of anthropogenic activity upon dust sources and pathways in the American West. Although the Sr-Nd isotope database in North America needs be expanded, our results provide a survey of windborne dust through the past 270 years.

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.

Recent declines in ice shelf and sea ice extent experienced in polar regions highlight the importance of evaluating variations in local weather patterns in response to climate change. Airborne mineral particles (dust) transported through the atmosphere and deposited on ice sheets and glaciers in Antarctica and Greenland can provide a robust set of tools for resolving the evolution of climatic systems through time. Here we present the first high time resolution radiogenic isotope (strontium and neodymium) data for Holocene dust in a coastal East Antarctic ice core, accompanied by rare earth element composition, dust concentration, and particle size distribution during the last deglaciation. We aim to use these combined ice core data to determine dust provenance, with variations indicative of shifts in either dust production, sources, and/or transport pathways. We analyzed a series of 17 samples from the Taylor Dome (77°47′47″S, 158°43′26″E) ice core, 113–391 m in depth from 1.1–31.4 ka. Radiogenic isotopic and rare earth element compositions of dust during the last glacial period are in good agreement with previously measured East Antarctic ice core dust records. In contrast, the Holocene dust dataset displays a broad range in isotopic and rare earth element compositions, suggesting a shift from long-range transported dust to a more variable, local input that may be linked to the retreat of the Ross Ice Shelf during the last deglaciation. Observed changes in the dust cycle inferred from a coastal East Antarctic ice core can thus be used to infer an evolving local climate.

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.

Dust provides ecosystem-sustaining nutrients to landscapes underlain by intensively weathered soils. Here we show that dust may also be crucial in montane forest ecosystems, dominating nutrient budgets despite continuous replacement of depleted soils with fresh bedrock via erosion. Strontium and neodymium isotopes in modern dust show that Asian sources contribute 18–45% of dust deposition across our Sierra Nevada, California study sites. The remaining dust originates regionally from the nearby Central Valley. Measured dust fluxes are greater than or equal to modern erosional outputs from hillslopes to channels, and account for 10–20% of estimated millennial-average inputs of bedrock P. Our results demonstrate that exogenic dust can drive the evolution of nutrient budgets in montane ecosystems, with implications for predicting forest response to changes in climate and land use., Dust is an important nutrient source to landscapes, but often the source of dust is poorly constrained. Here, the authors quantify the origin of different dust sources in the Sierra Nevada by analysing dust composition and suggest exogenic dust may drive nutrient budgets in montane ecosystems.

Mineral dust is transported in the atmosphere and deposited in oceans, ice sheets and the terrestrial biosphere. Temporal changes in locations of dust source areas and transport pathways have implications for global climate and biogeochemical cycles. The chemical and physical characterization of the dust record preserved in ice cores is useful for identifying of dust source regions, dust transport, dominant wind direction and storm trajectories. Here, we present a 50,000-year geochemical characterization of mineral dust entrapped in a horizontal ice core from the Taylor Glacier in East Antarctica. Strontium (Sr) and neodymium (Nd) isotopes, grain size distribution, trace and rare earth element (REE) concentrations, and inorganic ion (Cl− and Na+) concentrations were measured in 38 samples, corresponding to a time interval from 46 kyr before present (BP) to present. The Sr and Nd isotope compositions of insoluble dust in the Taylor Glacier ice shows distinct changes between the Last Glacial Period (LGP in this study ranging from ∼46.7–15.3 kyr BP) the early Holocene (in this study ranging from ∼14.5–8.7 kyr BP), and zero-age samples. The 87Sr/86Sr isotopic composition of dust in the Taylor Glacier ice ranged from 0.708 to 0.711 during the LGP, while the variability during the early Holocene is higher ranging from 0.707 to 0.714. The eNd composition ranges from 0.1 to −3.9 during the LGP, and is more variable from 1.9 to −8.2 during the early Holocene. The increased isotopic variability during the early Holocene suggests a shift in dust provenance coinciding with the major climate transition from the LGP to the Holocene. The isotopic composition and multiple physical and chemical constraints support previous work attributing Southern South America (SSA) as the main dust source to East Antarctica during the LGP, and a combination of both local Ross Sea Sector dust sources and SSA after the transition into the Holocene. This study provides the first high time resolution data showing variations in dust provenance to East Antarctic ice during a major climate regime shift, and we provide evidence of changes in the atmospheric transport pathways of dust following the last deglaciation.