Copper isotopes track the Neoproterozoic oxidation of cratonic mantle roots.

The oxygen fugacity (fO2) of the lower cratonic lithosphere influences diamond formation, melting mechanisms, and lithospheric evolution, but its redox evolution over time is unclear. We apply Cu isotopes (δ65Cu) of ~ 1.4 Ga lamproites and < 0.59 Ga silica-undersaturated alkaline rocks from the lithosphere-asthenosphere boundary (LAB) of the North Atlantic Craton to characterize fO2 and volatile speciation in their sources. The lamproites' low δ65Cu (-0.19 to -0.12‰) show that the LAB was metal-saturated with CH4 + H2O as the dominant volatiles during the Mesoproterozoic. The mantle-like δ65Cu of the < 0.59 Ga alkaline rocks (0.03 to 0.15‰) indicate that the LAB was more oxidized, stabilizing CO2 + H2O and destabilizing metals. The Neoproterozoic oxidation resulted in an increase of at least 2.5 log units in fO2 at the LAB. Combined with previously reported high fO2 in peridotites from the Slave, Kaapvaal, and Siberia cratonic roots, this oxidation might occur in cratonic roots globally.

Incipient carbonate melting drives metal and sulfur mobilization in the mantle.

We present results from high-pressure, high-temperature experiments that generate incipient carbonate melts at mantle conditions (~90 kilometers depth and temperatures between 750° and 1050°C). We show that these primitive carbonate melts can sequester sulfur in its oxidized form of sulfate, as well as base and precious metals from mantle lithologies of peridotite and pyroxenite. It is proposed that these carbonate sulfur-rich melts may be more widespread than previously thought and that they may play a first-order role in the metallogenic enhancement of localized lithospheric domains. They act as effective agents to dissolve, redistribute, and concentrate metals within discrete domains of the mantle and into shallower regions within Earth, where dynamic physicochemical processes can lead to ore genesis at various crustal depths.

Carbonate-rich crust subduction drives the deep carbon and chlorine cycles.

The flux balances of carbon and chlorine between subduction into the deep mantle and volcanic emissions into the atmosphere are crucial for the habitability of our planet1,2. However, pervasive loss of fluids from subducting slabs has been thought to cut off the delivery of both carbon and chlorine to the deep mantle owing to their high mobility under hydrous conditions3,4. Our new high-pressure experiments show that most carbonates (>75 wt%) in carbonate-rich crustal rocks-one of the main subducting carbon reservoirs-survive devolatilization and hydrous melting in cold and warm subduction zones, indicating that their subduction has driven the deep carbon cycle since the Mesoproterozoic. We found that KCl and NaCl, respectively, become stable phases crystallizing from hydrous carbonatite melts with low chlorine solubility in warm and hot subduction zones, resulting in the sequestration of chlorine in the solid residue in downwelling slabs. Accordingly, the subduction of carbonate-rich rocks facilitated highly effective recycling of both chlorine and carbon into the deep mantle at intermediate stages of Earth's history and led to declining atmospheric pCO2 and the formation of carbon-rich and chlorine-rich mantle reservoirs since the Mesoproterozoic. This period of optimal carbon and chlorine subduction may explain the ages of eclogitic diamonds and the formation of the HIMU mantle source.

Volcanic phosphorus supply boosted Mesozoic terrestrial biotas in northern China.

The Mesozoic terrestrial Jehol Biota of northern China exceeds the biomass and biodiversity of contemporaneous Lagerstätten. From 135 to 120 Ma, biotic radiation may have responded to the peak destruction of the North China Craton. However, the direct mechanistic link between geological and biological evolution is unclear. Phosphorus (P), a bio-essential nutrient, can be supplied by weathering of volcanics in terrestrial ecosystems. The middle-late Mesozoic volcanic-sedimentary sequences of northern China are amazingly rich in terrestrial organisms. Here we demonstrate episodic increases in P delivery, biological productivity, and species abundance in these strata to reveal the coevolution of volcanism and terrestrial biotas. A massive P supply from the weathering of voluminous volcanic products of craton destruction thus supported a terrestrial environment conducive to the high prosperity of the Jehol Biota. During the nascent stage of craton destruction, such volcanic-biotic coupling can also account for the preceding Yanliao Biota with relatively fewer fossils.

Rapid quench piston cylinder apparatus: An improved design for the recovery of volatile-rich geological glasses from experiments at 0.5-2.5 GPa.

The accurate and precise determination of the compositions of silicate glasses formed from melts containing volatile components H2O and CO2 recovered from high-pressure, high-temperature experiments is essential to our understanding of geodynamic processes taking place within the planet. Silicate melts are often difficult to analyze chemically because the formation of quench crystals and overgrowths on silicate phases is rapid and widespread upon quenching of experiments, preventing the formation of glasses in low-SiO2 and volatile-rich compositions. Here, we present experiments conducted in a novel rapid quench piston cylinder apparatus on a series of partially molten low-silica alkaline rock compositions (lamproite, basanite, and calk-alkaline basalt) with a range of water contents between 3.5 and 10 wt %. Quench modification of the volatile-bearing silicate glasses is significantly reduced compared to those produced in older piston cylinder apparatuses. The recovered glasses are almost completely free of quench modification and facilitate the determination of precise chemical compositions. We illustrate significantly improved quench textures and provide an analytical protocol that recovers accurate chemical compositions from both poorly quenched and well-quenched silicate glasses.

Origin of potassic postcollisional volcanic rocks in young, shallow, blueschist-rich lithosphere.

Potassium-rich volcanism occurring throughout the Alpine-Himalayan belt from Spain to Tibet is characterized by unusually high Th/La ratios, for which several hypotheses have brought no convincing solution. Here, we combine geochemical datasets from potassic postcollisional volcanic rocks and lawsonite blueschists to explain the high Th/La. Source regions of the volcanic melts consist of imbricated packages of blueschist facies mélanges and depleted peridotites, constituting a new mantle lithosphere formed only 20 to 50 million years earlier during the accretionary convergence of small continental blocks and oceans. This takes place entirely at shallow depths (<80 km) without any deep subduction of continental materials. High Th/La in potassic rocks may indicate shallow sources in accretionary settings even where later obscured by continental collision as in Tibet. This mechanism is consistent with a temporal trend in Th/La in potassic postcollisional magmas: The high Th/La signature first becomes prominent in the Phanerozoic, when blueschists became widespread.

Massive carbon storage in convergent margins initiated by subduction of limestone.

Remobilization of sedimentary carbonate in subduction zones modulates arc volcanism emissions and thus Earth's climate over geological timescales. Although limestones (or chalk) are thought to be the major carbon reservoir subducted to subarc depths, their fate is still unclear. Here we present high-pressure reaction experiments between impure limestone (7.4 wt.% clay) and dunite at 1.3-2.7 GPa to constrain the melting behaviour of subducted natural limestone in contact with peridotite. The results show that although clay impurities significantly depress the solidus of limestone, melting will not occur whilst limestones are still part of the subducting slab. Buoyancy calculations suggest that most of these limestones would form solid-state diapirs intruding into the mantle wedge, resulting in limited carbon flux to the deep mantle (< ~10 Mt C y-1). Less than 20% melting within the mantle wedge indicates that most limestones remain stable and are stored in subarc lithosphere, resulting in massive carbon storage in convergent margins considering their high carbon flux (~21.4 Mt C y-1). Assimilation and outgassing of these carbonates during arc magma ascent may dominate the carbon flux in volcanic arcs.

The largest negative carbon isotope excursions in Neoproterozoic carbonates caused by recycled carbonatite volcanic ash.

The late Ediacaran Shuram Excursion (SE) records the most prominent negative δ13C excursions (δ13C = -12‰) during Earth's history. It has been hypothesized to have resulted from oxidation of dissolved organic matter, diagenetic or authigenic precipitates. However, the origin of the SE remains enigmatic; current models face challenges regarding the significant amount of atmospheric oxygen needed to balance such extensive oxidation and sustained inputs of light carbon with extremely negative C isotope compositions. Here, we show that the Doushantuo Formation at the Jiulongwan section in South China, a key stratum recording the SE event, contains mineralogical and geochemical signatures related to igneous processes. Both the occurrence of ankerite, feldspar, moissanite and euhedral quartz in the SE samples and the relatively consistent Ce anomalies of carbonate and O isotopes of quartz indicate a contribution from an igneous source. In particular, the SE samples have trace element and C isotope compositions similar to those of recycled carbonatites formed by decarbonation and melting of sedimentary carbonate rocks. These observations suggest that the deep cycle of ancient carbonate rocks, which were subjected to decarbonation during subduction, melting and eruption related to the breakup of the Rodinia supercontinent, contributed to the SE. This igneous model for the SE may provide a connection between the deep and shallow carbon cycles of the Earth.

Displaced cratonic mantle concentrates deep carbon during continental rifting.

Continental rifts are important sources of mantle carbon dioxide (CO2) emission into Earth's atmosphere1-3. Because deep carbon is stored for long periods in the lithospheric mantle4-6, rift CO2 flux depends on lithospheric processes that control melt and volatile transport1,3,7. The influence of compositional and thickness differences between Archaean and Proterozoic lithosphere on deep-carbon fluxes remains untested. Here we propose that displacement of carbon-enriched Tanzanian cratonic mantle concentrates deep carbon below parts of the East African Rift System. Sources and fluxes of CO2 and helium are examined over a 350-kilometre-long transect crossing the boundary between orogenic (Natron and Magadi basins) and cratonic (Balangida and Manyara basins) lithosphere from north to south. Areas of diffuse CO2 degassing exhibit increasing mantle CO2 flux and 3He/4He ratios as the rift transitions from Archaean (cratonic) to Proterozoic (orogenic) lithosphere. Active carbonatite magmatism also occurs near the craton edge. These data indicate that advection of the root of thick Archaean lithosphere laterally to the base of the much thinner adjacent Proterozoic lithosphere creates a zone of highly concentrated deep carbon. This mode of deep-carbon extraction may increase CO2 fluxes in some continental rifts, helping to control the production and location of carbonate-rich magmas.

Kimberlite genesis from a common carbonate-rich primary melt modified by lithospheric mantle assimilation.

Quantifying the compositional evolution of mantle-derived melts from source to surface is fundamental for constraining the nature of primary melts and deep Earth composition. Despite abundant evidence for interaction between carbonate-rich melts, including diamondiferous kimberlites, and mantle wall rocks en route to surface, the effects of this interaction on melt compositions are poorly constrained. Here, we demonstrate a robust linear correlation between the Mg/Si ratios of kimberlites and their entrained mantle components and between Mg/Fe ratios of mantle-derived olivine cores and magmatic olivine rims in kimberlites worldwide. Combined with numerical modeling, these findings indicate that kimberlite melts with highly variable composition were broadly similar before lithosphere assimilation. This implies that kimberlites worldwide originated by partial melting of compositionally similar convective mantle sources under comparable physical conditions. We conclude that mantle assimilation markedly alters the major element composition of carbonate-rich melts and is a major process in the evolution of mantle-derived magmas.

Melting of sediments in the deep mantle produces saline fluid inclusions in diamonds.

Diamonds growing in the Earth's mantle often trap inclusions of fluids that are highly saline in composition. These fluids are thought to emerge from deep in subduction zones and may also be involved in the generation of some of the kimberlite magmas. However, the source of these fluids and the mechanism of their transport into the mantle lithosphere are unresolved. Here, we present experimental results showing that alkali chlorides are stable solid phases in the mantle lithosphere below 110 km. These alkali chlorides are formed by the reaction of subducted marine sediments with peridotite and show identical K/Na ratios to fluid inclusions in diamond. At temperatures >1100°C and low pressures, the chlorides are unstable; here, potassium is accommodated in mica and melt. The reaction of subducted sediments with peridotite explains the occurrence of Mg carbonates and the highly saline fluids found in diamonds and in chlorine-enriched kimberlite magmas.

Evolution of the Archaean crust by delamination and shallow subduction.

The Archaean oceanic crust was probably thicker than present-day oceanic crust owing to higher heat flow and thus higher degrees of melting at mid-ocean ridges. These conditions would also have led to a different bulk composition of oceanic crust in the early Archaean, that would probably have consisted of magnesium-rich picrite (with variably differentiated portions made up of basalt, gabbro, ultramafic cumulates and picrite). It is unclear whether these differences would have influenced crustal subduction and recycling processes, as experiments that have investigated the metamorphic reactions that take place during subduction have to date considered only modern mid-ocean-ridge basalts. Here we present data from high-pressure experiments that show that metamorphism of ultramafic cumulates and picrites produces pyroxenites, which we infer would have delaminated and melted to produce basaltic rocks, rather than continental crust as has previously been thought. Instead, the formation of continental crust requires subduction and melting of garnet-amphibolite--formed only in the upper regions of oceanic crust--which is thought to have first occurred on a large scale during subduction in the late Archaean. We deduce from this that shallow subduction and recycling of oceanic crust took place in the early Archaean, and that this would have resulted in strong depletion of only a thin layer of the uppermost mantle. The misfit between geochemical depletion models and geophysical models for mantle convection (which include deep subduction) might therefore be explained by continuous deepening of this depleted layer through geological time.