Subseafloor sulphide deposit formed by pumice replacement mineralisation.

Seafloor massive sulphide (SMS) deposits, modern analogues of volcanogenic massive sulphide (VMS) deposits on land, represent future resources of base and precious metals. Studies of VMS deposits have proposed two emplacement mechanisms for SMS deposits: exhalative deposition on the seafloor and mineral and void space replacement beneath the seafloor. The details of the latter mechanism are poorly characterised in detail, despite its potentially significant role in global metal cycling throughout Earth's history, because in-situ studies require costly drilling campaigns to sample SMS deposits. Here, we interpret petrographic, geochemical and geophysical data from drill holes in a modern SMS deposit and demonstrate that it formed via subseafloor replacement of pumice. Samples from the sulphide body and overlying sediment at the Hakurei Site, Izena Hole, middle Okinawa Trough indicate that sulphides initially formed as aggregates of framboidal pyrite and matured into colloform and euhedral pyrite, which were replaced by chalcopyrite, sphalerite and galena. The initial framboidal pyrite is closely associated with altered material derived from pumice, and alternating layers of pumiceous and hemipelagic sediments functioned as a factory of sulphide mineralisation. We infer that anhydrite-rich layers within the hemipelagic sediment forced hydrothermal fluids to flow laterally, controlling precipitation of a sulphide body extending hundreds of meters.

Site occupancy of Fe2+, Fe3+ and Ti4+ in titanomagnetite determined by valence-difference contrast in synchrotron X-ray resonant scattering.

A synchrotron X-ray diffraction study of a single crystal of titanomagnetite shows that the cation distribution of Fe2+, Fe3+ and Ti4+ is of the inverse-spinel type. The valence-difference contrast (VDC) method of resonant scattering was applied at a wavelength of λ = 1.7441 Š(E = 7.1085 keV) within the pre-edge of the Fe K absorption spectrum, utilizing the large difference in the real part of anomalous scattering factors, between -7.45 and -6.50, for Fe2+ and Fe3+, respectively. The most plausible atomic arrangement in Ti0.31Fe2.69O4 obtained from our analysis is [Fe3+1.00]A[Fe3+0.38Fe2+1.31Ti4+0.31]BO4, where A and B in an AB2O4-type structure correspond to the tetrahedral and octahedral sites, respectively. This result suggests that titanomagnetite has the complete inverse-spinel structure continuously from the end-member of magnetite, even in the case of relatively high Ti content. The physical properties may be described by the Néel model, which claims that Fe3+ preferentially occupies the tetrahedral site, within a Ti-poor half-region of the solid solution. Based on the ordering scheme the magnetic structure of titanomagnetite is considered to be analogous to that of magnetite. The combination of circularly polarized X-rays and a horizontal-type four-circle diffractometer used in this VDC technique has the advantage of increasing the experimental accuracy and freedom with the simultaneous reduction of experimental noise.

Rapid growth of mineral deposits at artificial seafloor hydrothermal vents.

Seafloor massive sulphide deposits are potential resources for base and precious metals (Cu-Pb-Zn ± Ag ± Au), but difficulties in estimating precise reserves and assessing environmental impacts hinder exploration and commercial mining. Here, we report petrological and geochemical properties of sulphide chimneys less than 2 years old that formed where scientific boreholes vented hydrothermal fluids in the Iheya-North field, Okinawa Trough, in East China Sea. One of these infant chimneys, dominated by Cu-Pb-Zn-rich sulphide minerals, grew a height of 15 m within 25 months. Portions of infant chimneys are dominated by sulphate minerals. Some infant chimneys are sulphide-rich similar to high-grade Cu-Pb-Zn bodies on land, albeit with relatively low As and Sb concentrations. The high growth rate reaching the 15 m height within 25 months is attributed to the large hydrothermal vent more than 50 cm in diameter created by the borehole, which induced slow mixing with the ambient seawater and enhanced efficiency of sulphide deposition. These observations suggest the possibility of cultivating seafloor sulphide deposits and even controlling their growth and grades through manipulations of how to mix and quench hydrothermal fluids with the ambient seawater.

Discovery of seifertite in a shocked lunar meteorite.

Many craters and thick regoliths of the moon imply that it has experienced heavy meteorite bombardments. Although the existence of a high-pressure polymorph is a stark evidence for a dynamic event, few high-pressure polymorphs are found in a lunar sample. α-PbO2-type silica (seifertite) is an ultrahigh-pressure polymorph of silica, and is found only in a heavily shocked Martian meteorite. Here we show evidence for seifertite in a shocked lunar meteorite, Northwest Africa 4734. Cristobalite transforms to seifertite by high-pressure and -temperature condition induced by a dynamic event. Considering radio-isotopic ages determined previously, the dynamic event formed seifertite on the moon, accompanying the complete resetting of radio-isotopic ages, is ~2.7 Ga ago. Our finding allows us to infer that such intense planetary collisions occurred on the moon until at least ~2.7 Ga ago.

Natural dissociation of olivine to (Mg,Fe)SiO3 perovskite and magnesiowustite in a shocked Martian meteorite.

We report evidence for the natural dissociation of olivine in a shergottite at high-pressure and high-temperature conditions induced by a dynamic event on Mars. Olivine (Fa(34-41)) adjacent to or entrained in the shock melt vein and melt pockets of Martian meteorite olivine-phyric shergottite Dar al Gani 735 dissociated into (Mg,Fe)SiO(3) perovskite (Pv)+magnesiowüstite (Mw), whereby perovskite partially vitrified during decompression. Transmission electron microscopy observations reveal that microtexture of olivine dissociation products evolves from lamellar to equigranular with increasing temperature at the same pressure condition. This is in accord with the observations of synthetic samples recovered from high-pressure and high-temperature experiments. Equigranular (Mg,Fe)SiO(3) Pv and Mw have 50-100 nm in diameter, and lamellar (Mg,Fe)SiO(3) Pv and Mw have approximately 20 and approximately 10 nm in thickness, respectively. Partitioning coefficient, K(Pv/Mw) = [FeO/MgO]/[FeO/MgO](Mw), between (Mg,Fe)SiO(3) Pv and Mw in equigranular and lamellar textures are approximately 0.15 and approximately 0.78, respectively. The dissociation of olivine implies that the pressure and temperature conditions recorded in the shock melt vein and melt pockets during the dynamic event were approximately 25 GPa but 700 °C at least.

New silica clathrate minerals that are isostructural with natural gas hydrates.

Silica clathrate compounds (clathrasils) and clathrate hydrates are structurally analogous because both materials have framework structures with cage-like voids occupied by guest species. The following three structural types of clathrate hydrates are recognized in nature: cubic structure I (sI); cubic structure II (sII); and hexagonal structure H (sH). In contrast, only one naturally occurring silica clathrate mineral, melanophlogite (sI-type framework), has been found to date. Here, we report the discovery of two new silica clathrate minerals that are isostructural with sII and sH hydrates and contain hydrocarbon gases. Geological and mineralogical observations show that these silica clathrate minerals are traces of low-temperature hydrothermal systems at convergent plate margins, which are the sources of thermogenic natural gas hydrates. Given the widespread occurrence of submarine hydrocarbon seeps, silica clathrate minerals are likely to be found in a wide range of marine sediments.

Evidence for fractional crystallization of wadsleyite and ringwoodite from olivine melts in chondrules entrained in shock-melt veins.

Peace River is one of the few shocked members of the L-chondrites clan that contains both high-pressure polymorphs of olivine, ringwoodite and wadsleyite, in diverse textures and settings in fragments entrained in shock-melt veins. Among these settings are complete olivine porphyritic chondrules. We encountered few squeezed and flattened olivine porphyritic chondrules entrained in shock-melt veins of this meteorite with novel textures and composition. The former chemically unzoned (Fa(24-26)) olivine porphyritic crystals are heavily flattened and display a concentric intergrowth with Mg-rich wadsleyite of a very narrow compositional range (Fa(6)-Fa(10)) in the core. Wadsleyite core is surrounded by a Mg-poor and chemically stark zoned ringwoodite (Fa(28)-Fa(38)) belt. The wadsleyite-ringwoodite interface denotes a compositional gap of up to 32 mol % fayalite. A transmission electron microscopy study of focused ion beam slices in both regions indicates that the wadsleyite core and ringwoodite belt consist of granoblastic-like intergrowth of polygonal crystallites of both ringwoodite and wadsleyite, with wadsleyite crystallites dominating in the core and ringwoodite crystallites dominating in the belt. Texture and compositions of both high-pressure polymorphs are strongly suggestive of formation by a fractional crystallization of the olivine melt of a narrow composition (Fa(24-26)), starting with Mg-rich wadsleyite followed by the Mg-poor ringwoodite from a shock-induced melt of olivine composition (Fa(24-26)). Our findings could erase the possibility of the resulting unrealistic time scales of the high-pressure regime reported recently from other shocked L-6 chondrites.

Metastable garnet in oceanic crust at the top of the lower mantle.

As oceanic tectonic plates descend into the Earth's lower mantle, garnet (in the basaltic crust) and silicate spinel (in the underlying peridotite layer) each decompose to form silicate perovskite-the 'post-garnet' and 'post-spinel' transformations, respectively. Recent phase equilibrium studies have shown that the post-garnet transformation occurs in the shallow lower mantle in a cold slab, rather than at approximately 800 km depth as earlier studies indicated, with the implication that the subducted basaltic crust is unlikely to become buoyant enough to delaminate as it enters the lower mantle. But here we report results of a kinetic study of the post-garnet transformation, obtained from in situ X-ray observations using sintered diamond anvils, which show that the kinetics of the post-garnet transformation are significantly slower than for the post-spinel transformation. Although metastable spinel quickly breaks down at a temperature of 1,000 K, we estimate that metastable garnet should survive of the order of 10 Myr even at 1,600 K. Accordingly, the expectation of where the subducted oceanic crust would be buoyant spans a much wider depth range at the top of the lower mantle, when transformation kinetics are taken into account.