In situ gold adsorption experiment at an acidic hot spring using a blue-green algal sheet.

Gold (Au), as one of the most precious metal resources that is used for both industrial products and private ornaments, is a global investment target, and mining companies are making huge investments to discover new Au deposits. Here, we report in situ Au adsorption in an acidic hot spring by a unique adsorption sheet made from blue-green algae with a high preferential adsorption ability for Au. The results of in situ Au adsorption experiments conducted for various reaction times ranging from 0.2 h to 7 months showed that a maximum Au concentration of 30 ppm was adsorbed onto the blue-green algal sheet after a reaction time of 7 months. The Au concentration in the hot spring water was below the detection limit (< 1 ppt); therefore, Au was enriched by preferential adsorption onto the blue-green algal sheet by a factor of more than ~ 3 × 107. Thus, our gold recovery method has a high potential to recover Au even from an Au-poor solution such as hot spring water or mine wastewater with a low impact on the environment.

Pelagic responses to oceanic anoxia during the Carnian Pluvial Episode (Late Triassic) in Panthalassa Ocean.

The Carnian Pluvial Episode (CPE) was a short interval of extreme rainfall in the Late Triassic that caused significant changes in marine ecosystems. Global warming induced by Wrangellia volcanism is thought to have resulted in oceanic anoxia during the CPE, but the global extent, duration, and severity of anoxia, and its effects on major marine taxa, remain unclear. To address this, we examined an equatorial record of conditions in the Panthalassa Ocean during the CPE, focusing on marine Os isotope data, redox conditions, and conodont and radiolarian biostratigraphy. The results show that Wrangellia volcanism peaked in the latest Julian (early Carnian), coinciding with development of reducing conditions in the deep-sea Panthalassa. A strong conodont turnover occurred during the period of oceanic anoxia, whereas radiolarians were less affected and their diversity increased after the recovery from anoxia. The increased radiolarian diversity during the early Tuvalian (late Carnian) can be attributed to chemical weathering and enhanced nutrient fluxes associated with global warming and the more humid climate of Pangea.

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.

Rapid coupling between solid earth and ice volume during the Quaternary.

The solid earth plays a major role in controlling Earth's surface climate. Volcanic degassing of carbon dioxide (CO2) and silicate chemical weathering are known to regulate the evolution of climate on a geologic timescale (> 106 yr), but the relationship between the solid earth and the shorter (< 105 yr) fluctuations of Quaternary glacial-interglacial cycles is still under debate. Here we show that the seawater osmium isotope composition (187Os/188Os), a proxy for the solid earth's response to climate change, has varied during the past 300,000 years in association with glacial-interglacial cycles. Our marine Os isotope mass-balance simulation reveals that the observed 187Os/188Os fluctuation cannot be explained solely by global chemical weathering rate changes corresponding to glacial-interglacial climate changes, but the fluctuation can be reproduced by taking account of short-term inputs of (1) radiogenic Os derived from intense weathering of glacial till during deglacial periods and (2) unradiogenic Os derived from enhanced seafloor hydrothermalism triggered by sea-level falls associated with increases of ice sheet volume. Our results constitute the first evidence that ice sheet recession and expansion during the Quaternary systematically and repetitively caused short-term (< 105 yr) solid earth responses via chemical weathering of glacial till and seafloor magmatism. This finding implies that climatic changes on < 105 yr timescales can provoke rapid feedbacks from the solid earth, a causal relationship that is the reverse of the longer-term (> 106 yr) causality that has been conventionally considered.

Author Correction: Fish proliferation and rare-earth deposition by topographically induced upwelling at the late Eocene cooling event.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Fish proliferation and rare-earth deposition by topographically induced upwelling at the late Eocene cooling event.

The deep-sea clay that covers wide areas of the pelagic ocean bottom provides key information about open-ocean environments but lacks age-diagnostic calcareous or siliceous microfossils. The marine osmium isotope record has varied in response to environmental changes and can therefore be a useful stratigraphic marker. In this study, we used osmium isotope ratios to determine the depositional ages of pelagic clays extraordinarily rich in fish debris. Much fish debris was deposited in the western North and central South Pacific sites roughly 34.4 million years ago, concurrent with a late Eocene event, a temporal expansion of Antarctic ice preceding the Eocene-Oligocene climate transition. The enhanced northward flow of bottom water formed around Antarctica probably caused upwelling of deep-ocean nutrients at topographic highs and stimulated biological productivity that resulted in the proliferation of fish in pelagic realms. The abundant fish debris is now a highly concentrated source of industrially critical rare-earth elements.

A Miocene impact ejecta layer in the pelagic Pacific Ocean.

Meteorite impacts have caused catastrophic perturbations to the global environment and mass extinctions throughout the Earth's history. Here, we present petrographic and geochemical evidence of a possible impact ejecta layer, dating from about 11 Ma, in deep-sea clayey sediment in the Northwest Pacific. This clay layer has high platinum group element (PGE) concentrations and features a conspicuous negative Os isotope anomaly (187Os/188Os as low as ~0.2), indicating an influx of extraterrestrial material. It also contains abundant spherules that include pseudomorphs suggestive of porphyritic olivine as well as spinel grains with euhedral, dendritic and spherical forms and NiO contents as great as 23.3 wt%, consistent with impact ejecta. Osmium isotope stratigraphy suggests a most plausible depositional age of ~11 Ma (Miocene) for this layer, as determined by fitting with the seawater evolution curve. No large impact crater of this age is known on land, even within the relatively large uncertainty range of the relative Os age. Thus, we suggest that an unrecognised impact event in the middle or late Miocene produced the impact ejecta layer of the Northwest Pacific.

Onboard experiment investigating metal leaching of fresh hydrothermal sulfide cores into seawater.

We observed the initial release rate of metals from four fresh (i.e., without long time exposure to the atmosphere) hydrothermal sulfide cores into artificial seawater. The sulfide samples were collected by seafloor drilling from the Okinawa Trough by D/V Chikyu, powdered under inert gas, and immediately subjected to onboard metal-leaching experiments at different temperatures (5 °C and 20 °C), and under different redox conditions (oxic and anoxic), for 1-30 h. Zinc and Pb were preferentially released from sulfide samples containing various metals (i.e., Mn, Fe, Cu, Zn, Cd, and Pb) into seawater. Under oxic experimental conditions, Zn and Pb dissolution rates from two sulfide samples composed mainly of iron disulfide minerals (pyrite and marcasite) were higher than those from two other sulfide samples with abundant sphalerite, galena, and/or silicate minerals. Scanning electron microscopy confirmed that the high metal-releasing sample contained several galvanic couples of iron disulfide with other sulfide minerals, whereas the low metal-releasing sample contained fewer galvanic couples or were coated by a silicate mineral. The experiments overall confirmed that the galvanic effects with iron disulfide minerals greatly induce the initial release of Zn and Pb from hydrothermal sulfides into seawater, especially under warm oxic conditions.

Evaluation of the toxicity of leaches from hydrothermal sulfide deposits by means of a delayed fluorescence-based bioassay with the marine cyanobacterium Cyanobium sp. NIES-981.

The commercial use of metals such as copper, lead, and zinc has markedly increased in recent years, resulting in increased interest in deep-sea mining of seafloor hydrothermal sulfide deposits. However, the full extent of the impact of deep-sea mining at hydrothermal field deposits on the environment remains unclear. In addition to impacting the deep sea, the leaching of heavy metals from extracted sulfide mineral may also affect the upper ocean zones as the sulfide rock is retrieved from the seafloor. Here, we used a delayed fluorescence-based bioassay using the marine cyanobacterium Cyanobium sp. NIES-981 to evaluate the toxicity of three sulfide core samples obtained from three drill holes at the Izena Hole, middle Okinawa Trough, East China Sea. Leaches from two of the cores contained high concentrations of zinc and lead, and they markedly inhibited delayed fluorescence in Cyanobium sp. NIES-981 compared with control. By examining the toxicity of artificial mixed-metal solutions with metal compositions similar to those of the leaches, we confirmed that this inhibition was a result of high zinc and lead concentrations into the leaches. In addition, we conclude that this delayed fluorescence-based bioassay is a viable method for use by deep-sea mining operations because it is quicker and requires less laboratory space and equipment than the standard assay.

The tremendous potential of deep-sea mud as a source of rare-earth elements.

Potential risks of supply shortages for critical metals including rare-earth elements and yttrium (REY) have spurred great interest in commercial mining of deep-sea mineral resources. Deep-sea mud containing over 5,000 ppm total REY content was discovered in the western North Pacific Ocean near Minamitorishima Island, Japan, in 2013. This REY-rich mud has great potential as a rare-earth metal resource because of the enormous amount available and its advantageous mineralogical features. Here, we estimated the resource amount in REY-rich mud with Geographical Information System software and established a mineral processing procedure to greatly enhance its economic value. The resource amount was estimated to be 1.2 Mt of rare-earth oxide for the most promising area (105 km2 × 0-10 mbsf), which accounts for 62, 47, 32, and 56 years of annual global demand for Y, Eu, Tb, and Dy, respectively. Moreover, using a hydrocyclone separator enabled us to recover selectively biogenic calcium phosphate grains, which have high REY content (up to 22,000 ppm) and constitute the coarser domain in the grain-size distribution. The enormous resource amount and the effectiveness of the mineral processing are strong indicators that this new REY resource could be exploited in the near future.

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.

Post-drilling changes in seabed landscape and megabenthos in a deep-sea hydrothermal system, the Iheya North field, Okinawa Trough.

There has been an increasing interest in seafloor exploitation such as mineral mining in deep-sea hydrothermal fields, but the environmental impact of anthropogenic disturbance to the seafloor is poorly known. In this study, the effect of such anthropogenic disturbance by scientific drilling operations (IODP Expedition 331) on seabed landscape and megafaunal habitation was surveyed for over 3 years using remotely operated vehicle video observation in a deep-sea hydrothermal field, the Iheya North field, in the Okinawa Trough. We focused on observations from a particular drilling site (Site C0014) where the most dynamic change of landscape and megafaunal habitation was observed among the drilling sites of IODP Exp. 331. No visible hydrothermal fluid discharge had been observed at the sedimentary seafloor at Site C0014, where Calyptogena clam colonies were known for more than 10 years, before the drilling event. After drilling commenced, the original Calyptogena colonies were completely buried by the drilling deposits. Several months after the drilling, diffusing high-temperature hydrothermal fluid began to discharge from the sedimentary subseafloor in the area of over 20 m from the drill holes, 'artificially' creating a new hydrothermal vent habitat. Widespread microbial mats developed on the seafloor with the diffusing hydrothermal fluids and the galatheid crab Shinkaia crosnieri endemic to vents dominated the new vent community. The previously soft, sedimentary seafloor was hardened probably due to barite/gypsum mineralization or silicification, becoming rough and undulated with many fissures after the drilling operation. Although the effects of the drilling operation on seabed landscape and megafaunal composition are probably confined to an area of maximally 30 m from the drill holes, the newly established hydrothermal vent ecosystem has already lasted 2 years and is like to continue to exist until the fluid discharge ceases and thus the ecosystem in the area has been altered for long-term.

Osmium isotope evidence for a large Late Triassic impact event.

Anomalously high platinum group element concentrations have previously been reported for Upper Triassic deep-sea sediments, which are interpreted to be derived from an extraterrestrial impact event. Here we report the osmium (Os) isotope fingerprint of an extraterrestrial impact from Upper Triassic chert successions in Japan. Os isotope data exhibit a marked negative excursion from an initial Os isotope ratio ((187)Os/(188)Osi) of ~0.477 to unradiogenic values of ~0.126 in a platinum group element-enriched claystone layer, indicating the input of meteorite-derived Os into the sediments. The timing of the Os isotope excursion coincides with both elevated Os concentrations and low Re/Os ratios. The magnitude of this negative Os isotope excursion is comparable to those found at Cretaceous-Paleogene boundary sites. These geochemical lines of evidence demonstrate that a large impactor (3.3-7.8 km in diameter) produced a global decrease in seawater (187)Os/(188)Os ratios in the Late Triassic.

Late Jurassic ocean anoxic event: evidence from voluminous sulphide deposition and preservation in the Panthalassa.

The historically productive copper-bearing Besshi-type sulphide deposits in the Japanese accretionary complex were formed as volcanogenic massive sulphide deposits on the deep-sea floor of the Panthalassa Ocean. Here we report that eleven typical Besshi-type deposits yielded Re-Os isochron ages around 150 Ma (148.4 ± 1.4 Ma from the composite isochron) in Late Jurassic time. This date coincides with the lowest marine (87)Sr/(86)Sr ratio and highest atmospheric CO2 concentration of the past 300 million years. We infer that intense mid-ocean ridge hydrothermal and volcanic activity in the Late Jurassic produced huge sulphide deposits and large emissions of CO2 gas, leading to global warming and a stratified Panthalassa Ocean with anoxic deep seas that favored preservation of sulphides in the pelagic environment. The emergence of ocean anoxia triggered by seafloor volcanism is also consistent with a positive δ(13)C excursion and widespread deposition of petroleum source rocks and black shales.