Chemical data from the MESSENGER spacecraft revealed that surface rocks on Mercury are unusually enriched in sulfur compared to samples from other terrestrial planets. In order to understand the speciation and distribution of sulfur on Mercury, we performed high temperature (1200-1750 • C), lowto high-pressure (1 bar to 4 GPa) experiments on compositions representative of Mercurian lavas and on the silicate composition of an enstatite chondrite. We equilibrated silicate melts with sulfide and metallic melts under highly reducing conditions (IW-1.5 to IW-9.4; IW = iron-wüstite oxygen fugacity buffer). Under these oxygen fugacity conditions, sulfur dissolves in the silicate melt as S 2− and forms complexes with Fe 2+ , Mg 2+ and Ca 2+ . The sulfur concentration in silicate melts at sulfide saturation (SCSS) increases with increasing reducing conditions (from <1 wt.% S at IW-2 to >10 wt.% S at IW-8) and with increasing temperature. Metallic melts have a low sulfur content which decreases from 3 wt.% at IW-2 to 0 wt.% at IW-9. We developed an empirical parameterization to predict SCSS in Mercurian magmas as a function of oxygen fugacity ( f O 2 ), temperature, pressure and silicate melt composition. SCSS being not strictly a redox reaction, our expression is fully valid for magmatic systems containing a metal phase. Using physical constraints of the Mercurian mantle and magmas as well as our experimental results, we suggest that basalts on Mercury were free of sulfide globules when they erupted. The high sulfur contents revealed by MESSENGER result from the high sulfur solubility in silicate melt at reducing conditions. We make the realistic assumption that the oxygen fugacity of mantle rocks was set during equilibration of the magma ocean with the core and/or that the mantle contains a minor metal phase and combine our parameterization of SCSS with chemical data from MESSENGER to constrain the oxygen fugacity of Mercury's interior to IW-5.4 ± 0.4. We also calculate that the mantle of Mercury contains 7-11 wt.% S and that the metallic core of the planet has little sulfur (<1.5 wt.% S). The external part of the Mercurian core is likely to be made up of a thin (<90 km) FeS layer.
We present crystallization experiments on silicate melt compositions related to the lunar magma ocean (LMO) and its evolution with cooling. Our approach aims at constraining the primordial internal differentiation of the Moon into mantle and crust. We used graphite capsules in piston cylinder (1.35-0.80 GPa) and internally-heated pressure vessels (<0.50 GPa), over 1580-1020°C, and produced melt compositions using a stepwise approach that reproduces fractional crystallization. Using our new experimental dataset, we define phase equilibria and equations predicting the saturation of liquidus phases, magma temperature, and crystal/melt partitioning for major elements relevant for the crystallization of the LMO. These empirical expressions are then used in a forward model that predicts the liquid line of descent and crystallization products of a 600 km-thick magma ocean. Our results show that the effects of changes in the bulk composition on the sequence of crystallization are minor. Our experiments also show the crystallization of a silica phase at ca. 1080°C and we suggest that this phase might have contributed to the building of the lower anorthositic crust. Calculation of crustal thickness clearly shows that a thin crust similar to that revealed by GRAIL cannot have been generated through solidification of whole Moon magma ocean. We discuss the role of magma ocean depth, trapped liquid fraction (with implication for the alumina budget in the mantle and the crust), and the efficiency of plagioclase flotation in producing the thin crust. We also constrain the potential range of pyroxene compositions that could be incorporated into the crust and show that delayed crustal building during ca. 4% LMO crystallization on the nearside of the Moon may explain the dichotomy for Mg-number. Finally, we show that the LMO can produce magnesian anorthosites during the first stages of plagioclase crystallization.
The MESSENGER spacecraft provided geochemical data for surface rocks on Mercury. In this study, we use the major element composition of these lavas to constrain melting conditions and residual mantle sources on Mercury. We combine modelling and high-temperature (1320-1580 • C), low-to high-pressure (0.1 to 3 GPa) experiments on average compositions for the Northern Volcanic Plains (NVP) and the high-Mg region of the Intercrater Plains and Heavily Cratered Terrains (High-Mg IcP-HCT). Near-liquidus phase relations show that the S-free NVP and High-Mg IcP-HCT compositions are multiply saturated with forsterite and enstatite at 1450 • C -1.3 GPa and 1570 • C -1.7 GPa, respectively. For S-saturated melts (1.5-3 wt.% S), the multiple saturation point (MSP) is shifted to 1380 • C -0.75 GPa for NVP and 1480 • C -0.8 GPa for High-Mg IcP-HCT. To expand our experimental results to the range of surface compositions, we used and calibrated the pMELTS thermodynamic calculator and estimated phase equilibria of ∼5800 compositions from the Mercurian surface and determined the P -T conditions of liquid-forsterite-enstatite MSP (1300-1600 • C; 0.25-1.25 GPa). Surface basalts were produced by 10 to 50% partial melting of variably enriched lherzolitic mantle sources. The relatively low pressure of the olivine-enstatite-liquid MSP seems most consistent with decompression batch melting and melts being segregated from their residues near the base of Mercury's ancient lithosphere. The average melting degree is lower for the young NVP (0.27 ± 0.04) than for the older IcP-HCT (0.46 ± 0.02), indicating that melt productivity decreased with time. The mantle potential temperature required to form Mercurian lavas and the initial depth of melting also decreased from the older High-Mg IcP-HCT terrane (1650 • C and 360 km) to the younger lavas covering the NVP regions (1410 • C and 160 km). This evolution supports strong secular cooling of Mercury's mantle between 4.2 and 3.7 Ga and explains why very little magmatic activity occurred after 3.7 Ga.
The origin of iron oxide-apatite deposits is controversial. Silicate liquid immiscibility and separation of an iron-rich melt has been invoked, but Fe–Ca–P-rich and Si-poor melts similar in composition to the ore have never been observed in natural or synthetic magmatic systems. Here we report experiments on intermediate magmas that develop liquid immiscibility at 100 MPa, 1000–1040 °C, and oxygen fugacity conditions (fO2) of ∆FMQ = 0.5–3.3 (FMQ = fayalite-magnetite-quartz equilibrium). Some of the immiscible melts are highly enriched in iron and phosphorous ± calcium, and strongly depleted in silicon (<5 wt.% SiO2). These Si-poor melts are in equilibrium with a rhyolitic conjugate and are produced under oxidized conditions (~FMQ + 3.3), high water activity (aH2O ≥ 0.7), and in fluorine-bearing systems (1 wt.%). Our results show that increasing aH2O and fO2 enlarges the two-liquid field thus allowing the Fe–Ca–P melt to separate easily from host silicic magma and produce iron oxide-apatite ores.
Over the first billion years of Mercury's history, mantle melting and surface volcanism produced a secondary magmatic crust varying spatially in composition and mineralogy. By combining geochemical mapping from MESSENGER with laboratory experiments on partial melting, we translate the surface mineralogy into lateral variations of surface density and calculate the degree of mantle melting required to produce surface rocks. If lateral density variations extend through the whole crust, the local crustal thickness correlates well with the degree of mantle melting. Low-degree mantle melting produced a thin crust below the northern volcanic plains (19 ± 3 km), whereas high-degree melting produced the thickest crust in the ancient high-Mg region (50 ± 12 km), refuting the hypothesis of an impact origin for that region. The thickness-melting correlation has also been observed for the oceanic crust on Earth and might be a common feature of secondary crust formation on terrestrial planets.Plain Language Summary Mercury's crust has a complex structure resulting from a billion years of volcanism. The surface variations in chemical composition have been identified from orbit by the spacecraft MESSENGER. Combining these measurements with laboratory experiments on partial melting, we estimate which variations in surface density and degree of mantle melting are required to produce surface rocks. If the surface density is representative of the deep crustal density, more than one half of crustal thickness variations in the Northern Hemisphere are explained by lateral variations in mantle melting. The crust is thin below the magnesium-poor northern volcanic plains, whereas the thickest crust is found in the magnesium-rich region located at middle northern latitudes in the Western Hemisphere. The magnesium-rich region is thus not due to an early impact but rather to extensive mantle melting. The thickness-melting relation has also been observed for the oceanic crust on Earth and might be a common feature of terrestrial planets.
PrefaceLayered intrusions have received continuous interest since the publication of the treatise on 'Layered Igneous Rocks' by Lawrence Wager and Malcolm Brown, updated in books edited by Ian Parsons in 1987 and Grant Cawthorn in 1996. The study of these fossilized magma chambers keep inspiring a number of scientists with a range of interests including petrology and igneous differentiation, geochronology, geochemistry, mineralogy, rock textures and fabric, fluid dynamics, and ore deposits. The goal of this book is to further our understanding of magma chamber processes and crystal-liquid relationship during magma cooling magma. Physical and chemical processes are now better quantified thanks to the development analytical and computing tools such as compositional mapping, 3D X-ray computed tomography, in situ analyses for trace elements and isotopes, development of new experimental facilities, and progress in instrument sensitivity.The book is subdivided into two parts. The first includes reviews and new views on chronological, textural, mineralogical, geochemical, and magnetic characteristics of layered igneous rocks. The second part reviews recent progress in the study of layered intrusions. A newcomer on the layered intrusions scene is the Panzhihua intrusion (SW China) that has been intensively studied recently. Reviews of recent findings for Sept Iles, Bushveld, Kiglapait, Ilímaussaq, and layered rocks in ophiolites are also presented. Interest in layered intrusions is also driven by their natural resources. Many intrusions host world-class ore bodies of chromium, platinum group elements (PGE), vanadium, titanium and phosphorous. Ore-forming processes and important deposits associated with layered intrusions are described and their origin is discussed.The objective of this book is to outline the most recent ideas and challenges in the study of layered igneous bodies. It has also the purpose to aid in teaching, and to encourage new studies to tackle major issues in the understanding of magma chamber processes and associated ore-forming processes.The book has benefited from detailed comments by a many reviewers, who are greatly acknowledged:
The chemistry of erupted magmas provides a crucial window into the composition and structure of Earth's convecting mantle. However, magmatic evolution in the crust makes it challenging to reconstruct mantle properties from volcanic rocks in important but incompletely understood ways. Here we investigate how mantle-derived compositional variability in primary oceanic basalts determines their phase equilibria relations and the nature of the geochemical signals they record. By performing experiments on synthetic analogues of compositionally extreme primitive lavas from the Reykjanes Peninsula of Iceland at realistic magma storage conditions (300 MPa, 1140-1260°C), we show that melts from enriched mantle domains retain higher melt fractions as they cool than those generated by melting of typical fertile lherzolite (i.e. they crystallise less mass over any interval of decreasing temperature). These melt fraction differences arise because plagioclase crystallisation is suppressed in Na-and H 2 O-rich but Ca-and Al-poor liquids derived from enriched source lithologies. Thus, compositional characteristics inherited from the mantle have a first-order control on the efficiency with which cooling basalts crystallise. This means that enriched melts will be more likely to survive crustal processing than depleted melts. Basalt chemistry will therefore be disproportionately influenced by melts from volumetrically minor enriched lithologies compared with melts from the upper mantle's most common lithology, lherzolite, 1 systematically biasing basaltic records towards melts from recycled mantle sources.We combine our experimental observations from Iceland with thermodynamic simulations on mid-ocean ridge basalt compositions and show that mantle-derived variability in crystallisation efficiency can explain two enigmatic features of the global oceanic basalt record: firstly, the anomalous over-enrichment of incompatible elements during the differentiation of mid-ocean ridge basalts, which may reflect a progressive bias towards enriched compositions as differentiation proceeds; and secondly, the frequently documented cargoes of highly anorthitic plagioclase crystals carried by evolved and enriched liquids from which they cannot have crystallised. These crystals can now be understood as the solidified remnants of depleted, lherzolite-derived melts that have been entrained into melt mixtures from more enriched sources. Increases in the degree of enrichment of cumulate rocks sampled from progressively shallower horizons of the oceanic crust can also be interpreted in terms of enriched melts surviving crustal processing in preference to depleted melts.
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