Fractionation mechanism of stable isotope in evaporating water body

Under Rayleigh equilibrium condition, stable isotopic ratio in residual water increases with the decrease of the residual water proportion f exponentially, and the fractionation rate of stable isotopes is inversely proportional to temperature. However, under kinetic evaporation condition, the fractionation of stable isotopes is not only related to the phase temperature but also influenced by the atmospheric humidity and the mass exchange between liquid and vapor phases. The ratio δ in residual water will not change with f after undergoing evaporation of a long time for great relative humidity. The rate that the evaporating water body reaches isotopic steady state is mainly dependent on the relative humidity in atmosphere. The analysis shows that the actual mean linear variety rates, about -30.0, of the δ18O in residual water versus the residual water proportion at Nagqu and Amdo stations are consistent with the simulated process under temperature of 20 oC and relative humidity of 50%. The distillation line simulated under Rayleigh equilibrium condition is analogous to the global meteoric water line (MWL) as the temperature is about 20 oC. Under non-equilibrium condition, the slope and constant values of distillation line are directly proportional to temperature and relative humidity. According to the basic data, the simulated distillation line is very consistent with the actual distillation line of Qinghai Lake.     

Determination of Lithium, Beryllium and Boron at Trace Levels by Laser Ablation-Inductively Coupled Plasma-Sector Field Mass Spectrometry

The analytical capabilities of laser ablation (LA)-ICP-MS in determining Li, Be and B at trace levels in geological samples have been tested on a series of glass reference materials and natural samples. The LA-ICP-MS instrument used consisted of a sector-field ICP-MS coupled with a laser ablation microprobe operating at either 266 or 213 nm wavelength. Reference glasses from NIST (SRM 612, 614 and 616) and MPI-DING (KL2-G, ML3B-G, StHs6/80-G, GOR128-G, GOR132-G, T1-G and ATHO-G) were selected to develop the analytical method and to assess the best instrumental configuration. A series of calcic amphiboles with different Li, Be and B concentrations were also analysed using both LA-ICP-MS and SIMS to test the applicability of the method to natural minerals. Results indicated that with a spot size of 40 μm the agreement between measured and reference values of Li, Be and B is generally better than 10% for NIST SRM 612 and 20% for NIST SRM 614. Average reproducibility at the 2s level was 10% for Li, 20% for Be and 15% for B. Limits of detection were approximately 100 ng g^-1 for Be and B and 200 ng g^-1 for Li. These results were confirmed by analyses carried out on natural amphiboles and compared well in terms of precision and accuracy with those commonly achieved by SIMS.     

Preliminary Characterisation of New Glass Reference Materials (GSA-1G, GSC-1G, GSD-1G and GSE-1G) by Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry Using 193 nm, 213 nm and 266 nm Wavelengths

New glass reference materials GSA-1G, GSC-1G, GSD-1G and GSE-1G have been characterised using a prototype solid state laser ablation system capable of producing wavelengths of 193 nm, 213 nm and 266 nm. This system allowed comparison of the effects of different laser wavelengths under nearly identical ablation and ICP operating conditions. The wavelengths 213 nm and 266 nm were also used at higher energy densities to evaluate the influence of energy density on quantitative analysis. In addition, the glass reference materials were analysed using commercially available 266 nm Nd:YAG and 193 nm ArF excimer lasers. Laser ablation analysis was carried out using both single spot and scanning mode ablation. Using laser ablation ICP-MS, concentrations of fifty-eight elements were determined with external calibration to the NIST SRM 610 glass reference material. Instead of applying the more common internal standardisation procedure, the total concentration of all element oxide concentrations was normalised to 100%. Major element concentrations were compared with those determined by electron microprobe. In addition to NIST SRM 610 for external calibration, USGS BCR-2G was used as a more closely matrix-matched reference material in order to compare the effect of matrix-matched and non matrix-matched calibration on quantitative analysis. The results show that the various laser wavelengths and energy densities applied produced similar results, with the exception of scanning mode ablation at 266 nm without matrix-matched calibration where deviations up to 60% from the average were found. However, results acquired using a scanning mode with a matrix-matched calibration agreed with results obtained by spot analysis. The increased abundance of large particles produced when using a scanning ablation mode with NIST SRM 610, is responsible for elemental fractionation effects caused by incomplete vaporisation of large particles in the ICP.     

Primary Ore Mineral Assemblage and Fluid Inclusion Study of the Batu Hijau Porphyry Cu-Au Deposit, Sumbawa, Indonesia

Abstract. The Batu Hijau porphyry Cu‐Au deposit, Sumbawa Island, Indonesia, is associated with a tonalitic intrusive complex. The temperature‐pressure condition of mineralization at the Batu Hijau deposit is discussed on the basis of fluid inclusion microthermometry. Then, the initial Cu‐Fe sulfide mineral assemblage is discussed. Bornite and chalcopyrite are major copper ore minerals associated with quartz veinlets. The quartz veinlets have been classified into ‘A’ veinlets associated with bornite, digenite, chalcocite and chalcopyrite, ‘B’ veinlets having chalcopyrite bornite along vuggy center‐line, rare ‘C’ chalcopyrite‐quartz veinlets, and late ‘D’ veinlets consisting of massive pyrite and quartz (Clode et al., 1999). Copper and gold mineralization is associated with abundant ‘A’ quartz veinlets. Abundant fluid inclusions are found in veinlet quartz consisting mainly of gas‐rich inclusions and polyphase inclusions throughout the veinlet types. The hydrothermal activity occurred in temperature‐pressure conditions of aqueous fluid immiscibility into hypersaline brine and dilute vapor. The halite dissolution (Tm[halite]) and liquid‐vapor homogenization (Th) temperatures of the polyphase inclusions in veinlet quartz range from 270 to 472d?C and from 280 to 454d?C, respectively. The estimated salinity ranges from 36 to 47 wt% (NaCl equiv.). The apparent pressures lower than 300 bars are estimated to have been along the liquid‐vapor‐halite curve for the fluid inclusions having the Th lower than the Tm that trapped the brine saturated with halite, or at slightly higher pressure relative to liquid‐vapor‐halite curve for the fluid inclusions having the Th higher than the Tm that trapped the brine unsaturated with halite. The actual temperature and pressure during the hydrothermal activity at the Batu Hijau deposit are estimated to have been around 300d?C and 50 bars. At such temperature‐pressure conditions, the principal and initial Cu‐Fe sulfide mineral assemblages are thought to be chalcopyrite + bornite solid solution (bnss) for the chalcopyrite‐bearing assemblage, and chalcocite‐digenite solid solution and bnss for the chalcopyrite‐free assemblage.     

Evolution of Hydrothermal System at the Dizon Porphyry Cu-Au Deposit, Zambales, Philippines

Abstract. Evolution of hydrothermal system from initial porphyry Cu mineralization to overlapping epithermal system at the Dizon porphyry Cu‐Au deposit in western central Luzon, Zambales, Philippines, is documented in terms of mineral paragen‐esis, fluid inclusion petrography and microthermometry, and sulfur isotope systematics. The paragenetic stages throughout the deposit are summarized as follows; 1) stockwork amethystic quartz veinlets associated with chalcopyrite, bornite, magnetite and Au enveloped by chlorite alteration overprinting biotite alteration, 2) stockwork quartz veinlets with chalcopyrite and pyrite associated with Au and chalcopyrite and pyrite stringers in sericite alteration, 3) stringer quartz veinlets associated with molybdenite in sericite alteration, and 4) WNW‐trending quartz veins associated with sphalerite and galena at deeper part, while enargite and stibnite at shallower levels associated with advanced argillic alteration. Chalcopyrite and bornite associated with magnetite in quartz veinlet stockwork (stage 1) have precipitated initially as intermediate solid solution (iss) and bornite solid solution (bnss), respectively. Fluid inclusions in the stockwork veinlet quartz consist of gas‐rich inclusions and polyphase inclusions. Halite in polyphase inclusions dissolves at temperatures ranging from 360d?C to >500d?C but liquid (brine) and gas (vapor) do not homogenize at <500d?C. The maximum pressure and minimum temperature during the deposition of iss and bnss with stockwork quartz veinlets are estimated to be 460 bars and 500d?C. Fluid inclusions in veinlet stockwork quartz enveloped in sericite alteration (stage 2) consist mainly of gas‐rich inclusions and polyphase inclusions. In addition to the possible presence of saturated NaCl crystals at the time of entrapment of fluid inclusions that exhibit the liquid‐vapor homogenization temperatures lower than the halite dissolution temperatures in some samples, wide range of temperatures of halite dissolution and liquid‐vapor homogenization of polyphase inclusions from 230d?C to >500d?C and from 270d?C to >500d?C, respectively, suggests heterogeneous entrapment of gaseous vapor and hypersaline brine. The minimum pressure and temperature are estimated to be about 25 bars and 245d?C. Fluid inclusions in veinlet quartz associated with molybdenite (stage 3) are dominated by gas‐rich inclusions accompanied with minor liquid‐rich inclusions that homogenize at temperatures between 350d?C and 490d?C. Fluid inclusions in vuggy veinlet quartz associated with stibnite (stage 4) consist mainly of gas‐rich inclusions with subordinate polyphase inclusions that do not homogenize below 500d?C. Fluid inclusions in veinlet quartz associated with galena and sphalerite (stage 4) are composed of liquid‐rich two‐phase inclusions, and they homogenize into liquid phase at temperatures ranging widely from 190d?C to 300d?C (suggesting boiling) and the salinity ranges from 1.0 wt% to 3.4 wt% NaCl equivalent. A pressure of about 15 bars is estimated for the dilute aqueous solution of 190d?C from which veinlet quartz associated with galena and sphalerite precipitated. In addition to a change in temperature‐pressure regime from lithostatic pressure during the deposition of iss and bnss with stockwork quartz veinlets to hydrostatic pressure during fracture‐controlled quartz veinlet associated with galena and sphalerite, a decrease in pressure is supposed to have occurred due to unroofing or removal of the overlying piles during the temperature decrease in the evolution of hydrothermal system. The majority of the sulfur isotopic composition of sulfides ranges from ±0 % to +5 %. Sulfur originated from an iso‐topically uniform and homogeneous source, and the mineralization occurred in a single hydrothermal system.     

Chemistry and Sulfur Isotopes in a Chert-dominant Sequence around the Stratiform Manganese Deposit of the Noda-Tamagawa Mine, Northern Kitakami Terrane, Northeast Japan: Implication for Paleoceanographic Environmental Setting

Abstract. Chemistry and sulfur isotopes are analyzed for a series of rocks in the chert‐dominant sequence around the stratiform manganese ore deposit of the Noda‐Tamagawa mine in the northern Kitakami Terrane, northeast Japan. The sequence is litholog‐ically classified into six units in ascending order: lower bedded chert, lower black shale, massive chert, manganese ore, upper black shale, and upper bedded chert. The rocks around the manganese ore deposit exhibit anomalous enrichment in Ni (max. 337 ppm), Zn (102) and U (30) in the upper part of lower bedded chert, Mo (122), Tl (79) and Pb (33) in the lower black shale, MnO, Cu (786) and Co (62) in the manganese ore, and As (247) and Sb (17) in the upper black shale. The aluminum‐normalized profiles reveal zonal enrichment of redox‐sensitive elements around the manganese bed: Zn‐Ni‐Fe‐Mo‐U(‐Co), Tl‐Pb(‐Mo), Mn‐Fe‐Cu‐V‐Cr‐Co(‐Zn) and As‐Sb in ascending order. The uppermost part of the lower bedded chert and black shale exhibit negative Ce/Ce* values, whereas the massive chert, manganese ore and lower part of the upper bedded chert display positive values. The isotopic δ³⁴S values are 0±6 % in the lower part of the lower bedded chert, ‐19 to ‐42 % in the upper part of the lower bedded chert, ‐36 to ‐42 % in the lower black shale, ‐28 to ‐35 % in the massive chert, manganese ore and upper black shale, and ‐23±5 % in the upper bedded chert. Thus, there is a marked negative shift in δ³⁴S values in the lower bedded chert, and an upward‐increasing trend in δ³⁴S through the manganese ore horizon. The present data provide evidence for a change in the paleoceanographic environmental resulting from inflow of oxic deepwater into the stagnant anoxic ocean floor below the manganese ore horizon. This event is likely to have triggered the precipitation of manganese oxyhydroxides. The redistribution of redox‐sensitive elements through the formation of metalliferous black shale and manganese carbonate ore may have occurred in association with bacterial decomposition of organic matter during early diagenesis of initial manganese oxyhydroxides.     

Chemical Profiles across a Jurassic Stratiform Manganese Deposit at Katsuyama in the Mino Terrane of Central Japan: Implications for Depositional Environment, Diagenetic Metal Redistribution and Paleoceanography

Abstract. Inorganic chemical compositions are determined for a series of rocks crossing an Early Jurassic stratiform manganese ore deposit in a chert‐dominant sequence at Katsuyama, in the Mino Terrane of central Japan. The lithology in the vicinity of the manganese ore bed is classified into lower bedded chert, black shale, massive chert, manganese ore and upper bedded chert, in ascending order. The rocks surrounding the manganese deposit are anomalously high in certain elements: Pb (max. 29 ppm), Ni (1140) and Co (336) in the lower bedded chert, Mo (438), As (149), Tl (29) and U (12) in the black shales, V (210) and Cr (87) in the massive chert, and MnO and W (24) in the manganese ore. The aluminum‐normalized profiles reveal a distinct zonation of redox‐sensitive elements: Pb‐Zn, Ni‐Co‐Cu(‐Zn) and U‐Cr in the lower bedded chert, Mo‐As‐Tl in the black shale, V(‐Cr) in the massive chert, and Mn‐Fe‐Ba‐W in the manganese ore, in ascending order. The lower and upper bedded cherts and manganese ore generally exhibit flat rare earth element patterns with positive Ce anomalies, whereas the uppermost part of the lower bedded chert, the black shale and massive chert have flat patterns with weak or nonexistent negative Ce anomalies and weak positive Eu anomalies. The strong enrichment in Ni, Co, W, Tl and As detected in the Katsuyama section is not recognized in other sediments, including those of anoxic deposition origin, but is identified in modern ferromanganese nodules, suggesting that metal enrichment in the Katsuyama section is essentially due to the formation of ferromanganese nodules rather than to deposition in an anoxic environment. The observed elemental zonation is well explained by equilibrium calculations, reflecting early diagenetic formation and associated gradual reduction with depth. The concentration profiles in combination with litho‐ and biostratigraphical features suggest that formation of these bedded manganese deposits was triggered by an influx of warm, saline and oxic water into a stagnant deep ocean floor basin in Panthalassa at the end of the middle Early Jurassic. Paleoceanographic environmental controls thus appear to be important factors in the formation and preservation of this type of stratiform manganese deposit.     

Rare Earth, Major and Trace Elements in the Kunimiyama Ferromanganese Deposit in the Northern Chichibu Belt, Central Shikoku, Japan

Abstract. Rare earth, major and trace element geochemistry is reported for the Kunimiyama stratiform ferromanganese deposit in the Northern Chichibu Belt, central Shikoku, Japan. The deposit immediately overlies greenstones of mid-ocean ridge basalt (MORB) origin and underlies red chert. The ferromanganese ores exhibit remarkable enrichments in Fe, Mn, P, V, Co, Ni, Zn, Y and rare earth elements (excepting Ce) relative to continental crustal abundance. These enriched elements/ Fe ratios and Post-Archean Average Australian Shale-normalized REE patterns of the ferromanganese ores are generally analogous to those of modern hydrothermal ferromanganese plume fall-out precipitates deposited on MOR flanks. However in more detail, Mn and Ti enrichments in the ferromanganese ores are more striking than the modern counterpart, suggesting a significant contribution of hydrogenetic component in the Kunimiyama ores. Our results are consistent with the interpretation that the Kunimiyama ores were umber deposits that primarily formed by hydrothermal plume fall-out precipitation in the Panthalassa Ocean during the Early Permian and then accreted onto the proto-Japanese island arc during the Middle Jurassic. The presence of strong negative Ce anomaly in the Kunimiyama ores may indicate that the Early Permian Panthalassa seawater had a more striking negative Ce anomaly due to a more oxidizing oceanic condition than today.