Centennial memorial event of Graduate School of Science and
Faculty of Science, Tohoku University
9 th INTERNATIONAL WORKSHOP ON WATER DYNAMICS DEEP CARBON CYCLE/BEYOND BRITTLE
March 7-9, 2012 Sendai International Center in Sendai, Japan
Sponsor Tohoku University Global-COE Program Global Education and Research Center for Earth and Planetary Dynamics
#
!"#$%&# We had the Great East Japan Earthquake and severe tsumani disaster on March 11 2011, and then we had spent unusual life after the earthquake. Tohoku University, the largest university in Tohoku District, was partly damaged by the earthquake; however, we can continue to perform high level research activities as well as previous conditions. We also notice and conform the importance of Earth Science for human beings. Global COE (Center Of Excellence) project organizes 9 th international workshop on WATER DYNAMICS around first year anniversary of the earthquake. The Workshop will review the fundamental properties and reactivity of WATER, which means not only pure water but also multicomponent geofluids, and the workshop involves the role of carbon in the Earths interior for dynamics and evolution of the Earth System. After the Fukushim Nuclear Power Disaster has drastically changed the energy policy of the Japanese government. The government, industry, and citizens are much more positive to develop stable, safe, locally-distributed, and clean energy resources. Renewable energy such as solar, wind and geothermal have been focused, and geothermal has been considered as one of the most promising solutions for currently occurring energy-related crisis in Japan. $
!"()"%* = Tachibana Conference Hall, Sendai International Center = Wednesday, March 7th, 2012 Time Speaker Title Chairman 10:00-10:10 Eiji Ohtani Opening Remarks N. Tsuchiya 10:10-10:40 Greg Bignall Scientific Rationale and Economic Benefits for Deep (5 km) Geothermal Drilling in the Taupo Volcanic Zone, New Zealand 10:40-11:20 Gudmundur Omar Iceland Deep Drilling Project IDDP-1 in Krafla drilled into >900C hot magma presently the worlds hottest production well (450C). Planning for drilling well IDDP-2 at Reykjanes 11:20-12:00 poster presentation (2min introduction) 12:00-13:00 Poster Session 13:00-14:00 Lunch 14:00-14:40 Alexey Kiryukhin Possible Scientific Drilling Targets in Kamchatka, Russia A. Okamoto 14:40-15:20 Hirofumi Muraoka Japan Beyond-Brittle Project proposed for a geothermal energy paradigm shift in northeastern Japan 15:20-15:50 Hiroshi Asanuma Seismicity from geothermal reservoirs prospects of seismicity from engineered geothermal systems in ductile zone 15:50-16:00 Break 16:00-17:00 ICDP Project Discussion N. Tsuchiya 17:45 Workshop Banquet Thursday, March 8th, 2012 Time Speaker Title Chairman 09:30-10:00 Yangting Lin H isotope constraints on the magmatic and meteoric water of Mars: Evidence from the GRV 020090 martian meteorite Konstantine Litasov 10:00-10:40 Katsuyoshi Michibayashi Tonga Trench: A window to explore a mantle wedge system 10:40-10:50 Break 10:50-11:30 Shun-ichiro Karato Water in the deep interior of the Moon: geophysical constraints and its origin 11:30-12:10 Craig E. Manning pH buffering of subduction-zone fluids: implications for Earths deep carbon cycle 12:10-13:00 Lunch 13:00-13:30 Poster Session 13:30-14:00 Konstantine Litasov Solidi and melting phase relations of alkaline carbonatite at the deep mantle conditions Takeshi Sakai 14:00-14:30 Anton Shatskiy Formation and extraction mechanism of primary kimberlite melt: experimental constrains. 14:30-14:40 Break 14:40-15:10 Seiichi Takami Experimental challenge to realize K4 crystals 15:10-15:50 Hiroaki Ohfuji Experimental study on the phase transition mechanism of graphite to diamond under high pressure and high temperature Anton Shatskiy 15:50-16:00 Break 16:00-16:30 Takeshi Sakai The effect of light elements on Earth's core properties 16:30-17:10 Oliver T. Lord The Earths core: the deepest carbon reservoir and other stories Friday, 9th March, 2012 Time Speaker Title Chairman 10:00-10:30 Noriyoshi Tsuchiya Hydrothermal Derived Fracturing: Natural and Experimental Evidences A. Okamoto 10:40-11:20 Craig E. Manning Element mobility in lower crustal and upper mantle aqueous fluids 11:20-12:00 Derek Elsworth Roles of Fluid Pressure, Thermal and Chemical Effects in Conditioning Permeability and Triggered Seismicity in Enhanced Geothermal Systems Lab Tour in Aobayama
%
+#,-# Sendai International Center
&
%./0"%&0 Oral Presentations Scientific Rationale and Economic Benefits for Deep (5 km) Geothermal .....p.08
Iceland Deep Drilling Project IDDP-1 in Krafla drilled into >900C hot magma presently the worlds hottest production well (450C). Planning for drilling well IDDP-2 at Reykjanes !!!!!!!!!!!!!!!!!!!!!!!...p.09
Possible Scientific Drilling Targets in Kamchatka, Russia !!!!!!!!.p.10
Japan Beyond-Brittle Project proposed for a geothermal energy paradigm shift in northeastern Japan !!!!!!!!!!!!!!!!!!!!!!..!p.11
Seismicity from geothermal reservoirs prospects of seismicity from engineered geothermal systems in ductile zone !!!!!!!!!!!!!!!!..!p.12
H isotope constraints on the magmatic and meteoric water of Mars: Evidence from the GRV 020090 martian meteorite !!!!!!!!!!!!!!!..p.13
Tonga Trench: A window to explore a mantle wedge system !!!!!!...p.14
Water in the deep interior of the Moon: geophysical constraints and its origin !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!.!!p.15
'
pH buffering of subduction-zone fluids: implications for Earths deep carbon cycle !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!p.18
Solidi and melting phase relations of alkaline carbonatite at the deep mantle conditions !!!!!!!!!!!!!!!!!!!!!!!!!!!...!p.19
Formation and extraction mechanism of primary kimberlite melt: experimental constrains !!!!!!!!!!!!!!!!!!!!!!!!!!!!..p.20
Experimental challenge to realize K4 crystals !!!!!!!!!!!!!.p.21
Experimental study on the phase transition mechanism of graphite to diamond under high pressure and high temperature !!!!!!!!!!!!!.!.p.22
The effect of light elements on Earth's core properties !!!!!!!!.!.p.23
The Earths core: the deepest carbon reservoir and other stories !!!!...p.24
Hydrothermal Derived Fracturing: Natural and Experimental Evidences !!p.25
Element mobility in lower crustal and upper mantle aqueous fluids !!!....p.26
Roles of Fluid Pressure, Thermal and Chemical Effects in Conditioning Permeability and Triggered Seismicity in Enhanced Geothermal Systems !p.27 (
Poster Presentations (P1) Thermal Decomposition of Polycyclic Aromatic Hydrocarbons at 800-1100 K and 6-9 GPa: Implication to Earth and Planetary Carbon Dynamics !...!p.28
(P2) Experimental Investigation of the Effect of Water on Fabric Development of Anorthite !!!!!!!!!!!!!!!!!!!!!!!!!!!..!..p.29
(P3) Melting of Carbonated Peridotite at 10-20 GPa: Implication to SiO 2 - Saturation of Carbonated Magma in the Deep Mantle !!!..!.!..!!!.p.30
(P4) Experimental Study on Calcite Precipitation in Hydrothermal Condition Modified after Geosphere Environment !!!!!!!!!!!!...!!!.p.31
(P5) Enhanced Hydrogen Production via Sulfur Redox Cycle by Application of Natural Hydrothermal Resource !!!!!!!!!!!!!!!!!!!.p.32
(P6) Sound Velocity Measurements in FeH using Inelastic X-ray Scattering: Implications for Hydrogen Abundance in the Earths Core !!!!!!...!.p.33
(P7) Thermal Evolution in Malabar Area, Northern Part of the Wayang Windu Geothermal Field: Evidence from Petrographic and Fluid Inclusion Studies ..p.34
(P8) Changes in Permeability and Flow Paths in a Carbonate Fracture during Dissolution Process under Confining Stress !!!!!!!!!!!!!!p.35
(P9) Melting relation of Fe 3 C by in-situ X-ray Diffraction Experiments ....!!p.36 )
Scientific Rationale and Economic Benefits for Deep (5Km) Geothermal Drilling in the Taupo Volcanic Zone, New Zealand
Greg Bignall
Institute of Geological and Nuclear Science Ltd., Wairakei Research Center, New Zealand
E-mail address: g.bignall@gns.cri.nz
The Taupo Volcanic Zone (New Zealand) is an active continental volcanic/back arc and fault- controlled extensional basin, produced by westward subduction of the Pacific Plate beneath the Australian-Indian Plate. The TVZ is a vast natural heat engine, and hosts several geothermal systems that are developed for electric power generation. New Zealands geothermal resources are utilised to ~3 km and temperatures to ~340C. Current geothermal generation is ~760 MWe (~13% of New Zealands total electricity generation). The theoretical deep (>4 km depth) energy potential in the TVZ is massive, but are the resources realizable, and a realistic part of New Zealands energy future? Since 2009, New Zealand Government-funded research has examined the nature of deep geothermal activity in the TVZ. Planning is underway for an ambitious and technically challenging project to drill, sample (fluid and host rock) and assess the permeability structure of deep-seated TVZ geothermal activity. Drilling is aligned with international research objectives involving International Continental Science Drilling Program (ICDP) and International Partnership for Geothermal Technology (IPGT) relationships. The New Zealand geothermal industry is motivated to maximise the potential of their resources, and their involvement in the TVZ science drilling project is essential. Scientific and engineering know-how obtained will help overcome barriers that restrict deep geothermal resource utilisation, whilst providing previously unobtainable insights into the structure and evolution of the TVZ. *
Iceland Deep Drilling Project IDDP-1 in Krafla drilled into >900 hot magma presently the worlds hottest production well (450). Planning for drilling well IDDP-2 at Reykianes
Gudmundur Omar Fridleifsson 1 , Wilfred A. Elders 2 and Bjarni Palsson 3
1. HS Orka hf, Brekkustigur36, Reykianesbr, Iceland 2. Dept. of Earth Science, University of California, Riverside, CA 92521 USA. 3. Landsvirkjun, Haaleitisbraut 68, IS 103, Reykjavik, Iceland
E-mail address: gof@hs.is
The Iceland Deep Drilling Project (IDDP) is investigating the economic feasibility of producing electricity from supercritical geothermal reservoirs. Modelling suggests that producing superheated steam from a supercritical reservoir could potentially increase power output of geothermal wells by an order of magnitude. To test this concept the consortium intends to drill 4-5 km deep wells in three different hightemperature geothermal fields in Iceland, Krafla, Hengill and Reykjanes. The drilling of the IDDP-1 took place in 2009, but had to be terminated at 2.1 km depth when drilling into >900C hot rhyolitic magma. Today the well is highly productive, estimated to be capable of generating 25-35 MWe from dry superheated steam produced from a contact zone above the magma intrusion. With the current wellhead flowing temperature of 450C and enthalpy around 3200 kJ/kg, it can be claimed to be the hottest producing geothermal well in the world. While flow testing to optimize utilization continues, plans are underway to drill a 4-5 km deep well at Reykjanes in 2013-2014. If the IDDP concept proves to be successful, such very high enthalpy geothermal systems may become significant resources worldwide in the future. International Science Workshop for IDDP-2 is being planned for September 2012.
!+
Possible Scientific Drilling Targets in Kamchatka, Russia
Alexey V. Kiryuhin
Institute of Volcanology & Seismology FEB RAS, Piip 9, Petropavlovsk-Kamchatsky, Russia 683006
E-mail address: avkiryukhin2@mail.ru
Mutnovsky magma-hydrothermal system connection. At Mutnovsky (located 75 km to the south of Petropavlovsk Kamchatsky) there are two strong arguments for a direct connection between geothermal production and active magma beneath the volcano. First, the main production zone in the Mutnovsky field is a plane of high permeability that if projected towards the volcano intersects the active conduit at shallow depth. Second, there is a component of the producing fluid, defined in terms of O and H isotopic composition, for which the only known equivalent is the Crater Glacier. The glacier apparently acts as the main source of meteoric water recharge area for the fluids producing by exploitation wells. Exploitation of power plants started in 2000-2002 years with total installed capacity of 62 MWe provides new information on geothermal reservoir formation conditions and connections with adjacent thermal features.
Avachinsky-Koryaksky volcanic basin. Both volcanoes are located 25-30 km to the north of Petropavlovsk Kamchatsky. High temperature fluid reservoir adjacent to the north-north-east flank of Koryaksky volcano is revealed by seismic activity distributions, fumaroles and thermal springs locations. The accessible drilling area was estimated as more than 3 km 2 . Geothermometers (Na-K) applied to thermal springs indicate temperatures above 260 o C. Koryaksky volcano phreatic eruption 2008-2009 seems to be recharged from this reservoir. Another fluid reservoir was penetrated at the south-eastern foothills of Avachinsky volcano, this reservoir reveals significant gas discharge (CH 4 ). The earthquakes precursors in wells and springs have been documented in both areas over the past 30 years of observations. !!
Japan Beyond-Brittle Project Proposed for a Geothermal Energy Paradigm Shift in Northeastern Japan
Hirofumi Muraoka 1 , Hiroshi Asanuma 2 and Hisao Ito 3
1. North Japan Research Institute for Sustainable Energy, Hirosaki University 2. Graduate School of Environmental Studies, Tohoku University 3. Center for Deep Earth Exploration, Japan Agency for Marine-Earth Science and Technology
E-mail address: hiro@cc.hirosaki-u.ac.jp
For an energy paradigm shift in northeastern Japan after the tsunami disasters at March 2011, geothermal energy is one of the most prospective candidates because northeastern Japan is blessed with abundant geothermal resources. However, conventional geothermal power generation is not necessarily enough to supply large amounts of electricity. The next generation geothermal power is an engineered geothermal system (EGS). EGS power generation methods have two types bottle necks for practical utilization; one is that the recoverability of injected water is about 50 % or less than that in fracture- dominant regions like Japan inevitably requiring replenishment of voluminous injected water throughout the power generation operation, and the other is that the injected water raises pore fluid pressures of crustal rocks causing induced felt earthquakes. We propose a new type power generation method using EGS that the two types bottle necks can be solved at the same time by the nucleation of an artificial brittle fracture reservoir system completely surrounded in the ductile zones at a temperature around 500 C which are already confirmed such as in the Kakkonda geothermal field, northeastern Japan. This method would dramatically expand the exploitable geothermal resources to the thermal conduction type resources beyond the brittle zones. !#
Seismicity from Geothermal Reservoirs Prospects of Seismicity from Engineered Geothermal Systems in Ductile Zone
1. Graduate School of Environmental Studies, Tohoku University 2. NJRISE, Hirosaki University
E-mail address: asanuma@ni2.kankyo.tohoku.ac.jp
Seismic events from many of hydrothermal reservoirs and most of the engineered geothermal systems (EGS) reservoirs have been used as one of the few methods which enables us to monitor reservoir characteristics, including reservoir extension, distribution of flow paths, and dynamic response to human operation to the reservoirs. Meanwhile, occurrence of seismic events with unexpectedly large magnitude has been focused as one of the most serious negative impacts of the geothermal development. Common risk of large induced seismicity has been pointed out in EOR in oil industry, CCS, gas storage, and injection of wasted water. Large seismic events collected at hydrothermal and EGS sites showed unique characteristics in critical pore pressure for shear slip, spatio-temporal distribution of their hypocenters, stress drop, and FPSs suggesting that the mechanism can not be simply modeled by asperity model which has been commonly used in global seismology. We consider that development of EGS reservoirs in the ductile zone have potential to avoid occurrence of large magnitude of induced seismicity because of expected relatively homogeneous stress state in the ductile zone and isolated brittle zone in the ductile rock mass, although basic studies should be made to scientifically discuss on seismicity from ductile EGS reservoirs. !$
Isotope Constraints on the Magmatic and Meteoric Water of Mars: Evidence from the GRV 020090 Martian Meteorite
Yangting Lin, Sen Hu, Jianchao Zhang, Jialong Hao, Lu Feng, Wei Yang, Xuchao Zhao
Institute of Geology and Geophysics, Chinese Academy of Sciences
E-mail address: linyt@mail.igcas.ac.cn
GRV 020090 is a lherzolitic shergottite probably derived from the enriched Martian mantle and/or contaminated by the oxidized and enriched crust as the magma intruding into the subsurface of Mars. D/H ratios and water contents of silicate glass of melt inclusions in olivine and pyroxene oikocrysts and apatite in the interstitial part were measured with CAMECA nanoSIMS 50L. Our analyses show distinct correlation of the D/H ratios and water contents between the melt inclusions and apatite. The negative relationship of the D/H and water content of apatite is consistent with previous reports, which can be explained by crystallization of apatite from a melt contaminated by the crust that contained meteoric water. The D/H ratios and water contents of the melt inclusions are positively correlated, which was produced by H diffusion from the wall rock into the inclusions as the igneous unit cooled down below the boiling temperature of water on Mars. This is a solid evidence for temporary presence of liquid water on Mars, which was likely melted from H 2 O ice in wall rock by the intruded magma.
!%
Tonga Trench: A Window to Explore a Mantle Wedge System
Katsuyoshi Michibayashi, Shinkai Yuri
Institute of Geosciences, Shizuoka University
E-mail address: sekmich@ipc.shizuoka.ac.jp
The Tonga trench is one of the deepest oceanic regions in the world (10,866 m). Various types of rocks have been dredged and drilled at several localities on the landward slopes of the trench. In particular, very pristine peridotites occur at the most deep landward trench slope. We show that the trench can be divided into two regions: central region and northern region. The peridotites in the central region have high-Cr# (0.46-0.83) which were typical of forearc peridotites, whereas the peridotites in the northern region have evidences of the reaction with magma during partial melting. Moreover, they remarkably reacted with melt and/or fluid. Olivine fabrics are characterized by E-type and D-type. Although E-type and D-type are no clear relationship of mineral composition, grain size and equilibrium temperature, the only difference between E-type and D-type were fabric intensities. This difference suggests that pristine and serpentinized peridotites in the Tonga trench are deformed in the region where high strain field occurred due to the dragged flow. Eventually, they expose in a very neat condition (i.e. active tectonic erosion and fast ascent rate) resulting from an unique tectonic setting including fast subducting plate (24 cm/yr), fast spreading plate (15 cm/yr) and slab rollback. !&
Water in the Deep Interior of the Moon: Geophysical Constraints and Its Origin
Shun-ichiro Karato
Yale University, Department of Geology and Geophysics, New Haven, USA
E-mail address: shun-ichiro.karato@yale.edu
The recent measurements of some of the Apollo samples showed that some of the lunar samples have evidence for a substantial amount of water in the interior of the Moon (e.g., [Hauri et al., 2011]). This is surprising because a commonly accepted compositional model of the Moon is highly depleted in volatile elements (based on the compositions of many basaltic samples). Such a model is generally considered to be consistent with a giant impact model for the origin of the Moon where extremely high temperature after the impact likely removed a majority of volatile elements. However, the interpretation of petrological observations is non-unique because of the large uncertainties in the processes by which these samples might have been transported to the surface of the Moon. Consequently, the wet deep mantle model of the Moon is still controversial. In this presentation, I will provide additional evidence for the wet deep mantle of the Moon from the analyses of geophysical observations (electrical conductivity and tidal energy dissipation). The high-quality (better than Earth) model of electrical conductivity-depth profile is available for the Moon due to the lack of the surface oceans. The conductivity in the deep mantle reaches ~0.1 S/m that would require unacceptably high temperatures (T > 2000 K) if dry conditions and the low oxygen fugacity are assumed. However, such conductivity values can be explained by modest temperatures if a substantial amount of water is assumed. The tidal Q of the Moon is also surprisingly small (high energy dissipation) although the Q in the shallow mantle (and the crust) of the Moon is very high. The tidal Q is mostly determined by the rheological properties of the deep mantle, and consequently, this observation also suggests that the deep mantle of the moon is soft, that is consistent with wet deep mantle model of the Moon. !'
Why does the (deep) mantle of the Moon have such high water content if the Moon was formed by giant impact? [Elkins-Tanton and Grove, 2011] developed a model to explain some of the recent observations of wet samples through the modeling of crystallization of the initially wet magma ocean. Although such a model provides some insights into the depth variation of water content, this model does not explain why the initial materials of the Moon were wet if the Moon was formed by a giant impact. I propose that a key to this puzzle is the fact that condensation after the giant impact likely occurred in the high-pressure environment compared to the condensation in the solar nebula. The pressure of the Moon forming nebula can be calculated from the mass and the size of the nebular materials, and turns out to be on the order of 1-10 MPa at the distance close to the Roche limit where much of accretion occurred [Kokubo et al., 2000]. Such a pressure is much higher than the pressure in the representative region of the solar nebula (~10 -5 MPa (~10 Pa)). At this level of high pressure, condensation from the gas should occur as gas ! liquid (! solid) as opposed to gas ! solid that should occur in the high-vacuum environment [Mysen and Kushiro, 1988]. Consequently, if the cooling time scale of the nebula is longer than the time scale of accretion, then the Moon will be formed by the accretion of liquids that have much higher water solubility than solid minerals. Currently available modeling results suggest that such a condition is feasible although the uncertainties in the accretion time scale are large. According to this model, the high water content in the deep Moon is essentially due to the Moon formation from the dense proto-lunar nebula in which liquids phase are accumulated to form the Moon rather than the solid particles. After the formation of the Moon, solidification and chemical differentiation likely occurred and the stratification in water content resulted as shown by [Elkins-Tanton and Grove, 2011]. Consequently, the shallow part of the Moon is relatively depleted with water but the deep part contains a substantial amount of water. However, due to the extremely high temperature in the proto-lunar nebula, dissociation of water into hydrogen + oxygen likely occurred that resulted in the hydrodynamic loss of hydrogen leading to the increase in D/H ratio, a result consistent with the isotopic observations [Greenwood et al., 2011].
Elkins-Tanton, L., and T. L. Grove (2011), Water (hydrogen) in the lunar mantle: Results from petrology and magma ocean modeling, Earth and Planetary Science Letters, 307, 173-179. Greenwood, J. P., S. Itoh, N. Sakamoto, P. Warren, L. A. Taylor, and H. Yurimoto (2011), Hydrogen isotope ratios in lunar rocks indicate delivery of cometary water to the Moon, Nature Geoscience, 4, 79-82. !(
Hauri, E. H., T. Weinreich, A. E. Saal, M. C. Rutherford, and J. A. Van Orman (2011), High pre- eruptive water contents preserved in lunar melt inclusions, Science, 333, 213-215. Kokubo, E., S. Ida, and J. Makino (2000), Evolution of a circumterrestrial disk and formation of a single Moon, Icarus, 148, 419-436. Mysen, B. O., and I. Kushiro (1988), Condensation, evaporation, melting, and crystallization in the primitive solar nebula: Experimental data in the system MgO-SiO 2 -H 2 to 10 -9 bar and 1870 0 C with variable oxygen fugacity, American Mineralogist, 73, 1-19. !)
pH Buffering of Subduction-Zone Fluids: Implications for Earths Deep Carbon Cycle
Craig E. Manning
University of California, Los Angeles, CA, 90095, USA
E-mail address: manning@ess.ucla.edu
Volcanic arcs return CO 2 to the Earths surface, but the transfer mechanism is problematic. Phase equilibrium studies of subduction zones indicate that, in the absence of fluids, carbonate minerals are quite stable along slab P-T paths, so their simple breakdown cannot be a significant mechanism by which CO 2 is transferred, at least to subarc depths. Alternatively, CO 2 can be stripped from slab carbonates by infiltration of H 2 O-rich fluid, driving reactions that can be modeled by aragonite + quartz = wollastonite + CO 2 . However, the high P and low T of subduction zones such as Cascadia, western North America, causes maximum fluid CO 2 concentrations to remain low at depths <100 km. In contrast, the equation of Caciagli and Manning (2003, CMP, 146, 275) for the solubility of CaCO 3 in H 2 O yields C concentrations up to 10x greater along the Cascadia slab-mantle interface to depths of ~80 km. The capacity for carbon transport also depend strongly on pH. At 1.8 GPa, 500C, the pH of pure H 2 O equilibrated with CaCO 3 is 6.7 (neutral pH is 3.8), whereas the pH of the jadeite-paragonite- quartz buffer is 6.0, yielding a ~10X increase in dissolved carbon in slab fluids. Because carbonic acid is the predominant form of oxidized carbon at subduction zone conditions, pH effects play a key role in the operation of the Earths deep carbon cycle. !*
Solidi and Melting Phase Relations of Alkaline Carbonatite at the Deep Mantle Conditions
Litasov K.D., Shatskiy A., Ohtani E.
Department Earth Planetary Materials Science, Tohoku University
E-mail address: klitasov@m.tohoku.ac.jp
Studies of melting relations in carbonate peridotite and eclogite often fail to determine true solidus due to low-temperature stability of poorly resolvable small fractions of alkali-bearing carbonatite melt or solid phases. In this report we determined solidi and phase relations in model K- and Na-bearing carbonatite systems and discuss stability of alkali carbonates and their effect for mantle melting and carbon transport. Two starting materials of Ca-Mg carbonatite melt enriched in Na 2 O and K 2 O, respectively (2 and 7 wt% and vice versa), were examined. Minor SiO 2 and FeO were also added. Experiments were conducted using multianvil technique at 3-21 GPa and 750-1400 o C. The solidus temperature of Na- and K-carbonatite is located near 750 o C at 3 GPa and 850 o C at 6 GPa. Significant increase of the solidus temperature up to 1150 o C was found between 6 and 10 GPa. Then, between 10 and 21 GPa the solidi are flat. In the Na-bearing system 6-10 wt% Na 2 O can be dissolved in aragonite, which is nearly all Na 2 O added to the system. Several stable alkali-bearing carbonates were observed in the both K-bearing and Na-bearing systems. Most important of them are (K,Na) 2 Mg(CO 3 ) 2 and (K,Na) 2 Ca 4 (CO 3 ) 5 . The K 2 O content in these carbonates is always dominates over Na 2 O even in the Na-bearing system. Silicate phases include diopside at pressures below 15 GPa, Ca-Fe-bearing melilite- like phase at 15 GPa, and Ca-perovskite and stishovite at 21 GPa. Low-degree partial melts are Na- and K-rich for Na- and K-bearing carbonatite, respectively, due to early melting of alkali carbonatite. Magnesite is the liquidus carbonate phase along with silicate at all pressures. Comparison of solidi for Na- and K- bearing carbonatite with subduction geotherms indicate stability of alkali carbonates along cold subduction paths. Melting of subducting alkaline carbonates would likely occur at the transition zone depths to produce mobile carbonatite melt diapirs, migrating upwards, modifying and oxidizing the upper mantle and initiating volcanism at the surface. #+
Formation and Diapiric Mobilization of Primary Kimberlite Melts: Experimental Constrains
Shatskiy A., Sharygin I.S., Litasov K.D., Ohtani E.
Department Earth Planetary Materials Science, Tohoku University
E-mail address: shatskiy@m.tohoku.ac.jp
Kimberlites are the deepest probe into Earths mantle (>150-250 km). However, our understanding of kimberlite ascent is hampered by uncertainty about the compositions of primary kimberlite melts. It is generally considered that kimberlite rocks represent the ultramafic nature of the parental melt composition. Numerous findings of water depleted alkali-Ca-carbonatite melt inclusions enriched in Fe, Ti, Cl, P, and S in olivine and ilmenite from kimberlites and xenogenic nature of ! 40 vol.% of olivine in a groundmass from kimberlites worldwide make questionable ultramafic paradigm. To clarify this problem we performed experiments on melting phase relations in an exceptionally fresh kimberlite group I from Udachnaya-East kimberlite (UEK) pipe at 3.0-6.5 GPa and 900-1500C. Observed crystallization sequence at 6 GPa includes Al-spinel, olivine, perovskite, Ca- rich garnet, aragonite, and apatite. The system did not achieve complete melting even at 1500C and 6.5 GPa. Based on the partial melt composition we suggest that during its ascent via the lithospheric mantle UEK was a mixture of carbonatite melt and xenoliths. Primary group I kimberlitic magma was Na-K-Ca-carbonatite containing <15 wt.% SiO 2 , Na 2 O + K 2 O = 5-18 wt%, Na/K " 2, Cl >1.5 wt%, and Ca/(Ca+Mg) > 0.5. We also suggest diapiric ascent of parental kimberlite (carbonatite) melt from deep source region to the base of lithospheric mantle. The carbonatite melt chamber should be unavoidably surrounded by aureole impregnated with carbonatite melt due to difference in surface energies of wetted and dry rock. Taking into account excellent wetting properties of high-diffusive carbonatite melt and small grain size of wall-rock (i.e. sheared peridotites), the pressure-solution creep of wetted wall- rocks could be predominant deformation mechanism allowing rapid diapiric ascent. Based on our experimental data on diffusivity of silicate components in carbonatite melt the rate of diapiric ascent of parental kimberlite (carbonatite) melt is estimated to be 0.5 m/year for 2-km body. #!
Experimental Challenge to Realize K4 Crystal
Seiichi Takami
Institute of Multidisciplinary Research for Advanced Materials, Tohoku University
E-mail address: stakami@tagen.tohoku.ac.jp
Recently, Sunada proposed three dimensional K4 crystal structure that comprises all-equivalent sp2 carbon atoms based on topological study. Inspired from this mathematic proposal, we studied the properties of K4 crystals using computational chemistry. The results suggested that the K4 crystals would be synthesized under high pressure with co-existing elements including Na, Mg etc. We also proposed similar K4 structure of BN with co-existing elements. This presentation will focus on the predicted properties of K4 crystals and its periphery. We will also show our efforts to synthesize K4 crystals ##
Phase Transition Mechanism and Microstructure Evolution through GraphiteDiamond Transition under High Pressure and High Temperature
Hiroaki Ohfuji
Geodynamics Research Center, Ehime University, Japan
E-mail address: ohfuji@sci.ehime-u.ac.jp
The phase transition mechanism of graphite-diamond transition was studied through the microstructural observation of diamond samples synthesized by the direct conversion of graphite under a wide range of PT conditions (15-50 GPa and ~1000-3000C). The results showed that the transition mechanism and the resultant microstructure of diamond synthesized depend largely on the crystallinity of initial graphite sources but less on PT conditions and local stress. When well-crystalline graphite is used as a starting material, it transforms to diamond by a diffusion-less, martensitic process via hexagonal-diamond as an intermediate phase. In this process, the original layered structure of graphite is substantially maintained after phase transition, resulting in the formation of lamellar structure. On the other hand, when started with poorly crystalline graphite, which involves a significant number of sp3- like bonds at lattice defects and crystal surfaces, spontaneous nucleation of diamond occurs preferentially at those active bonds. As the result, granular microstructure is produced by diffusion- controlled nucleation and growth of nano-diamonds. This suggests that microstructure and the corresponding physical properties of synthetic polycrystalline diamond can be controlled by carefully choosing initial graphite sources based on their crystallinity. #$
The Effect of Light Elements on Earth's Core Properties
1. Department of Earth and Planetary Materials Science, Graduate school of Science, Tohoku University 2. Department of Geology, University of Illinois 3. Department of Earth and Space Science, Osaka University
E-mail address: t-sakai@m.tohoku.ac.jp
Since Earths core density is lower than that of pure iron, it should contain a few percent of light elements such as carbon (C), hydrogen (H), sulfur (S), oxygen (O), and silicon (Si). The existence of light element has large effects on the core material properties (density, melting temperature, sound velocity, etc.). We investigated about the melting and phase relation for Fe-C, Fe-Si, Fe-O-S system, and the equation of state of Fe-H, Fe-S and Fe-Si alloys, and also the sound velocity of FeH x . We conducted the high pressure and temperature experiments using laser heated diamond anvil cell. The melting, phase, and density of samples were determined by powder X-ray diffraction study at SPring-8 BL10XU. The sound velocity of FeH x was measured by the inelastic X-ray scattering experiment at SPring-8 BL35XU. Our results show that the hexagonal close-packed structure is plausible for the inner core in the cases of Fe-H, Fe-Si, and Fe-S system. The inner core boundary temperature is estimated to be 5630 K for Fe-O-S system. We suggest three compositional models for the inner core based on the equation of state (and the sound velocity of FeH x ). Fe-5wt.%Ni-5.7wt.%S, Fe-5.4wt.%Ni- 5.8wt.%Si, and FeH 0.13 (0.23 wt.%H) can explain the inner core density. #%
The Earths core: The Deepest Carbon Reservoir and Other Stories
Oliver T Lord 1 , Michael J. Walter 2 , Rajdeep Dasgupta 3 , Dave Walker 4 and Simon M. Clark 5
1. Department of Earth Sciences, University College London, Gower Street, London, WC1E 6BT, UK 2. School of Earth Sciences, University of Bristol, Wills Memorial Building, Queens Road, Bristol, BS81RJ, UK 3. Department of Earth Sciences, Rice University, 6100 Main Street, MS 126, Houston, Texas, USA 4. Lamont-Doherty Earth Observatory, P. O. Box 1000, 61 Route 9Q, Palisades, NY 10964-1000, USA 5. Department of Earth and Planetary Sciences, Macquarie University, Sydney, NSW2109, Australia
E-mail address: oliver.lord@bristol.ac.uk
We have determined the Fe-C phase diagram up to 70 GPa using a range of techniques, including synchrotron-based x-ray imaging of spatially resolved components within the laser-heated diamond anvil cell. These investigations suggest that the carbon content of the eutectic drops rapidly with pressure, becoming negligible by ~50 GPa and that at ~120 GPa, Fe 3 C (cementite) will be replaced at the solidus by Fe 7 C 3 . Whether Fe 7 C 3 crystallises within the inner core, or whether the carbon budget dissolves into the iron phase depends on the bulk core carbon content and the composition of this new Fe+Fe 7 C 3 eutectic. I will also discuss some of the implications that these results may have for the mantle, which is expected to contain both metallic iron and free carbon. These results represent a tiny fraction of the numerous exciting advances which are currently being made within the field of core science. These are being driven by rapid improvements in our capability to reach extreme pressures and temperatures in the laboratory and to make an ever widening range of useful measurements once we are there. #&
Hydrothermal Derived Fracturing: Natural and Experimental Evidences
Noriyoshi Tsuchiya
Graduate School of Environmental Studies, Tohoku University
E-mail address: tsuchiya@mail.kankyo.tohoku.ac.jp
Veins are intimately related to fracture mechanics, since most veins form by crystal growth into space generated by fractures. Here, problems are why and how host rocks can be failed in certain conditions. We could observe hydrothermal brecciation in several geological settings, such as accretionary prism, mineralized area, and metamorphic rocks. Hydrothermal breccias was formed by explosive failure without any chemical reactions such as dissolution and precipitate. According to field observation and lab work, we have to consider about meanings of "hydrothermal" and "brecciation", and then their relation. We already proposed "HDF: Hydrothermally Derived Fracturing". Fluids has great role to create fracture networks as an explosive failure. Recent progress in field observational, experimental and theoretical research concerning "Hydrothermal Brecciation" and "Hydrothermally Derived Fracturing" will be presented. #'
Element Mobility in Lower Crustal and Upper Mantle Aqueous Fluids
Craig E. Manning
University of California, Los Angeles
E-mail address: manning@ess.ucla.edu
Mineral solubility in pure H 2 O is a poor guide to assessing minor-element transfer by high- pressure fluids. This is because interactions with the major solutes derived from host lithologies control on element mobility. This can be seen with three examples. First, solubility of Al is low in pure H2O; however, in the presence of SiO2 its solubility is dramatically higher. This arises from formation of polymerized Al-Si clusters. Even higher solubilities result from addition of alkalis. In deep fluids, Al is one of the most soluble elements in deep fluids. A second example is that low rutile solubility in pure H 2 O at subduction zone conditions fails to explain occurrence of this phase in veins in high P rocks. However, TiO 2 solubility is greatly enhanced dissolved Na-Al silicates, via incorporation in Na-Ti complexes or Na-Al-Si oligomers. Experimentally constrained solubility data indicate that at 600 C along model slab geotherms, rutile solubility in H 2 O is 2 ppm Ti, whereas in H 2 O equilibrated with cpx+mica+quartz the high dissolved Na-Al-Si yield 88 ppm Ti. If albite-H 2 O fluids are supercritical, even greater Ti transport is possible. Finally, alkali halides are also important complexing agents. At 800C, 1 GPa, CePO 4 monazite and YPO 4 xenotime solubilities are very low in pure H 2 O but are significantly enhanced by NaCl via REE/Y-chloride and Na-phosphate complexing. This strongly increases REE mobility. In general, the influence of aqueous complexing on element solubility highlights that the role of fluids in element recycling can vary widely. #(
Roles of Fluid Pressure, Thermal and Chemical Effects in Conditioning Permeability and Triggered Seismicity in Enhanced Geothermal Systems
Department of Energy and Mineral Engineering, EMS Energy Institute and G3 Center, Pennsylvania State University, University Park, Pennsylvania, USA 2. Helmholtz Center for Environmental Research, Leipzig, Germany
E-mail address: elsworth@psu.edu
The evolution of permeability, heat or diffusive transfer area and triggered seismicity are intimately linked in forced-circulation systems such as EGS, CCS and unconventional hydrocarbon reservoirs where conditions are pushed far-from-equilibrium. We explore this evolution subject to coupled THMC processes in a prototypical EGS reservoir. We accommodate the influence of early- time changes in effective stress, mid-time changes in thermal stresses and ultimately incorporate long- term changes due to chemical effects. We develop a micromechanical model to represent the failure process and apply this model to represent energy release from individual critically oriented fractures. The changing stress state is calculated from the pore pressure, thermal drawdown and chemical effects for a coupled THMC model with dual porosity. This model is applied to a doublet geometry to explore the spatial and temporal migration for permeability evolution, access to reactive surface area and the triggering of seismicity as stimulation then production proceeds. Seismic activity is initially concentrated around the near-wellbore injection region. It is earliest for closely spaced fractures in reservoir rocks where the thermal drawdown of stress is largest at early times and results in numerous low-magnitude events. These observations are used to define the evolution of spatial changes within the reservoir and their migration with production, dependent on the mobilization of relic fractures.
#)
(P1) Thermal Decomposition of Polycyclic Aromatic Hydrocarbons at 800-1100 K and 6-9 GPa: Implication to Earth and Planetary Carbon Dynamics
Chanyshev, A.D. 1 , Litasov, K.D. 1,2 *, Shatskiy, A. 1,2 , Furukawa, Y. 2 , Nemoto, M. 3 , Mochizuki, S. 3 , Ohtani, E. 2 , Funakoshi, K. 4
1. V.S. Sobolev Institute of Geology and Mineralogy, Novosibirsk, Russia 2. Department of Earth Planetary Materials Science, Tohoku University 3. Instrumental Analysis Group, Graduate School of Engineering, Tohoku University 4. SPring-8, Japan Synchrotron Radiation Research Institute, Kouto, Hyogo 678-5198, Japan
E-mail address: klitasov@m.tohoku.ac.jp
The origin of various deep-seated hydrocarbons was widely discussed in relation to the nature of C-O-H fluid. Some theoretical calculations of equations of state for a range of hydrocarbons indicate their possible increased stability in the deep mantle. These components, especially, polycyclic aromatic hydrocarbons (PAHs), were found in natural samples inclusions in deep diamonds and garnets, meteorites, as well as detected in the other planets and satellites and interstellar matters. To date we have several important contributions from experimental petrology. Composition of C-O-H fluids under controlling oxygen fugacity was measured in samples quenched after piston-cylinder and multianvil experiments. They reveal CH 4 - and H 2 -bearing compositions with subordinate H 2 O at 3-6 GPa and 1200-1600 o C. Direct observation of methane formation from carbonate and methane dissociation to heavy alkanes was demonstrated in the diamond anvil cell experiments at 5-10. In present project we studied temperature stability and decomposition products of a range of PAHs at pressures up to 20 GPa using multianvil high-pressure apparatus and in situ X-ray diffraction at SPring-8. We successfully observed X-ray diffraction patterns of PAHs at high pressure. Disappearance of diffraction lines of PAHs was used as a detection of their decomposition. The decomposition of several PAH, ranging in atomic mass from naphthalene to pyrene and coronene was observed at 550-650 o C and 6-9 GPa. We observed strong polymerization of PAHs in the experiments at 500 o C and 7 GPa analyzed by MALDI #*
and gas chromatography. Our data clearly show that PAHs cannot be stable at the average PT- conditions of the upper mantle. (P2) Experimental Investigation of the Effect of Water on Fabric Development of Anorthite
Jun-ichi Fukuda, Jun Muto, Hiroyuki Nagahama
Department of Earth Sciences, Graduate School of Science, Tohoku University
E-mail address: jfukuda@dges.es.tohoku.ac.jp
We performed deformation experiments of polycrystalline anorthite using a pressure-medium (Griggs-type) deformation apparatus under lower-middle crustal conditions. An100 polycrystal with the average grain size of 3 #m was sintered as a starting material. Water was introduced into the sample at high temperature (up to 950 C) and pressure (1.0 GPa), and the samples were deformed under differential stress (up to 800 MPa) with the strain rate of up to 10 5 /sec. After the experiments, development of crystal preferred orientation (CPO) was inferred at 500 #m from the rim of the sample, as concentration of interference color under a polarized optical microscope. In this region also, the reaction of An100 + H 2 O to zoisite was seen in an infrared spectrum as OH vibrational bands due to zoisite around 3200 cm 1 , and these bands were decreased from the rim. These observations indicate that both plastic deformation and reaction occurred due to concentration gradient of water. We will discuss changes in stress/strain due to concentration gradient of water in a polycrystalline anorthite which is a load-bearing framework of the lower-middle crust. $+
(P3) Melting of Carbonated Peridotite at 10-20 GPa: Implication to SiO 2 -Saturation of Carbonated Magma in the Deep Mantle
Ghosh S., Litasov K.D., Ohtani E.
Department of Earth Planetary Materials Science, Tohoku University
E-mail address: klitasov@m.tohoku.ac.jp
It is thought that kimberlite magma is originated from enriched deep mantle in the cratonic roots or asthenosphere. Recent models suggest primary SiO 2 -depleted or even carbonatitic compositions for primary kimberlite magmas. Experimental studies of the systems, containing C-O-H volatiles, are critical for understanding the origin of kimberlite and carbonatite magma. In this work we performed a series of multianvil experiments on two carbonate-bearing peridotite compositions (ACP: alkali-rich carbonated peridotite + 5.0 wt% CO 2 ; and PERC: peridotite + 2.5 wt% CO 2 ) from 10 to 20 GPa and temperature from 1500 to 2100 o C to determine the phase relations and melt compositions of carbonated peridotite in the upper mantle and transition zone in relation to generation of kimberlite- and carbonatite-like magmas. Near-solidus (ACP: 1400-1630 o C between 10 and 20 GPa) carbonatitic partial melts with <10 wt% SiO 2 and >40 wt% CO 2 gradually change to carbonated silicate melts with >25 wt% SiO 2 and <25 wt% CO 2 between 1480-1650 o C in the presence of residual majorite garnet, olivine/wadsleyite and clinoenstatite. The temperature of the first appearance of CO 2 -bearing silicate melt at 10 GPa is ~400 o C lower than the solidus of CO 2 -free peridotite. Majorite garnet is a liquidus phase in natural carbonated peridotite (ACP and PERC) from 10 to 20 GPa and liquidus is likely to be at 2100 o C or higher at pressures of the present experiments, which gives more than 600 o C melting interval in the carbonated systems. In this work we parameterized the levels of SiO 2 and CO 2 saturation of carbonate-silicate melt at 10-20 GPa and compared the results with the previous data at lower pressures. These data allow new constraints on PT-path and temperature of kimberlite magma generation in the H 2 O-free or H 2 O-poor sources. $!
(P4) Experimental Study on Calcite Precipitation in Hydrothermal Condition Modified after Geosphere Environment
To reduce greenhouse gas (CO 2 , CH 4 etc) in the atmosphere, the carbon storage underground has been tried; however, it is considered to be difficult to precipitate calcite in reasonable timescale. In contrast, calcite veins are very common in the oceanic crusts, metamorphic rocks, and accretionary prisms. The purpose of this study is to understand the controlling factors on calcite precipitation under conditions of calcite-vein formation (fluid compositions, P-T conditions, host rock types). As a first step, we conducted hydrothermal flow-through experiments to precipitate calcite on limestone substrates by using the temperature dependency of solubility. After the run of 240 h (10 days), observation of the surface morphologies of the substrates by SEM and thin sections by optical microscope reveal that euhedral calcite crystals with size of 0.02-0.03 mm grew from the calcite in the substrates. Second, we conducted flow-through experiments at 300 to precipitate calcite from natural rock samples with NaHCO 3 solution (pH 8.4). After the run of 240 h, observation of the surface of the substrates by SEM and EDS reveal that calcite crystals with size of 0.01 mm precipitated on the substrates with clay minerals and apatite. Our results suggest that calcite veins could be formed at high temperature around 300 C, in alkaline fluids, if fluids saturated with calcite by Ca from host rocks and CO 3 2- in the crustal fluids. $#
(P5) Enhanced Hydrogen Production via Sulfur Redox Cycle by Application of Natural Hydrothermal Resource
1. Graduate School of Environmental Studies, Tohoku University 2. Frontier Research Center for Energy and Resources (FRCER), School of Engineering, Tokyo University
E-mail address: putri@geo.kankyo.tohoku.ac.jp
Hydrothermal condition is known to be beneficial as a reaction medium due to its effectiveness and environmental benignity. This condition of high temperature water is naturally provided in the earth interior, e.g. in geothermal system. On the other hand, hydrogen is known as an important substance in industries and also a promising energy carrier. This study proposes a hydrogen production method that could utilize the natural hydrothermal resources as an environmentally friendly heat source for the reactions. In this method, hydrogen produced via sulfur redox-cycle which consists of two half cycles: (1) hydrogen production from an aqueous alkaline solution at hydrothermal condition where sulfide, HS - and S 2- , acts as reducing agent of water, and (2) sulfide regeneration at milder condition with an organic compound, i.e. glucose acting as reducing agent of polysulfide and sulfur oxyanion formed in the first half cycle. A hydrogen production through the sulfur redox cycle was also demonstrated by following procedure: 1 st hydrogen production - sulfide regeneration - 2 nd hydrogen production, where the hydrogen production and sulfide regeneration were conducted at 300 C and 105 C, respectively. As sulfide is regenerable, glucose is considered as the raw material. Results indicated that hydrogen production from 1 mol glucose was greater than that by hydrothermal gasification at much higher temperatures up to 500 C. $$
(P6) Sound Velocity Measurements in FeH using Inelastic X-ray Scattering: Implications for Hydrogen Abundance in the Earths Core
1. Department of Earth and Planetary Material Sciences, Tohoku University 2. Materials Dynamics Laboratory, RIKEN SPring-8 Center 3. Graduate School of Material Science, University of Hyogo 4. Japan Synchrotron Radiation Research Institute (SPring-8/JASRI) 5. Advanced Materials Laboratory (AML), National Institute for Materials Science (NIMS)
E-mail address: y-shibazaki-g@s.tohoku.ac.jp
The Earths interior has been directly investigated by seismic wave propagation and normal mode oscillation. In particular, the distributions of density and sound velocity are available to study the Earths core (e.g. PREM). The inner core, which is solid state, is approximately 3 % less dense than pure iron, and it is considered that the core consists of iron and light elements. In this work, we determined the compressional sound velocity (V p ) of iron hydride (FeH) at high pressure using inelastic X-ray scattering (IXS) in order to constrain the abundance of hydrogen in the Earths core by matching the density and sound velocity of FeHx to those of PREM. The IXS experiments and in situ X-ray diffraction (XRD) experiments were conducted up to 70 GPa and room temperature at BL35XU and BL10XU of the SPring-8 facility in Japan, respectively. High-pressure conditions were generated using a symmetric diamond anvil cell (DAC) with tungsten gaskets. We show that FeH follows Birchs law for V p above 37 GPa, namely a linear dependence between velocity and density. The estimated V p , extrapolated to core conditions, is compared with PREM. Our results provide that the Earths inner core could contain ~ 0.2 wt% hydrogen. $%
(P7) Thermal Evolution in Malabar Area, Northern Part of the Wayang Windu Geothermal Field: Evidence from Petrographic and Fluid Inclusion Studies
1. Graduate School of Environmental Studies, Tohoku University, Japan; 2. Faculty of Earth Sciences and Technology, Institut Teknologi Bandung, Indonesia; 3. Star Energy Geothermal (Wayang Windu) Ltd., Jakarta 11410, Indonesia
E-mail address: arifs@geo.kankyo.tohoku.ac.jp
The Malabar area, northern part of the Wayang Windu geothermal field is located in the West Java province of Indonesia. Hydrothermal alteration and fluid inclusion studies was conducted to characterize subsurface hydrothermal alteration and thermal evolution in the Malabar area. Cutting and core samples were collected from five wells in Malabar area, subjected to petrographic, X-ray diffraction and fluid inclusion analyses. The subsurface hydrothermal alteration study in MBA-2 and MBB-1 wells reveals three types of alteration: advanced argillic, subpropylitic and propylitic alterations. Temperatures ranging from 120 to 340 o C with acid and neutral pH fluid alterations. The fluid inclusion analyses in MBB-1, MBA-1, MBD-5 and WWR-SH yielded wide range of homogenization temperature, ranging from 124 o C to 332 o C suggest hydrothermal activity in this area occur more than once period. The low salinity fluids (0.18 to 3.0 wt% NaCl equivalent) may represent mixtures of condensate and the original reservoir fluids. $&
(P8) Changes in Permeability and Flow Paths in a Carbonate Fracture during Dissolution Process under Confining Stress
A flow-through experiment with HCl aqueous solution (pH: approximately 3.4) was conducted on fractured Ryukyu limestone (Okinawa, Japan), which contained either a single tensile or single saw- cut fracture, under stress at the room temperature. The tensile fracture was used to mimic a natural (variable-aperture) fracture. The saw-cut fracture was used for a comparison because a natural fracture is sometimes assumed as such a non-variable aperture fracture. Experimental results showed different rates of permeability increase between the tensile and saw-cut fractures, where the rate of permeability increase in the tensile fracture was smaller than that in the saw-cut fracture. Results of a numerical analysis of fracture flow, in which fracture surface topographies before and after the experiment were used, showed that fluid flow occurred along preferential flow paths, and increased aperture points seemed to have a relation to the flow paths. Experimental and numerical results indicated that the rate of permeability increase in a natural fracture is smaller than a prediction using a non-variable aperture fracture, because dissolution of fracture surfaces occurred in smaller area of the fracture plane due to the preferential flow paths. $'
(P9) Melting relation of Fe 3 C by in-situ X-ray Diffraction Experiments
1. Department of Earth and Planetary Materials Science, Graduate School of Science, Tohoku University, 2. Japan Synchrotron Radiation Research Institute
E-mail address: stakahashi@s.tohoku.ac.jp
The Earths core is regarded as an Fe-Ni alloy but the density of the core is lower than that of pure Fe at pressures and temperatures corresponding to the core conditions. Therefore, the Earths core is supposed to contain light elements and carbon is one of the candidates of the light elements to explain the density deficit of the Earths core. Until now, many studies on physical and chemical properties of Fe-carbides, such as Fe 3 C and Fe 7 C 3 , have been carried out at high pressure. Especially, the recent studies on the melting of Fe 3 C were reported by Nakajima et al. (2009) and Lord et al. (2009). However, there are obvious discrepancies between the melting curves of Fe 3 C in the previous studies. In order to reveal the uncertainty of the melting temperature of Fe 3 C and discuss the behaviors of carbon in the Earths core, the melting temperatures of Fe 3 C were determined based on in situ X-ray diffraction experiments. We determined the melting relation of Fe 3 C up to 70 GPa. The melting temperature (both solidus and liquidus) of Fe 3 C is close to Nakajima et al. (2009) up to 30 GPa but becomes close to that reported by Lord et al. (2009) at higher pressure conditions. The present experiments revealed that Fe 3 C was stable as a subsolidus phase at least up to 70 GPa. This indicates that Fe 3 C is a potential candidate of the Earths inner core.