Determination of the oxidation state of radiogenic Pb in natural zircon using X-ray absorption near-edge structure

We examined the L_III-edge Pb X-ray absorption near-edge structure (XANES) of three natural zircon samples with different amounts of radiation doses (1.9 × 10¹⁵ to 6.8 × 10¹⁵ α-decay events/mg). The results suggest that the oxidation state of radiogenic Pb in the zircon sample with the highest radiation dose is divalent. The XANES spectra of the two other samples with lower radiation doses suggest that radiogenic Pb(II) is present, and further that some Pb may be tetravalent. This is the first work on the determination of the oxidation state of radiogenic Pb in natural zircon using XANES.     

Instability of a highly reducing atmosphere on the primitive Earth

The eddy diffusion coefficient in the primitive upper atmosphere of highly reducing type (CH₄H₂) is estimated to be of the order of 10⁸ cm²sec^?1 or a little less, by solving the dissipation equation of internal gravity waves. Such a strong atmospheric mixing is clearly inconsistent with the previous assumption by McGovern that photochemical equilibrium was established in the upper atmosphere. By taking into account the mixing effect, the exospheric temperature of the highly reducing atmosphere has been computed to be higher than 1300°K. The result indicates that the hypothetical reducing atmosphere might have disappeared, if it existed, in a short time due to the gravitational escape of hydrogen and, consequently, that an anoxygenous but non-reducing atmosphere might be a more plausible environment for the origin of life.     

Application of the sphalerite geobarometer to some skarn-type ore deposits

Based on the equation recently determined, formation pressures of skarn-type ore deposits were estimated from the composition of sphalerite coexisting with pyrite and hexagonal pyrrhotite. As criteria for equilibrium among sphalerite, pyrite and hexagonal pyrrhotite, the following three points were carefully checked on each specimen: 1) the presence of hexagonal pyrrhotite, 2) no time sequences among the formation of sulfide minerals, and 3) no compositional variation in sphalerite. Most of the Cu-Fe skarn deposits studied were formed under pressures of more than 1 kb, whereas Zn-Pb(-Cu-Fe) deposits tend to have formed at relatively shallow environments, namely under less than 1 kb. The calculated pressures are qualitatively consistent with the depth of formation of deposits estimated from the geological evidences. The sphalerite geobarometry is quite sensitive even at low pressure ranges, and it is applicable to the deposits formed under shallow conditions.     

Rare earth elements in garnets and clinopyroxenes from garnet lherzolite nodules in kimberlites

Six pairs of coexisting garnets and clinopyroxenes were separated from the sheared and granular garnet lherzolite nodules in kimberlites and analyzed for rare earth elements (REE). The sheared and granular nodules can be distinguished in terms of REE pattern of both clinopyroxene and garnet. However, there are no significant differences in REE partitioning between clinopyroxene and garnet, indicating that the partitioning may be insensitive toP, T and composition. REE partition coefficients between garnet and liquid were estimated by using clinopyroxene-liquid partition coefficients found in the literature and clinopyroxene-garnet partitioning reported here. The estimated values agree with those reported by Philpotts et al. (1972). The estimated whole-rock REE pattern for the sheared nodules is similar to a chondritic pattern suggesting that the sheared nodules appear to be close to the primary mantle material. The REE data suggest that the granular nodules were originally garnet-free assemblages equilibrated with kimberlitic or nepheline-melilite basalt-like liquid, and later recrystallized as a garnet lherzolite assemblage.     

Rare earth element concentrations in a suite of basanitoids and alkali olivine basalts from Grenada,Lesser Antilles

A suite of basanitoids and alkali olivine basalts from Grenada, Lesser Antilles were analyzed for rare earth elements. The REE concentrations of these rocks are characterized by a small variation in the heavy REE (7 to 9 times chondrite) and a large variation in the light REE (17 to 93 times chondrite). Among the possible mechanisms to account for the REE variations, fractional crystallization processes at low and high pressures, and partial melting processes (both batch melting and fractional melting) were examined, using the partition relationships of REE among silicate minerals and melts. It is suggested that the observed REE variations are best explained by variable degrees of batch partial melting, in which garnet is present as one of the solid phases through 2 to 17% melting of a garnet lherzolite parent rock.     

Overview of the MITI Nankai Trough Wells: A Milestone in the Evaluation of Methane Hydrate Resources

Abstract. Bottom-simulating reflectors suggestive of the presence of methane hydrates are widely distributed below the ocean floor around Japan. In late 1999, drilling of the MITI Nankai Trough wells was conducted to explore this potential methane hydrate resource and a Tertiary conventional structure. The wells are located in the Northwest Pacific Ocean off Central Japan at a water depth of 945 m. A total of six wells were drilled, including the main well, two pilot wells, and three post survey wells at intervals of 10–100 m. All wells except the first confirmed the occurrence of hydrates based on logging-while-drilling, wire-line logging and/or coring using a pressure and temperature coring system in addition to conventional methods. Based on the various well profiles, four methane hydrate-bearing sand-rich intervals in turbidite fan deposits were recognized. Methane hydrates fill the pore spaces in these deposits, reaching saturation of up to 80 % in some layers. The methane hydrate-bearing turbiditic sand layers are less than 1 m thick, with a total thickness of 12–14 m. The bottom depth of high hydrate concentration correlates well with the depth of the bottom-simulating reflector. Based on these exploration results, the Japanese government inaugurated a 16-year methane hydrate exploitation program in 2001.     

Sulfur Isotope Geochemistry of the Supergiant Xikuangshan Sb Deposit, Central Hunan, China: Constraints on Sources of Ore Constituents

Abstract. The supergiant Xikuangshan Sb deposit is located in the Middle to Upper Devonian limestone of central Hunan, China. Primary ores are composed of early-stage stibnite and calcite with rare pyrite, early main-stage stibnite and quartz, and late main-stage stibnite and calcite. New sulfur isotope data reveal the clustering of δ³⁴S values (+5 ∼ +8 %) for both early and late main-stage stibnite; a single early-stage stibnite exhibits δ³⁴S value (+7.5 %) identical to its main ore-stage counterparts and the coexisting calcite has almost unmodified carbon isotope composition (-4.4 %). The data suggest a probable common source of sulfur for stibnite that was deposited at different paragenetic stages. A much wider variation in δ³⁴S values for early main-stage stibnite (+3.5 to +16.3 %, av. +7.5 %) compared to that for late main-stage stibnite (+5.3 to +8.1 %, av. +6.2 %) can be interpreted to be due to local interaction of earlier ore fluid with Devonian host rocks. The previous studies show that the Precambrian basement contains elevated Sb concentrations, and two distinctive sulfur reservoirs with δ³⁴S_pyrite values at ca. +11 ∼ +24 % and -7.0 ∼-11 %. The homogenizing effect for sulfur hydrothermally leached from the two reservoirs might have provided ore constituents for the Xikuangshan fluids.     

Element partitioning between metallic liquid, silicate liquid, and lower-mantle minerals: implications for core formation of the Earth

We determined the partition coefficients of 19 elements between metallic liquid and silicate liquid at 20 GPa and 2500°C, and between metallic liquid and silicate perovskite at 27 GPa and 2200°C. Remarkable differences were observed in the partitioning behaviors of Si, P, W, Re, and Pb among the silicate liquid, perovskite, and magnesiowüstite coexisting with metallic liquid, reflecting incompatibility of the elements in the silicate or oxide phase. We could not observe any significant difference in the partitioning behaviors of V, Cr, Mn, Co, Ni, and Cu among the phases coexisting with metallic liquid.

Comparison of the present partitioning data with those obtained previously at lower pressure and temperature suggests that the exchange partition coefficients, K_met/sil, of Co, Ni, Mo, and W decrease, whereas those of V, Cr, and Mn increase and tend to approach unity with increasing pressure and temperature. We also made preliminary experiments to clarify the effect of sulfur on the partitioning behaviors. Sulfur lowers the exchange partition coefficients, K_met/sil, of Mo and W between metallic liquid and silicate liquid significantly at 20 GPa and 2300°C.

The mantle abundances of Co, Ni, Cu, Mo, and W calculated for the metal-silicate equilibrium model are lower than those of the real mantle, whereas P, K, and Mn are overabundant in the calculated mantle. The discrepancies in the abundances of Co and Ni could be explained by the chemical equilibrium at higher pressure and temperature. Large discrepancies in Mo and W between the calculated and real mantles could be accounted for by the effect of sulfur combined with the effects of pressure and temperature on the chemical equilibrium. The mantle abundances of P, K, and Cu could be accounted for by volatile loss in the nebula, perhaps before accretion of the Earth, combined with the chemical equilibrium at higher pressure and temperature. Thus the observed mantle abundances of P, K, Co, Ni, Cu, Mo, and W may be consistent with a model of sulfur-bearing metal-silicate equilibrium in lower-mantle conditions.     

The effective failure modes and stability of slopes in rock mass with two discontinuity sets

Summary The stability of rock slopes in discontinuous rock mass associated with the construction of power plants, highways and open pits is always of paramount importance during the lifetime of these structures. The likely forms of instabilities observed in the excavation of rock slopes and some mathematical methods for the stability analyses are well documented in literature. Since most of the mathematical approaches used are based on the limiting-equilibrium concept, there seems a need to check the validity of these approaches under some controlled conditions. In this paper, the authors describe methods for the stability of a blocky column and discontinuous rock slopes derived on the basis of dynamic equilibrium equations and compare the results calculated according to the developed method with those of experiments on model blocky columns and model slopes in the laboratory. Test results confirm that the limiting equilibrium approache is valid and an effective way of dealing with the stability problems in discontinuous rock mass as long as the likely forms of instability are properly treated in these approaches.