Crystal scavenging from mush piles recorded by melt inclusions

Olivine-hosted melt inclusions are commonly used to determine pre-eruptive storage conditions. However, this approach relies on the assumption that co-erupted olivines have a simple association with their carrier melts. We show that primitive olivine crystal cargoes and their melt inclusions display a high degree of geochemical disequilibrium with their carrier melts at Kīlauea Volcano, Hawai’i. Within a given eruption, melt inclusions trapped in primitive olivine crystals exhibit compositional diversity exceeding that in erupted lava compositions since 1790 CE. This demonstrates that erupting liquids scavenge crystal cargoes from mush piles accumulating diverse melt inclusion populations over timescales of centuries or longer. Entrainment of hot primitive olivines into cooler, evolved carrier melts drives post-entrapment crystallization and sequestration of CO2 into vapour bubbles, producing spurious barometric estimates. While scavenged melt inclusion records may not be suitable for the investigation of eruption-specific processes, they record timescales of crystal storage and remobilization within magmatic mush piles

Chalcophile element processing beneath a continental arc stratovolcano

The chalcophile elements are important both in terms of their economic value and as potential tracers of magmatic processes at convergent margins. However, because of analytical difficulties, comprehensive datasets of chalcophile element concentrations for volcanic rocks are rare. Here, we present analyses of a near complete suite of chalcophile elements (S, Cu, Ag, Se, As, Sb, Sn, W, Mo, Pb, Bi, Tl, Zn, Ga, Co) for volcanic rock samples collected from a typical continental arc stratovolcano in southern Chile (Antuco). Enrichment in Pb, Bi, W, Tl, Sb and As relative to Parental-MORB indicates that these elements have been mobilised from the subducting slab into the sub-arc mantle wedge, in contrast to Cu and Ag. Very low Se concentrations suggest that Se, like S, was lost during co-eruptive degassing of the Antuco magmas. Previous studies on oceanic arcs have demonstrated that as higher fO2 subduction-related magmas ascend through the overlying lithosphere, magnetite fractionation may trigger sulfide fractionation during crystallisation. If such a process is extensive and has a sharp onset, this would result in a plummet in the Cu, Se and Ag contents of the residual melt. At Antuco, although a decrease in the Fe2O3(T) and TiO2 concentrations at ∼55 wt.% SiO2 (∼3 wt.% MgO) indicates magnetite fractionation, this is not associated with a corresponding drop in Cu contents. Instead, we observe a general decrease in Cu and a decrease in Cu/Ag with increasing SiO2 and decreasing MgO. Furthermore, Cu/Ag in the most primitive Antuco rocks are lower than the global MORB array, indicating that the melts were sulfide saturated at an early stage in their crustal evolution. Through modelling fractional crystallisation, we show that only a minor volume (0.5–0.6 vol.%) of fractionating sulfide is needed to produce divergent trends in Cu and Ag, as observed in the Antuco samples. Our results show that sulfide fractionation occurred from an early stage during the crustal evolution of Antuco's magmas. We infer that this was promoted by stalling in the lower crust, which for oxidised magmas at depths >20 km is within the sulfide stability field. However, elevated DyN/YbN of the Antuco magmas compared to oceanic island arc magmas provides an additional, or alternate mechanism to inducing sulfide fractionation in the lower crust prior to ascent, through initial garnet fractionation. Fractional crystallisation within this depth range meant that later magnetite fractionation had only a minor impact on the partitioning behaviour of the chalcophile elements. In contrast, arc magmas transiting thinner crust may not experience sulfide saturation until a later stage in their evolution, induced by magnetite fractionation. Our results imply that convergent margin crustal thickness, and therefore the depth range of magmatic differentiation, determines the dominant control on initial magmatic sulfide saturation and therefore the primary distribution of chalcophile elements. This implies that secondary processes are required to explain the transport and concentration of sulfides and chalcophile elements at shallower crustal levels

Crystal scavenging from mush piles recorded by melt inclusions

Abstract: Olivine-hosted melt inclusions are commonly used to determine pre-eruptive storage conditions. However, this approach relies on the assumption that co-erupted olivines have a simple association with their carrier melts. We show that primitive olivine crystal cargoes and their melt inclusions display a high degree of geochemical disequilibrium with their carrier melts at Kīlauea Volcano, Hawai’i. Within a given eruption, melt inclusions trapped in primitive olivine crystals exhibit compositional diversity exceeding that in erupted lava compositions since 1790 CE. This demonstrates that erupting liquids scavenge crystal cargoes from mush piles accumulating diverse melt inclusion populations over timescales of centuries or longer. Entrainment of hot primitive olivines into cooler, evolved carrier melts drives post-entrapment crystallization and sequestration of CO2 into vapour bubbles, producing spurious barometric estimates. While scavenged melt inclusion records may not be suitable for the investigation of eruption-specific processes, they record timescales of crystal storage and remobilization within magmatic mush piles

Widespread tephra dispersal and ignimbrite emplacement from a subglacial volcano (Torfajökull, Iceland)

The tephra dispersal mechanisms of rhyolitic glaciovolcanic eruptions are little known, but can be investigated through the correlation of eruptive products across multiple depositional settings. Using geochemistry and geochronology, we correlate a regionally important Pleistocene tephra horizon—the rhyolitic component of North Atlantic Ash Zone II (II-RHY-1)—and the Thórsmörk Ignimbrite with rhyolitic tuyas at Torfajökull volcano, Iceland. The eruption breached an ice mass >400 m thick, leading to the widespread dispersal of II-RHY-1 across the North Atlantic and the Greenland ice sheet. Locally, pyroclastic density currents traveled across the ice surface, depositing the variably welded Thórsmörk Ignimbrite beyond the ice margin and ~30 km from source. The widely dispersed products of this eruption represent a valuable isochronous tie line between terrestrial, marine, and ice-core paleoenvironmental records. Using the tephra horizon, estimates of ice thickness and extent derived from the eruption deposits can be directly linked to the regional climate archive, which records the eruption at the onset of Greenland Stadial 15.2

Arc crust formation of Lesser Antilles revealed by crustal xenoliths from Petit St. Vincent

The Lesser Antilles volcanic arc is known for its magmatic diversity and unusually abundant plutonic xenoliths. Xenoliths from Petit St. Vincent (Grenadines archipelago) are particularly interesting because of their textural and petrogenetic range. Here we combine petrographic observations, Electron Backscatter Diffraction (EBSD) analysis, major and trace element chemistry of xenoliths and lavas, and geochemical and thermal modelling to explore the construction of arc crust beneath Petit St. Vincent. Petit St. Vincent xenoliths are dominated by calcic plagioclase, clinopyroxene and amphibole, and can be divided into two main categories, igneous and meta-igneous. Igneous xenoliths typically have cumulate textures; meta-igneous xenoliths range texturally from those that preserve vestiges of primary magmatic fabrics to intensely deformed varieties characterised by grain-size reduction and foliation development. Meta-igneous xenoliths also contain the most calcic plagioclase (An98-100)

Evolution of the crustal phosphorus reservoir

The release of phosphorus (P) from crustal rocks during weathering plays a key role in determining the size of Earth's biosphere, yet the concentration of P in crustal rocks over time remains controversial. Here, we combine spatial, temporal, and chemical measurements of preserved rocks to reconstruct the lithological and chemical evolution of Earth's continental crust. We identify a threefold increase in average crustal P concentrations across the Neoproterozoic-Phanerozoic boundary (600 to 400 million years), showing that preferential biomass burial on shelves acted to progressively concentrate P within continental crust. Rapid compositional change was made possible by massive removal of ancient P-poor rock and deposition of young P-rich sediment during an episode of enhanced global erosion. Subsequent weathering of newly P-rich crust led to increased riverine P fluxes to the ocean. Our results suggest that global erosion coupled to sedimentary P-enrichment forged a markedly nutrient-rich crust at the dawn of the Phanerozoic

The competing effects of sulfide saturation versus degassing on the behavior of the chalcophile elements during the differentiation of hydrous melts

There is a lack of consensus regarding the roles of sulfide saturation versus volatile degassing on the partitioning of Cu and Ag during differentiation and eruption of convergent margin magmas. Because of their oxidized character, volatile-rich magmas from the Eastern Manus Back-arc Basin (EMBB) only reach sulfide saturation following magnetite-driven reduction of the melt: the so-called “magnetite crisis.” If sulfide saturation typically precedes volatile saturation, the magnetite crisis will limit the proportion of Cu and Ag that can partition from the melt into an exsolving volatile-rich phase, which may contribute to the sporadic occurrence of magmatic-hydrothermal ore deposits at convergent margins. However, it is unclear whether the magnetite crisis is a common or rare event during differentiation of volatile-rich magmas. We report major and trace element data for submarine volcanic glasses from the Tonga arc-proximal Valu Fa Ridge (VFR; SW Pacific). Cu-Se-Ag systematics of samples erupting at the southern VFR suggest magnetite fractionation-triggered sulfide saturation. The similarity in chalcophile element systematics of the southern VFR and EMBB samples is unlikely to be coincidental, and may indicate that the magnetite crisis is a common event during differentiation of hydrous melts. However, unlike many convergent margin magmas, it is unlikely that the evolving VFR and EMBB were saturated in a S-bearing volatile phase prior to magnetite fractionation. Hence, the metal-depleting magnetite crisis may be restricted to back-arc basin magmas that do not degas volatiles prior to magnetite fractionation and potentially convergent margin magmas fractionating at high pressures in the continental crust

Fractionation of Li, Be, Ga, Nb, Ta, In, Sn, Sb, W and Bi in the peraluminous Early Permian Variscan granites of the Cornubian Batholith: precursor processes to magmatic-hydrothermal mineralisation

The Early Permian Variscan Cornubian Batholith is a peraluminous, composite pluton intruded into Devonian and Carboniferous metamorphosed sedimentary and volcanic rocks. Within the batholith there are: G1 (two-mica), G2 (muscovite), G3 (biotite), G4 (tourmaline) and G5 (topaz) granites. G1-G2 and G3-G4 are derived from greywacke sources and linked through fractionation of assemblages dominated by feldspars and biotite, with minor mantle involvement in G3. G5 formed though flux-induced biotite-dominate melting in the lower crust during granulite facies metamorphism. Fractionation enriched G2 granites in Li (average 315 ppm), Be (12 ppm), Ta (4.4 ppm), In (74 ppb), Sn (18 ppm) and W (12 ppm) relative to crustal abundances and G1 granites. Gallium (24 ppm), Nb (16 ppm) and Bi (0.46 ppm) are not significantly enriched during fractionation, implying they are more compatible in the fractionating assemblage. Sb (0.16 ppm) is depleted in G1-G2 relative to the average upper and lower continental crust. Muscovite, a late-stage magmatic/subsolidus mineral, is the major host of Li, Nb, In, Sn and W in G2 granites. G2 granites are spatially associated with W-Sn greisen mineralisation. Fractionation within the younger G3-G4 granite system enriched Li (average 364 ppm), Ga (28 ppm), In (80 ppb), Sn (14 ppm), Nb (27 ppm), Ta (4.6 ppm), W (6.3 ppm) and Bi (0.61 ppm) in the G4 granites with retention of Be in G3 granites due to partitioning of Be into cordierite during fractionation. The distribution of Nb and Ta is controlled by accessory phases such as rutile within the G4 granites, facilitated by high F and lowering the melt temperature, leading to disseminated Nb and Ta mineralisation. Lithium, In, Sn and W are hosted in biotite micas which may prove favourable for breakdown on ingress of hydrothermal fluids. Higher degrees of scattering on trace element plots may be attributable to fluid–rock interactions or variability within the magma chamber. The G3-G4 system is more boron-rich, evidenced by a higher modal abundance of tourmaline. In this system, there is a stronger increase of Sn compared to G1-G2 granites, implying Sn in tourmaline-dominated mineral lodes may represent exsolution from G4 granites. G1-G4 granite abundances can be accounted for by 20–30% partial melting and 10–40% fractionation of a greywacke source. G5 granites are analogues of Rare Metal Granites described in France and Germany. These granites are enriched in Li (average 1363 ppm), Ga (38 ppm), Sn (21 ppm), W (24 ppm), Nb (52 ppm) and Ta (15 ppm). Within G5 granites, the metals partition into accessory minerals such as rutile, columbite-tantalite and cassiterite, forming disseminated magmatic mineralisation. High observed concentrations of Li, In, Sn, W, Nb and Ta in G4 and G5 granites are likely facilitated by high F, Li and P, which lower melt temperature and promote retention of these elements in the melt, prior to crystallisation of disseminated magmatic mineralisation

Mortality and pulmonary complications in patients undergoing surgery with perioperative SARS-CoV-2 infection: an international cohort study

Background: The impact of severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) on postoperative recovery needs to be understood to inform clinical decision making during and after the COVID-19 pandemic. This study reports 30-day mortality and pulmonary complication rates in patients with perioperative SARS-CoV-2 infection. Methods: This international, multicentre, cohort study at 235 hospitals in 24 countries included all patients undergoing surgery who had SARS-CoV-2 infection confirmed within 7 days before or 30 days after surgery. The primary outcome measure was 30-day postoperative mortality and was assessed in all enrolled patients. The main secondary outcome measure was pulmonary complications, defined as pneumonia, acute respiratory distress syndrome, or unexpected postoperative ventilation. Findings: This analysis includes 1128 patients who had surgery between Jan 1 and March 31, 2020, of whom 835 (74·0%) had emergency surgery and 280 (24·8%) had elective surgery. SARS-CoV-2 infection was confirmed preoperatively in 294 (26·1%) patients. 30-day mortality was 23·8% (268 of 1128). Pulmonary complications occurred in 577 (51·2%) of 1128 patients; 30-day mortality in these patients was 38·0% (219 of 577), accounting for 81·7% (219 of 268) of all deaths. In adjusted analyses, 30-day mortality was associated with male sex (odds ratio 1·75 [95% CI 1·28–2·40], p\textless0·0001), age 70 years or older versus younger than 70 years (2·30 [1·65–3·22], p\textless0·0001), American Society of Anesthesiologists grades 3–5 versus grades 1–2 (2·35 [1·57–3·53], p\textless0·0001), malignant versus benign or obstetric diagnosis (1·55 [1·01–2·39], p=0·046), emergency versus elective surgery (1·67 [1·06–2·63], p=0·026), and major versus minor surgery (1·52 [1·01–2·31], p=0·047). Interpretation: Postoperative pulmonary complications occur in half of patients with perioperative SARS-CoV-2 infection and are associated with high mortality. Thresholds for surgery during the COVID-19 pandemic should be higher than during normal practice, particularly in men aged 70 years and older. Consideration should be given for postponing non-urgent procedures and promoting non-operative treatment to delay or avoid the need for surgery. Funding: National Institute for Health Research (NIHR), Association of Coloproctology of Great Britain and Ireland, Bowel and Cancer Research, Bowel Disease Research Foundation, Association of Upper Gastrointestinal Surgeons, British Association of Surgical Oncology, British Gynaecological Cancer Society, European Society of Coloproctology, NIHR Academy, Sarcoma UK, Vascular Society for Great Britain and Ireland, and Yorkshire Cancer Research

Search for eccentric black hole coalescences during the third observing run of LIGO and Virgo

Despite the growing number of confident binary black hole coalescences observed through gravitational waves so far, the astrophysical origin of these binaries remains uncertain. Orbital eccentricity is one of the clearest tracers of binary formation channels. Identifying binary eccentricity, however, remains challenging due to the limited availability of gravitational waveforms that include effects of eccentricity. Here, we present observational results for a waveform-independent search sensitive to eccentric black hole coalescences, covering the third observing run (O3) of the LIGO and Virgo detectors. We identified no new high-significance candidates beyond those that were already identified with searches focusing on quasi-circular binaries. We determine the sensitivity of our search to high-mass (total mass M>70 M⊙) binaries covering eccentricities up to 0.3 at 15 Hz orbital frequency, and use this to compare model predictions to search results. Assuming all detections are indeed quasi-circular, for our fiducial population model, we place an upper limit for the merger rate density of high-mass binaries with eccentricities 0<e≤0.3 at 0.33 Gpc−3 yr−1 at 90\% confidence level