Platinum-group mineral formation: Evidence of an interchange process from the entropy of activation values

Small grains of Ru–Os–Ir sulfides or alloys that formed in the early stages of the crystallization of basaltic magmas occur as inclusions in chromitites from many ophiolite complexes, Ural/Alaskan-type and layered intrusions. The nature of platinum-group elements is debated, i.e., whether they originally occurred in a metallic state or bonded with sulfur or other ligands. The application of kinetics and suggestions regarding the mechanisms of PGE formation may contribute to a better understanding of the genetic processes for platinum-group mineral (PGM) formation. The aim of the present study is to investigate the type of mechanism (associative, dissociative or interchange) and the possibility of direct formation of PGM from the reaction of free metals with sulfur, defining also the structure of possible intermediate species.The literature on the grain sizes (r) of platinum-group minerals (PGM) and their formation temperatures (range between 700 and 1100 °C) reveals an Arrhenius temperature dependence. The activation energy was estimated to be 450 ± 45 kJ mol⁻¹. Applying the Eyring equation to the same data, a linear relationship between 2.5ln(r) + ln(T) versus 1/T was obtained, leading to an estimation of the free energy of activation, ΔG^≠ = 440 ± 43 kJ mol⁻¹. The thermodynamic relation ΔG^≠ = ΔH^≠ − TΔS^≠, used together with the relation ΔΗ^≠ = E_act − RT leads to the calculation of ΔS^≠ at various temperatures. The estimated entropy of activation at various temperatures being almost zero, we suggest an interchange mechanism for PGM formation.The possibility of PGM formation from the direct reaction of free metals with sulfur would be inconsistent with the estimated entropy of activation values (ΔS^≠  0) at various temperatures. In the cases of PGMs of known r, the formation temperatures can be estimated, and then the free energy of activation obtained, applying 2.5ln(r) + ln(T) versus 1/T (straight line). From that value, the entropy of activation can be calculated [ΔS^≠ = −R + (E_act − ΔG^≠)/T], and an interchange mechanism is proposed. Furthermore, applying the relation of 2.5ln(r) + ln(T) versus 1/T on PGM grains of known r and T, an interchange mechanism for their formation can be suggested if they fit the above line.     

Cordierite gneisses and associated lithologies of the Guri area,Northwest Guayana Shield,Venezuela

Gneisses in the Guri area of the Venezuelan Guayana Shield contain mineral assemblages with cordierite, garnet, sillimanite, hypersthene, biotite and Fe-Ti oxide intergrowths.Analysis of mineral assemblages and compositional relationships in the light of experimental data indicate metamorphic conditions of 725–800° C, 5–6 kb P _T , <P _T for the highest grade rocks and 650–700° C, 5–7 kb P _T , approximating P _T for the lowest grade rocks. Oxygen fugacities in different lithologies ranged between those of the MH and QFM buffers.The distribution coefficient K _D (Mg-Fe) (gar-bio), decreases by 0.006 per atom percent increase in (Mn/Mn+Mg+Fe)gar, falls in the range of K _D typical of the sillimanite-K feldspar zone and granulite facies, and is systematically lower in lower grade rocks-all in accord with observation in other localities. K _D (Mg-Fe) (cord-bio) ranges from 3.0 in the highest grade rocks to 10.0 in the lowest grade rocks, appears independent of FeO/MgO of cordierite or biotite, and varies systematically with grade. In contrast with conclusions based on observation in other localities, data from the Guri area suggest -K_D(cord-bio) may be a sensitive index of grade.A number of mineralogic and geologic observations are difficultly reconciled with existing experimental data.     

Geochronological problems related to polymetamorphism in the Limpopo Complex, South Africa

The integration of new and published geochronologic data with structural, magmatic/anatectic and pressure–temperature (P–T) process information allow the recognition of high-grade polymetamorphic granulites and associated high-grade shear zones in the Central Zone (CZ) of the Limpopo high-grade terrain in South Africa. Together, these two important features reflect a major high-grade D₃/M₃ event at ~ 2.02 Ga that overprinted the > 2.63 Ga high-grade Neoarchaean D₂/M₂ event, characterized by SW-plunging sheath folds. These major D₂/M₂ folds developed before ~ 2.63 Ga based on U–Pb zircon age data for precursors to leucocratic anatectic gneisses that cut the high-grade gneissic fabric. The D₃/M₃ shear event is accurately dated by U–Pb monazite (2017.1 ± 2.8 Ma) and PbSL garnet (2023 ± 11 Ma) age data obtained from syntectonic anatectic material, and from sheared metapelitic gneisses that were completely reworked during the high-grade shear event. The shear event was preceded by isobaric heating (P = ~ 6 kbar and T = ~ 670–780 °C), which resulted in the widespread formation of polymetamorphic granulites. Many efforts to date high-grade gneisses from the CZ using PbSL garnet dating resulted in a large spread of ages (~ 2.0–2.6 Ga) that reflect the polymetamorphic nature of these complexly deformed high-grade rocks.     

A two-phase model for the description of the influence of cracks on the P- and S-wave velocities in dry and saturated rock samples

The premonitory variations of seismic-wave velocities before earthquakes originate from various cracking processes before the fracture. It can be shown that these variations are comparable with wave-velocity variations in porous model samples with defined pore sizes. Furthermore, it is possible to describe analytically the variation of wave velocities as a function of the parameter K₀, which describes the fracturing process, and a material/depth parameter AP. On the basis of the wave velocity vs. pressure curves of rocks, it is possible to determine K₀ and A. Using the material/depth parameter AP sediments in covering strata and eruptive rocks in regions of earthquakes of shallow to medium depth can be descirbed. A relationship between Δυ_D and ΔK₀ can be established. For acid to ultrabasic rocks, a variation of up to 2 km/s indicates a variation of K₀ of 0.1–1.0.Moreover, it is possible to establish a relationship between K₀ and the number as well as the mean length of cracks in the rock. The solutions differ depending on the cracks being closed or open. For closed cracks a wave-velocity minimum of 6% results. For oper cracks the variations of the number and mean length of cracks are taken into account by means of a stochastic process; the resulting variations of K₀ and the wave velocity car adequately explain the variations in seismic-wave velocity. Variations of the pore pressure have an influence on K₀and the wave velocity only under most favourable geologica conditions; generally they are insignificant. Also for S-wavc velocities and for the ratio υ_p/υ_s the wave velocity vs. pressure equations are valid; it is possible to state K₀ and A-values.     

Temperature-dependent distribution of Cr between olivine and pyroxenes in lherzolite xenoliths

The temperature effect on the exchange reaction Cr₂O₃(ol)=Cr₂O₃(px) was studied for coexisting olivine and both clino and ortho pyroxenes. The distribution of Cr between olivine and clinopyroxene in 31 coarse garnet lherzolites and 10 porphyroclastic garnet lherzolites from kinberlites, and in 17 coarse spinel lherzolites from basalts, obeys a van't Hoff relation (c.f. Stosch 1981) with the Wells two-pyroxene temperature: T(Kelvin)=8,787 (In D _Cr+ 2.87) where D _Cr(opx/ol)=wt.% Cr(clinopyroxene)/Cr(olivine). An analogous exchange for olivine and orthopyroxene with 0.7–1.6 wt.% Al₂O₃ in 41 garnet lherzolites from kimberlites shows considerable scatter about the following relation: T(Kelvin)=5,540/(ln D _cr+1.86) where D _cr(opx/ol)= wt.% Cr(orthopyroxene)/Cr(olivine). Spinel lherzolites and a garnet lherzolite from the Malaita alnöite do not obey the second relation. For orthopyroxene with 2.5–5.1 wt.% Al₂O₃, D _cr(opx/ol) is 1.7 to 3 times higher, and for 0.1 wt.% Al₂O₃ is 2 times lower than for the garnet lherzolites. Experimental calibration is needed, especially to check the possible effect of Al on D _cr(opx/ol).     

Diffusive transport of water in porous feldspars from granitic saprolites: In situ experiments using FTIR spectroscopy

A novel experimental cell was developed for in situ measurements of transport phenomena in porous media using Fourier-Transform Infrared (FTIR) Spectroscopy. The technique was employed at ambient pressure in the temperatures range of 11–44 °C to study the H₂O → D₂O exchange between water-saturated weathered feldspars (bulk porosity of 5–19 vol% for feldspar) from granitic saprolites and a surrounding aqueous liquid. Such measurements are an important step for understanding internal weathering reactions of feldspars in soils and aquifers. Effective diffusion coefficients D_eff for water in water-saturated porous feldspars were determined assuming one-dimensional diffusion in a quasi-homogeneous medium. The values of D_eff vary from 7.2 × 10⁻¹⁰ to 1.9 × 10⁻¹¹ m²/s and are 1–2 orders of magnitude lower than the diffusion coefficients (D) of protons and molecular H₂O in liquid water. The activation energy for the H₂O → D₂O exchange process in porous feldspars ranges from 7.8 to 18.8 kJ/mol.The results imply that the effective diffusivity of water is mainly controlled by physical properties of the feldspars like porosity, pore connectivity, pore geometry and distribution. Perthitic feldspars with homogeneous pore distribution in the albitic lamellas have diffusional tortuosity factors X = D/D_eff between 3 and 10 while alkali feldspars with inhomogeneously distributed and disconnected pores have much higher X values up to 129. Diffusion anisotropy has been verified for a vein perthite with diffusion perpendicular to the lamellas being faster by 0.3–0.5 log units than within the lamellas. It has to be emphasized that the study is based only on few selected feldspars, including perthitic feldspar, and additional work on samples with different weathering stages is needed to test the importance of the different parameters controlling diffusive transport in the pore system.     

Long-term prediction of intermediate depth earthquakes in the southern Aegean region based on a time-predictable model

Repeat times of strong intermediate depth (60 km h 180 km) earthquakes have been determined by the use of instrumental and historical data for six seismogenic sources in the Benioff zone of the southern Aegean area. For four of these sources, at least two interevent times (three mainshocks) are available for each source. By using the repeat times for these four sources, the following relation has been determined: logT _t = 0.20M _min + 0.19M _p +a, whereT _t is the repeat time (in years),M _min the surface wave magnitude of the smallest earthquake considered,M _p the magnitude of the preceding mainshock and a parameter which varies from source to source. A multilinear correlation coefficient equal to 0.91 was determined for this relation, which indicates that the time predictable model holds to a satisfactory degree for the strong mainshocks of intermediate focal depth in the southern Aegean.By assuming that the ratioT/T _t, whereT is the observed andT _t the calculated repeat time, follows a lognormal distribution, the conditional probabilities for the occurrence of strong (M _s 6.5) and very strong (M _s 7.5) earthquakes during the period 1991–2001 in these four seismogenic sources have been calculated. These probabilities are very high (P > 0.9) for the strong and high (P > 0.5) for the very strong intermediate depth earthquakes which occur in the three sources of the shallower (h < 100 km) part of the Benioff zone where coupling occurs between the front parts of the Mediterranean lithosphere (downgoing) and the Aegean lithosphere.     

Neoproterozoic subductions and differential exhumation of western Hoggar (southwest Algeria): new structural, petrological and geochronological evidence

The western terranes exposed east of the Pan-African suture in western Hoggar (southwest Algeria), are reexamined in the light of new structural, petrologic and by the ⁴⁰Ar/³⁹Ar laser probe data on metamorphic micas and amphiboles. To the north, the Tassendjanet nappe includes the Paleoproterozoic basement, its Mesoproterozoic cover and mafic rocks representing the roots of a ca. 680 Ma arc overlain by Late Neoproterozoic andesites and volcanic greywackes. The nappe preserved at rather shallow crustal level in the east was emplaced southward (D_1a) to southeastward (D₂). In the south, two metamorphic suites are distinguished. The Tideridjaouine–Tileouine high-pressure metamorphic belt (T=550–600 °C, P=1.4–1.8 GPa) represents a slab of subducted continental material exposed along the western edge of the In Ouzzal granulite unit interpreted as a microcontinent. Differential exhumation of tectonic slices from the high-pressure belt occurred around 615–600 Ma through a system of west-directed recumbent folds (D_1b). The Egatalis high grade belt in the west was intruded by syn-metamorphic gabbro–norite bodies. It includes unretrogressed low-pressure granulite facies rocks (T around 750–800 °C, P0.45 GPa) cooled at a rate of 15°/m.y. between 600 and 580 Ma, and followed by the emplacement of several late-kinematic granitic plutons. Final exhumation of the low-pressure, high-temperature metamorphic rocks, that are not found as pebbles in the molasse, took place in the Late Cambrian. The early and relatively fast cooling of the high-pressure and high-temperature metamorphic rocks of the southern part of the Tassendjanet terrane is at variance with the slow cooling of central Hoggar where repeated magmatic activity as young as Late Cambrian occurred [Lithos 45 (1998) 245].     

Raman spectroscopy and heat capacity measurement of calcium ferrite type MgAl2O4 and CaAl2O4

Raman spectroscopy of calcium ferrite type MgAl₂O₄ and CaAl₂O₄ and heat capacity measurement of CaAl₂O₄ calcium ferrite were performed. The heat-capacity of CaAl₂O₄ calcium ferrite measured by a differential scanning calorimeter (DSC) was represented as C_P(T)=190.6–1.116 × 10⁷T^–2 + 1.491 × 10⁹T^–3 above 250 K (T in K). The obtained Raman spectra were applied to lattice dynamics calculation of heat capacity using the Kieffer model. The calculated heat capacity for CaAl₂O₄ calcium ferrite showed good agreement with that by the DSC measurement. A Kieffer model calculation for MgAl₂O₄ calcium ferrite similar to that for CaAl₂O₄ calcium ferrite was made to estimate the heat capacity of the former. The heat capacity of MgAl₂O₄ calcium ferrite was represented as C_P(T)=223.4–1352T ^–0.5 – 4.181 × 10⁶T ^–2 + 4.300 × 10⁸T ^–3 above 250 K. The calculation also gave approximated vibrational entropies at 298 K of calcium ferrite type MgAl₂O₄ and CaAl₂O₄ as 97.6 and 114.9 J mol^–1 K^–1, respectively.     

Tsunami magnitudes in Taiwan, the Philippines and Indonesia

The regional characteristics of tsunami magnitudes in the SE Asia region are discussed in relation to earthquake magnitudes during the period from 1960 to 1994. Tsunami magnitudes on the Imamura-Iida scale are investigated by the author's method (Hatori 1979, 1986) using the data of inundation heights near the source area and tide-gauge records observed in Japan. The magnitude values of the Taiwan tsunamis showed relatively to be small. On the contrary, the magnitudes of tsunamis in the vicinities of the Philippines and Indonesia exceed more than 1–2 grade (tsunami heights: 2–5 times) compared to earthquakes with similar size on the circum-Pacific zone. The relation between tsunami magnitude, m, and earthquake magnitude, M _s, is expressed as m = 2.66 M _s– 17.5 for these regions. For example, the magnitudes for the 1976 Mindanao tsunami (M _s= 7.8, 3702 deaths) and the 1992 Flores tsunami (M _s= 7.5, 1713 deaths) were determined to be m = 3 and m = 2.5, respectively. The focal depth of tsunamigenic earthquakes is shallower thand< 36 km, and the detectively of tsunamis is small for deep earthquakes being d > 40 km. For future tsunamis, it is indispensable to take precautions against shallow earthquakes having the magnitudes M _s> 6.5.     

Comparison between thermal–viscous coupling and frictional sliding

We investigated the similarity between thermal–viscous coupling (TVC) and frictional sliding, proposed by Kameyama and Kaneda [Pure Appl. Geophys. 159 (2002) 2011]. We consider a one-dimensional layer composed of viscous material, which is sandwiched and sheared by two thick elastic layers. The rate of viscous deformation depends on the temperature T_c in the viscous layer as well as shear stress τ. The temperature T_c changes owing to heating by viscous dissipation and conductive cooling. We carried out velocity-stepping tests for the steady-state deformation both numerically and analytically, and compared the temporal evolution of small perturbations with that of the spring-block model with rate- and state-dependent friction (RSF). We found that, as is the case of frictional slip stability, the manner of temporal evolution is classified into four regimes depending on whether it is stable or not and whether it is monotonous or oscillatory with time. By further interpreting TVC in terms of general RSF theory by Ruina [J. Geophys. Res. 88 (1983) 10359], we obtained the relations between the parameters appearing in the phenomenological RSF law and the nondimensional parameters which characterize the nature of TVC. A further improvement of this approach might be important for estimating the actual values of frictional constitutive parameters at the deeper portion of seismogenic faults of interplate or inland earthquakes where a ductile deformation is expected to be significant.     

On the assessment of maximum earthquakes in the alps and adjacent areas

Strong tectonic earthquakes within the crust always occur on already existing faults, and they have the property of a shear rupture. Such earthquakes with surface-wave magnitudes M < 7 obviously have a geometric similarity. Because of this similarity and the validity of the Gutenberg and Richter's energy—magnitude relation, the expression M = 2 log₁₀ L + const., with L = focal length, is valid.The expression L_maxL^* for the maximum focal length, is also valid if L^* is the length of the rectilinear extent of the seismic line on which the maximum earthquake occurs. The bounds of L^* may be given by sharp bends and/or by traversing deep faults. Thus the maximum imaginable earthquake on a seismic line with the length L^* has the magnitude M_max = 2 log₁₀ L^* + const.For the investigated region — the Alps and adjacent areas — from the data of recent and historical strong earthquakes, it follows that M_max = 2 log₁₀ L^* + 1.7, if L^* is measured in kilometres. These limiting values lie in the centre-field of the magnitude range for maximum earthquakes, published by Shebalin in 1970. By the aid of this equation it is also possible to assess the upper limiting value of the accompanying maximum scale intensity.     

Internally-consistent geothermometry and H2O barometry in metamorphic rocks: The example garnet-chlorite-quartz

Temperature and H₂O activity can be determined with high precision using metamorphic mineral assemblages that define both a dehydration equilibrium and a temperature-sensitive cation-exchange equilibrium. Such determinations are obtained by applying the Gibbs method and then integrating two resulting differential equations, as illustrated here for the assemblage garnet-chlorite-quartz. The first equation, a geothermometer that monitors temperature based upon Fe–Mg exchange between garnet and chlorite, was calibrated using rocks at Pecos Baldy, New Mexico: 0=0.05 P(bars)–19.02 T(K)+4607 ln K _D+24,156 with errors of ±8°C based upon analytical precision. The second equation monitors differences in the activity of water between specimens (1) and (2): 0=(0.1 X _{Mg–chl, 1} – 2.05)(P ₂ – P ₁) +[–33.02+5.96 ln(X _{Fe–chl, 1}/X _{alm, 1})][T ₂–T ₁ –2.67 RT ₁ln[a(H₂O)₂/a(H₂O)₁] +5.96 T ₁ln(X _{Fe–chl, 2} X _{alm, 1}/X _{Fe–chl, 1} X _{alm, 2}).For samples equilibrated at the same pressure and temperature, microprobe analytical errors of 1% limit precision to ±0.01 a(H₂O). For samples equilibrated at the same pressure but variable temperature, uncertainty of ±8°C limits precision to ±0.06 a(H₂O). Extreme presure sensitivity requires that the H₂O-barometer be applied only to rocks where pressure gradients are absent or well-constrained. The geothermometer gives temperatures in agreement with two other garnet-chlorite geothermometers (Dickenson and Hewitt 1986; Ghent et al. 1987) and with garnet-biotite geothermometry (ferry and Spear 1978) over the temperature range 350–520°C. Application of the relative H₂O barometer shows variations in the activity of water approaching 0.30 in several study areas. Either pelitic schists commonly equilibrate with a fluid that is not pure H₂O, or some pelitic rocks undergo metamorphism in the absence of a free fluid phase.     

Correlation Fractal and Multifractal Characteristics of Seismic Activity in the Taiwan Area, China

Based on the analysis of newly collected data of plate tectonics, distribution of active faults and crustal deformation, the Taiwan area is divided into two seismic regions and six seismic belts. Then, correlation fractal dimensions of all the regions and belts are calculated, and the fractal characteristics of hypocenteral distribution can be quantitatively analyzed. Finally, multifractal dimensions Dq and f(α) are calculated by using the earthquake catalog of the past 11 years in the Taiwan area. This study indicates that (1) there exists a favorable corresponding relationship between spatial images of seismic activity described with correlation fractal dimension analysis and tectonic settings; (2) the temporal structure of earthquakes is not single but multifractal fractal, and the pattern of Dq variation with time is a good indicator for predicting strong earthquake events.     

Kinetics of high-pressure phase transformations: Implications to the evolution of the olivine → spinel transition in the downgoing lithosphere and its consequences on the dynamics of the mantle

The rate of a high-pressure phase transition increases exponentially with temperature (T) and overpressure or pressure beyond equilibrium (ΔP). It is also greatly promoted by introducing shear stress, diminishing grain size, and adding water or other catalysts to the reactants. For an isothermal and isobaric transition with no compositional change, if steady state of nucleation on grain surfaces is attained, the rate equation can be expressed: (1) before site saturation by: X = 1 − exp(−Kt⁴), where

Full-size image (2K)

and (2) after site saturation by: X = 1 − exp(−K′T), where

Full-size image (1K)

, where X is volume fraction of completion of transformation, t is time, and the C's are characteristic constants. C₁ and C₉ are functions of grain size, C₃ and C₆ are functions of shear stress. All the C's are almost independent of temperature and pressure. Thus, if X as a function of T, ΔP, and t over a narrow P-T range can be experimentally determined, the C's can be calculated and the effect of grain size and shear stress on the rate of transformation can be evaluated. The isothermal and isobaric rate equations for a given composition, shear stress, and grain size are then experimentally determinable. The non-isothermal and non-isobaric rate equation can be calculated from the isothermal and isobaric ones if the rate of penetration into the metastability field is known. The important feature of the kinetics of high-pressure phase transitions predicted by these rate equations is that for a given rate of penetration into the metastability field, there can be defined a characteristic temperature, T_ch, below which the rate of the transition is virtually zero no matter how metastable the material is. For the olivine → spinel transition in the mantle, this characteristic temperature may be as high as 700° C. Thus, in a fast moving downgoing slab, the temperature at its cold center may remain below T_ch even down to depths in excess of 600 km, thereby greatly depressing the olivine—spinel phase boundary.At an early stage in the development of a downgoing slab, the plunging speed is slow. This allows the interior of the slab to heat up and the olivine → spinel transition to proceed rapidly and near equilibrium. As a result, the olivine—spinel phase boundary in the slab will be distorted upwards. The rising of the denser spinel phase then provides an additional driving force which accelerates the plate. Since the upper portion of the slab is pulled from below and the lower portion pushed from above, earthquakes of down-dip extension will occur in the upper mantle while those of down-dip compression will originate in the transition zone. Because the transformation occurs close to equilibrium, there will be an aseismic region separating the two seismic zones. When the plate velocity exceeds a certain limit, the temperature in the cold interior becomes low enough to depress the olivine → spinel transition. The phase boundary is then distorted downwards. The buoyant force thereby created will reduce the driving force, and the plunging speed of the plate will approach a steady state. In addition, the buoyant force will compress the slab from below and result in earthquakes of down-dip compression throughout the length of the slab. Now the olivine → spinel transition is so far from equilibrium that the reaction becomes implosive. A rise in frequency of deep earthquakes towards the implosion region in the lower transition zone is thus predicted. Therefore, as well as stabilizing the plate velocity, the olivine → spinel transition may also control earthquake distributions throughout the downgoing slab.     

Genetic significance of fluid inclusions in the CSA Cu–Pb–Zn deposit, Cobar, Australia

CSA mine exploits a ‘Cobar-type’ Cu–Pb–Zn±Au±Ag deposit within a cleaved and metamorphosed portion of the Cobar Supergroup, central New South Wales. The deposit comprises systems of ‘lenses’ that encompass veins, disseminations and semi-massive to massive Cu–Pb–Zn ores. The systems and contained lenses truncate bedding, are approximately coplanar with regional cleavage and similarly oriented shear zones and plunge parallel to the elongation lineation. Systems have extreme vertical continuity (>1000 m), short strike length (400 m) and narrow width (100 m), exhibit vertical and lateral ore-type variation and have alteration haloes. Models of ore formation include classical hydrothermalism, structurally controlled remobilisation and polymodal concepts; syntectonic emplacement now holds sway.Fluid inclusions were examined from quartz±sulphide veins adjacent to now-extracted ore, from coexisting quartz–sulphide within ore, and from vughs in barren quartz veins. Lack of early primary inclusions precluded direct determination of fluids associated with D₂–D₃ ore and vein emplacement. Similarly, decrepitation (by near-isobaric heating) of the two oldest secondary populations precluded direct determination of fluid phases immediately following D₂–D₃ ore and vein emplacement. Post-decrepitation outflow (late D₃ to early post-D₃) is recorded by monophase CH₄ inclusions. Entrained outflow of deeply circulated meteoric fluid modified the CH₄ system; modification is recorded by H₂O+CH₄ and H₂O+(trace CH₄) secondary populations and by an H₂O+(trace CH₄) primary population. The contractional tectonics (D₂–D₃) of ore emplacement was superseded by relaxational tectonics (D_4P) that facilitated meteoric water penetration and return flow.Under D₂ prograde metamorphism, entrapment temperatures (Tt) and pressures (Pt) for pre-decrepitation secondary inclusions are estimated as Tt300–330 °C and Pt1.5–2 kbar≈Plith (the lithostatic pressure). Decrepitation accompanied peak metamorphism (T350–380 °C) in mid- to late-D₃, while in late-D₃ to early post-D₃, essentially monophase CH₄ secondary inclusions were entrapped at Tt350 °C and Pt=1.5–2 kbar≈Plith. Subsequently, abundant CH₄ and entrained meteoric water were entrapped as H₂O+CH₄ secondaries under slowly decreasing temperature (Tt330–350 °C) and constant pressure (Pt1.5–2 kbar). Finally, with increasingly dominant meteoric outflow, H₂O+(trace CH₄) populations record decreasing temperatures (Tt>300 to <350 down to 275–300 °C) at pressures of Phydrostatic<Pt (1 kbar) <Plith (1.5 kbar).The populations of inclusions provide insight into fluid types, flow regimes and P–T conditions during parts of the deposit's evolution. They indirectly support the role of basin-derived CH₄ fluids in ore formation, but provide no insight into a basement-sourced ore-forming fluid. They fully support post-ore involvement of meteoric water. The poorly constrained entrapment history is believed to span 10 Ma from 395 to 385 Ma.     

Evaluation of the uncertainty in estimation of metal resources of skarn tin in Southern China

This study is concerned with the problem of how many undiscovered mineral deposits can be expected to occur in the vicinity of any known deposit, especially if the deposit is nearly mined out. Skarn tin deposits in southern China were chosen to demonstrate that fractal modeling can be a useful tool to characterize the spatial–temporal distribution of mineral deposits, and to quantify their grades and tonnages. The results show that the spatial–temporal distribution of skarn tin deposits as well as their grades and tonnages satisfy fractal statistic, and suggest that 14 skarn tin deposits could be found around a known skarn tin deposit within a radius of 80 km. Monte Carlo simulation was used to combine the number of deposits and the frequency distributions of grade and tonnage and to capture the uncertainty in estimation of metal resources. At the 90%, 50% and 10% confidence levels, tin metal resources amount to 6 ton, 200 ton, and 1.0 × 10⁴ ton around a known tin deposit within a radius of 80, respectively.     

Stress fields and fault reactivation angles of the 2000 western Tottori aftershocks and the 2001 northern Hyogo swarm in southwest Japan

We estimated the stress fields of the aftershocks of the 2000 western Tottori earthquake (M_w 6.6) and the northern Hyogo swarm (max M_w 5.2) by a stress tensor inversion of moment tensor solutions reported from the National Research Institute for Earth Science and Disaster Prevention (Japan). The maximum principal stress direction of the western Tottori sequence was estimated as N107°E with a strike–slip regime. In the northern Hyogo swarm, the orientations of the principal stress directions could not be well constrained by the observed data, but after examining the detailed characteristics of the solution, we obtained a most probable solution of N113°E for the σ₁ direction. These solutions are consistent with the maximum horizontal directions roughly estimated from the strike directions of large earthquakes occurring geographically between these two seismic activities. We measured the angle between each fault–slip direction and maximum principal stress direction to investigate the frictional properties of earthquakes. The distribution of the angles was forward modeled to estimate the coefficient of friction and the stress ratio, assuming uniformly distributed fault orientations. For the western Tottori sequence, a homogeneous stress field with a coefficient of friction less than 0.4 was estimated. A high stress level was also suggested because very little change occurred in the stress field during the mainshock. For the northern Hyogo sequence, the coefficient of friction was estimated to be between 0.5 and 1.0.     

Migration of large earthquakes along the great fault zones in Middle Asia

An analysis of the distribution (both spatial and temporal) of large earthquakes (M 6.5) along the Gissar—Kokshaal and the Hindu-Kush—Darvaz—Karakul fault zones in Middle Asia has revealed the linear character of migration from the ends to the centre of the Pamir arcs at a rate of 1–2 km/year to 3–6 km/year. Migration of large earthquakes at a similar rate has also been found in some of the other great fault zones. An attempt has been made to evaluate the duration of a migration cycle.The regularity found, although it needs further confirmation, has been used to tentatively predict the possible sites of future large earthquakes likely to occur in the present century.     

Deformation features within an active normal fault zone in carbonate rocks: The Gubbio fault (Central Apennines, Italy)

The Gubbio fault is an active normal fault defined by an important morphological scarp and normal fault focal mechanism solutions. This fault truncates the inherited Miocene Gubbio anticline and juxtaposes Mesozoic limestones in the footwall against Quaternary lacustrine deposits in the hanging wall. The offset is more than 2000 m of geological throw accumulated during a poly-phased history, as suggested by previous works, and has generated a complex zone of carbonate-rich fault-related structures. We report the results of a multidisciplinary study that integrates detailed outcrop and petrographic analysis of two well-exposed areas along the Gubbio fault zone, geochemical analysis (fluid inclusions, stable isotopes, and trace elements) of calcite-sealed fault-related structures and fault rocks, and biostratigraphic controls. Our aims are: (i) the characterization of the deformation features and their spatial–temporal relationships, and (ii) the determination of the P/T conditions and the fluid behaviour during deformation to achieve a better understanding of fluid–rock interaction in fault zones.We show that few of the observed structures can be attributed to an inherited shortening phase while the most abundant structures and fault rocks are related to extensional tectonics. The outcropping extensional patterns formed at depths less than 2.5–3 km, in a confined fluid system isolated from meteoric water, and the fault structures are the response to a small amount of cumulated displacement, 12–19% of the total geological throw.