Mineralogy of the Boroo Gold Deposit in the North Khentei Gold Belt,Central Northern Mongolia

Mineral assemblages and chemical compositions of ore minerals from the Boroo gold deposit in the North Khentei gold belt of Mongolia were studied to characterize the gold mineralization, and to clarify crystallization processes of the ore minerals. The gold deposit consists of low‐grade disseminated and stockwork ores in granite, metasedimentary rocks and diorite dikes. Moderate to high‐grade auriferous quartz vein ores are present in the above lithological units. The ore grades of the former range from about 1 to 3 g/t, and those of the latter from 5 to 10 g/t, or more than 10 g/t Au. The main sulfide minerals in the ores are pyrite and arsenopyrite, both of which are divisible into two different stages (pyrite‐I and pyrite‐II; arsenopyrite‐I and arsenopyrite‐II). Sphalerite, galena, chalcopyrite, and tetrahedrite are minor associated minerals, with trace amounts of bournonite, boulangerite, geerite, alloclasite, native gold, and electrum. The ore minerals in the both types of ores are variable in distribution, abundance and grain size. Four modes of gold occurrence are recognized: (i) “invisible” gold in pyrite and arsenopyrite in the disseminated and stockwork ores, and in auriferous quartz vein ores; (ii) microscopic native gold, 3 to 100 µm in diameter, that occurs as fine grains or as an interstitial phase in sulfides in the disseminated and stockwork ores, and in auriferous quartz vein ores; (iii) visible native gold, up to 1 cm in diameter, in the auriferous quartz vein ores; and (iv) electrum in the auriferous quartz vein ores. The gold mineralization of the disseminated and stockwork ores consists of four stages characterized by the mineral assemblages of: (i) pyrite‐I + arsenopyrite‐I; (ii) pyrite‐II + arsenopyrite‐II; (iii) sphalerite + galena + chalcopyrite + tetrahedrite + bournonite + boulangerite + alloclasite + native gold; and (iv) native gold. In the auriferous quartz vein ores, five mineralization stages are defined by the following mineral assemblages: (i) pyrite‐I; (ii) pyrite‐II + arsenopyrite; (iii) sphalerite + galena + chalcopyrite; (iv) Ag‐rich tetrahedrite‐tennantite + bournonite + geerite + native gold; and (v) electrum. The As–Au relations in pyrite‐II and arsenopyrite suggest that gold detected as invisible gold is mostly attributed to Au⁺¹ in those minerals. By applying the arsenopyrite geothermometer to arsenopyrite‐II in the disseminated and stockwork ores, crystallization temperature and logfs₂ are estimated to be 365 to 300 °C and –7.5 to –10.1, respectively.     

Early Carboniferous HP metamorphism in the Hida Gaien Belt,Japan: Implications for the Palaeozoic tectonic history of proto‐Japan

We report two new eclogite localities (at Kanayamadani and Shinadani) in the high‐P (HP) metamorphic rocks of the Omi area in the western most region of Niigata Prefecture, Japan, which form part of the Hida Gaien Belt, and determine metamorphic conditions and pressure–temperature (P–T) paths. The metamorphic evolution of the eclogites is characterized by a tight hairpin‐shaped P–T path from prograde epidote–blueschist facies to peak eclogite facies and then retrograde blueschist facies. The prograde metamorphic stage is characterized by various amphibole (winchite, barroisite, glaucophane) inclusions in garnet, whereas the peak eclogite facies assemblage is characterized by omphacite, garnet, phengite and rutile. Peak P–T conditions of the eclogites were estimated to be ~600°C and up to 2.0 GPa by conventional cation‐exchange thermobarometry, Ti‐in‐zircon thermometry and quartz inclusion Raman barometry respectively. However, the Raman spectra of carbonaceous material thermometry of metapelites associated with the eclogites gave lower peak temperatures, possibly due to metamorphism at different conditions before being brought together during exhumation. The blueschist facies overprint following the peak of metamorphism is recognized by the abundance of glaucophane in the matrix. Zircon grains in blueschist facies metasedimentary samples from two localities adjacent to the eclogites have distinct oscillatory‐zoned cores and overgrowth rims. Laser ablation inductively coupled plasma mass spectrometry U–Pb ages of the detrital cores yield a wide range between 3,200 and 400 Ma, with a peak at 600–400 Ma. In the early Palaeozoic, proto‐Japan was located along the continental margin of the South China craton, providing the source of the older population of detrital zircon grains (3,200–600 Ma) deposited in the trench‐fill sediments. In addition, subduction‐related magmatism c. 500–400 Ma is recorded in the crust below proto‐Japan, which might have been the source for the younger detrital zircon grains. The peak metamorphic age was constrained by SHRIMP dating of the overgrowth rims, yielding Tournaisian ages of 347 ± 4 Ma, suggesting subduction in the early Carboniferous. Our results provide clear constraints on the initiation of subduction, accretion and the development of an arc‐trench system along the active continental margin of the South China craton and help to unravel the Palaeozoic tectonic history of proto‐Japan.     

Salinity in Soils and Tsunami Deposits in Areas Affected by the 2010 Chile and 2011 Japan Tsunamis

The accumulation of data sets of past tsunamis is the most basic but reliable way to prepare for future tsunamis because the frequency of tsunami occurrence and their magnitude can be estimated by historical records of tsunamis. Investigation of tsunami deposits preserved in geological layers is an effective measure to understand ancient tsunamis that occurred before historical records began. However, the areas containing tsunami deposits can be narrower than the area of tsunami inundation, thus resulting in underestimation of the magnitude of past tsunamis. A field survey was conducted after the 2010 Chile tsunami and 2011 Japan tsunami to investigate the chemical properties of the tsunami-inundated soil to examine the applicability of tsunami inundation surveys considering water-soluble salts in soil. The soil and tsunami deposits collected in the tsunami-inundated areas are rich in water-soluble ions (Na⁺, Mg²⁺, Cl^?, Br^? and SO ₄ ^2? ) compared with the samples collected in the non-inundated areas. The analytical result that the ratios of Na⁺, Mg²⁺, Br^? and SO ₄ ^2? to Cl^? are nearly the same in the tsunami deposits and in the tsunami-inundated soil suggests that the deposition of these ions resulting from the tsunami inundation does not depend on whether or not tsunami deposits exist. Discriminant analysis of the tsunami-inundated areas using the ion contents shows the high applicability of these ions to the detection of tsunami inundation during periods when the amount of rainfall is limited. To examine the applicability of this method to palaeotsunamis, the continuous monitoring of water-soluble ions in tsunami-inundated soil is needed as a future study.     

Hydrothermal synthesis of pumpellyite–okhotskite series minerals

Summary ?Hydrothermal experiments to synthesize pumpellyite group minerals of the pumpellyite–okhotskite series and to investigate their stability have been carried out at 200, 300 and 400 MPa P _fluid and 250–500 °C by using cold-seal pressure vessels and solid buffers of MnO₂–Mn₂O₃, Cu₂O–CuO and Cu₂O–Cu buffer assemblages. Okhotskite and pumpellyite rich in the okhotskite component crystallized from an oxide mixture starting material of Ca₄MgMn³⁺ ₃Al₂Si₆O_24.5-oxide+excess H₂O at P _fluid of 200, 300 and 400 MPa and temperatures of 300 and 400 °C. However, a single phase of okhotskite was not produced, and associated piemontite, hausmannite, wollastonite, clinopyroxene, corundum, braunite–neltnerite solid solution and alleghanyite also formed. Mn-pumpellyite of the okhotskite–pumpellyite join occurs as aggregates of needle crystals, rounded grains or flaky crystals. Chemical compositions are variable and range from pumpellyite-(Mn²⁺) to okhotskite: 31–36 SiO₂, 13–21 Al₂O₃, 12–25 total Mn₂O₃, 0.6–4 MgO and 20–24 wt.% CaO. Reconnaissance experiments using a starting material of synthetic Ca₂Mn³⁺Al₂Si₃O₁₂(OH)-piemontite at 300 MPa and temperatures of 250, 300, 400 and 500 °C indicate that Mn-rich pumpellyite can crystallize from piemontite at lower temperatures than the stability field of piemontite. The Mn-rich pumpellyite was accompanied by garnet, wollastonite and alleghanyite. The chemical compositions of the Mn-pumpellyites are 32–36 SiO₂, 18–27 Al₂O₃, 8–18 total Mn₂O₃ and 20–23 wt.% CaO. This study shows that the stability fields of piemontite, piemontite+Mn-pumpellyite, and Mn-pumpellyite range in this order with decreasing temperature under high fO₂ conditions. The maximum stability temperature of Mn-rich pumpellyite lies between 400 and 500 °C at 200–400 MPa in high fO₂ conditions. Received March 3, 2000; revised version accepted December 28, 2001     

The stability and equation of state for the cotunnite phase of TiO2 up to 70 GPa

The stability and equation of state for the cotunnite phase in TiO₂ were investigated up to a pressure of about 70 GPa by high-pressure in situ X-ray diffraction measurements using a laser-heated diamond anvil cell. The transition sequence under high pressure was rutile → α-PbO₂ phase → baddeleyite phase → OI phase → cotunnite phase with increasing pressure. The cotunnite phase was the most stable phase at pressures from 40 GPa to at least 70 GPa. The equation of state parameters for the cotunnite phase were established on the platinum scale using the volume data at pressures of 37–68 GPa after laser annealing, in which the St value, an indicator of the magnitude of the uniaxial stress component in the samples, indicates that these measurements were performed under quasi-hydrostatic conditions. The third-order Birch-Murnaghan equation of state at K ₀′ = 4.25 yields V ₀ = 15.14(5) cm³/mol and K ₀ = 294(9), and the second-order Birch-Murnaghan equation of state yields V ₀ = 15.11(5) cm³/mol and K ₀ = 306(9). Therefore, we conclude that the bulk modulus for the cotunnite phase is not comparable to that of diamond.     

57Fe mössbauer study of synthetic Fe3+-melilites

Synthetic Fe³⁺-melilites containing NaCaFe³⁺-Si₂O₇-, Ca₂Fe³⁺AlSiO₇- or Sr₂Fe³⁺AlSiO₇-components have been studied by ⁵⁷Fe Mössbauer spectroscopy. The spectrum of åkermanite containing an NaCaFe³⁺Si₂O₇-component consists of one doublet identified to belong to Fe³⁺ in T1 sites. The spectra of åkermanite and gehlenite containing Ca₂Fe³⁺ AlSiO₇- or Sr₂Fe³⁺ AlSiO₇-component consist of two doublets. The inner and outer doublets are identified to belong to Fe³⁺ in the less distorted T1 and that in the more distorted T2 sites, respectively. The area ratios of the spectra show that the site occupancy of Fe³⁺ (T1) in gehlenite is less than that in åkermanite in which the distribution of Fe³⁺ in T1 and T2 sites is apparently random. The different distributions can be explained in terms of competition between minimizing the deficiency in the electrostatic valence and the preference of Al for T1 sites which the isomer shift measurements show to be more ionic.     

Development of density measurement for metals at high pressures and high temperatures using X-ray absorption imaging combined with externally heated diamond anvil cell

A technique for density measurement under high pressure and high temperature was developed using the X-ray absorption imaging method combined with an externally heated diamond anvil cell. The densities of solid and liquid In were measured in the pressure and temperature ranges of 3.2–18.6 GPa and 294–719 K. The densities obtained through the X-ray absorption imaging method were in good agreement (less than 2.0% difference) with those obtained through X-ray diffraction. Based on the measured density, the isothermal bulk modulus of solid In is determined as 48.0 ± 1.1?40.9 ± 0.8 GPa at 500 K, assuming K′ = 4 to 6. The compression curve of liquid In approaches that of solid In at higher pressures and does not cross over the solid compression curve in the measurement range. The present technique enables us to determine the densities of both solids and liquids precisely in a wide pressure and temperature range.     

Iron-water reaction at high pressure and temperature, and hydrogen transport into the core

We observed a direct reaction of metallic iron with water to form iron hydride and iron oxide, 3Fe + H₂O–>2FeH_x + FeO, at pressures from 6 GPa to 84 GPa and temperatures above 1,000 K in diamond anvil cell (DAC). Iron hydride is dhcpFeH_x or -FeH_x, and iron oxide has the rhombohedral or B1 structure at pressures at least up to 37 GPa. The formation of an assembly composed of dhcpFeH_x and FeO with the B8 structure was observed at 84 GPa. In primordial Earth, water formed by dehydration of the low temperature primitive materials reacts with metallic iron in the high temperature component to form iron hydride FeH_x and iron oxide FeO. The former would be incorporated in the iron forming the core. Thus hydrogen could be an important element of the Earths core. This reaction would be essential for transport of hydrogen into the core in the accretion stage of the Earth.     

Distribution of Fe among octahedral sites and its effect on the crystal structure of pumpellyite

Two pumpellyites with the general formula W ₈ X ₄ Y ₈ Z ₁₂O_56-n (OH) _n were studied using ⁵⁷Fe Mössbauer spectroscopic and X-ray Rietveld methods to investigate the relationship between the crystal chemical behavior of iron and structural change. The samples are ferrian pumpellyite-(Al) collected from Mitsu and Kouragahana, Shimane Peninsula, Japan. Rietveld refinements gave Fe(X):Fe(Y) ratios (%) of 41.5(4):58.5(4) for the Mitsu pumpellyite and 46(1):54(1) for the Kouragahana pumpellyite, where Fe(X) and Fe(Y) represent Fe content at the X and Y sites, respectively. The Mössbauer spectra consisted of two Fe²⁺ and two Fe³⁺ doublets for the Mitsu pumpellyite, and one Fe²⁺ and two Fe³⁺ doublets for the Kouragahana pumpellyite. In terms of the area ratios of the Mössbauer doublets and the Fe(X):Fe(Y) ratios determined by the Rietveld refinements, Fe²⁺(X):Fe³⁺(X):Fe³⁺(Y) ratios are determined to be 22:14:64 for the Mitsu pumpellyite and 27:8:65 for the Kouragahana pumpellyite. By applying the Fe²⁺:Fe³⁺-ratio determined by the Mössbauer analysis and the site occupancies of Fe at the X and Y sites given by the Rietveld method together with chemical analysis, the resulting formula of the Mitsu and Kouragahana pumpellyites are established as Ca₈(Fe _0.88 ²⁺ Mg_0.68Fe _0.77 ³⁺ Al_1.66)_Σ3.99(Al_5.67Fe _2.34 ³⁺ )_Σ8.01Si₁₂O_42.41(OH)_13.59 and Ca₈(Mg_1.24Fe _0.65 ²⁺ Fe _0.46 ³⁺ Al_1.66)_Σ4.01(Al_6.71Fe _1.29 ³⁺ )_Σ8.00Si₁₂O_42.14(OH)_13.86, respectively. Mean Y–O distances and volumes of the YO₆ octahedra increase with increasing mean ionic radii, i.e., the Fe³⁺→Al substitution at the Y site. However, change of the sizes of XO₆ octahedra against the mean ionic radii at the X site is not distinct, and tends to depend on the volume change of the YO₆ octahedra. Thus, the geometrical change of the YO₆ octahedra with Fe³⁺→Al substitution at the Y site is essential for the structural changes of pumpellyite. The expansion of the YO₆ octahedra by the ionic substitution of Fe³⁺ for Al causes gradual change of the octahedra to more symmetrical and regular forms.     

Structural variation of babingtonite depending on cation distribution at the octahedral sites

Babingtonite, Ca₂Fe²⁺Fe³⁺[Si₅O₁₄(OH)] (Z?=?2, space group $ P\overline{1} $ ) from Yakuki mine (Japan), Grönsjöberget (Sweden), Kandivali Quarry (India), Baveno Quarry (Italy), Bråstad Mine (Norway), and Kouragahana (Japan), and manganbabingtonite, Ca₂(Mn²⁺, Fe²⁺)Fe³⁺[Si₅O₁₄(OH)], from Iron Cap mine (USA) were studied using electron-microprobe analysis (EMPA), ⁵⁷Fe Mössbauer analysis and single-crystal X-ray diffraction methods to determine the cation distribution at M1 and M2 and to analyze its effect on the crystal structure of babingtonite. Although all studied babingtonite crystals are relatively homogeneous, chemical zonation due to mainly Fe ? Mn substitution is observed in manganbabingtonite. Mössbauer spectra consist of two doublets with isomer shift (I.S.)?=?1.16–1.22 mm/s and quadrupole splitting (Q.S.)?=?2.33–2.50 mm/s and with I.S.?=?0.38–0.42 mm/s and Q.S.?=?0.82–0.90 mm/s, assigned to Fe²⁺ and Fe³⁺ at the M1 and M2 octahedral sites, respectively. The determined ratio of Fe²⁺/total Fe in manganbabingtonite (0.26) was smaller than that in the others (0.35–0.44) because of high Mn²⁺ content instead of Fe²⁺. The unit-cell parameters of babingtonite are a?=?7.466–7.478, b?=?11.624–11.642, c?=?6.681–6.690 Å, α?=?91.53–91.59, β?=?93.86–93.94, γ?=?104.20–104.34º, and V?=?560.2–562.3 Å³, and those of manganbabingtonite are a?=?7.4967(3), b?=?11.6632(4), c?=?6.7014(2) Å, α?=?91.602(2), β?=?93.989(2), γ?=?104.574(3)º, and V =565.09(5) ų. Structural refinements converged to R ₁ values of 1.64–3.16 %. The <M1-O> distance was lengthened due to the substitution of large octahedral cations such as Mn²⁺ for Fe²⁺. The increase of the M1-O8, M1-O8’ and M1-O13 lengths with mean ionic radii is slightly more pronounced than of the other M1-Oi lengths. The lengthened M1-O13 distance leads the positive correlation between Si5-O15-Si1 angle and M1-O13 distance. The increase of Si2-O3-Si1 and Si5-O12-Si4 angles due to the increase of mean ionic radius of M2 is also observed.