Sulfur Isotopic Study of the Toyoha Deposit, Hokkaido, Japan Comparison between the Earlier-Stage and the Later-Stage Veins

Abstract: The sulfur isotopic ratios (δ³⁴S) of ore minerals from the Toyoha deposit, Hokkaido, one of the largest Pb–Zn–Ag polymetallic vein-type deposits in Japan, were studied. More than 90% of the δ³⁴S values of the studied sulfide minerals collected from the Toyoha deposit range from +5 to +9%, with an average of approximately +7% irrespective of the mineral species, veins, elevations, depth, mineralization stages and mineral assemblages. Relatively uniform δ³⁴S values obtained in this study suggest that the reduced aqueous sulfur species predominated over the oxidized sulfur in the ore solution throughout the mineralization stages. Thus, the source of sulfur for the ore sulfides is postulated to be magmatic.
The temperature obtained from the fluid inclusion study and the temperature of the sulfur isotopic geothermometer are not consistent. This suggests that each mineral precipitated under disequilibrated conditions with respect to the sulfur isotope.
The change in redox conditions presumably encountered between the mineralization stages did not account for the isotopic fluctuations since the isotopic exchanges between the oxidized and reduced aqueous sulfurs are much slower than the rate of oxidation of the ore solution.     

Geochronology of Middle and Upper Pleistocene Loess Sections in Hungary

The application of both thermoluminescence and infrared stimulated luminescence dating to the extensively studied “classical” Hungarian loess/paleosol sequences from Basaharc, Mende, and Paks provides a reliable chronological framework and climatostratigraphic reconstruction for the last interglacial/glacial cycle. Based on this combined luminescence dating study a new chronology is proposed for the “Young Loess” in Hungary. Luminescence dating suggests that the loess below the MF2 horizon formed during the penultimate glaciation. The MF1 horizon probably formed during an interstade within oxygen isotope stage 3. For the youngest loess, overlying MF1, a very high accumulation rate was determined. Large time gaps occur above MF2 and MF1, indicating that most of the record of the last glaciation is missing in the standard sections at Basaharc, Mende, and Paks. Either large discontinuities or a very low accumulation rate occurred in all three type sections during the soil-forming periods. High-resolution studies of climatic proxies using this combined luminescence dating approach provide a reliable chronological framework for loess and loess derivatives of the last glacial cycle in Hungary, although a precise and complete chronostratigraphic reconstruction cannot be achieved from the incomplete records found at these sites.     

Crystal-Melt Separation and the Development of Isotopic Heterogeneities in Hybrid Magmas

If a magma is a hybrid of two (or more) isotopically distinctend-members, at least one of which is partially crystalline,separation of melt and crystals after hybridization will leadto the development of isotopic heterogeneities in the magmaas long as some of the pre-existing crystalline material (antecrysts)retains any of its original isotopic composition. This holdstrue whether the hybridization event is magma mixing as traditionallyconstrued, bulk assimilation, or melt assimilation. Once a magma-scaleisotopic heterogeneity is formed by crystal–melt separation,it is essentially permanent, persisting regardless of subsequentcrystallization, mixing, or equilibration events. The magnitudeof the isotopic variability resulting from crystal–meltseparation can be as large as that resulting from differentialcontamination, multiple isotopically distinct sources, or insitu isotopic evolution. In one model, a redistribution of one-thirdof the antecryst cargo yielded a crystal-enriched sample with⁸⁷Sr/⁸⁶Sr of 0·7058, whereas the complementary crystal-poorsample has ⁸⁷Sr/⁸⁶Sr of 0·7068. In other models, crystal-richsamples are enriched in radiogenic Sr. Isotopic heterogeneitiescan be either continuous (controlled by the modal distributionof crystals and melt) or discontinuous (when there is completeseparation of crystals and liquid). The first case may be exemplifiedby some isotopically zoned large-volume rhyolites, formed bythe eruptive inversion of a modally zoned magma chamber. Inthe latter case, the isotopic composition of any (for example)interstitial liquid will be distinct from the isotopic compositionof the bulk crystal fraction. The separation of such an interstitialliquid may explain the presence of isotopically distinct late-stageaplites in plutons. Crystal–melt separation provides anadditional option for the interpretation of isotopically zonedor heterogeneous magmas. This option is particularly attractivefor systems whose chemical variation is otherwise explicableby fractionation-dominated processes. Non-isotopic chemicalheterogeneities can also develop in this fashion. KEY WORDS: isotopic heterogeneity; zoning; hybrid magma; crystal separation; Sr isotopes; aplite; rhyolite     

The origin of the Maozu carbonate-hosted Pb–Zn deposit,southwest China: Constrained by C–O–S–Pb isotopic compositions and Sm–Nd isotopic age

The Maozu Pb–Zn deposit, located on the western margin of the Yangtze Block, southwest China, is a typical carbonate-hosted deposit in the Sichuan–Yunnan–Guizhou Pb–Zn metallogenic province with Pb + Zn reserves of about 2.0 million tonnes grading 4.15 wt.% Pb and 7.25 wt.% Zn. Its ore bodies are hosted in Sinian (635–541 Ma) Dengying Formation dolostone and show stratiform, vein and irregular textures. Ores are composed of sphalerite, galena, pyrite, calcite, dolomite, quartz and fluorite with massive, banded, disseminated and veined structures. The C–O–Sm–Nd isotopic compositions of hydrothermal calcites and S–Pb isotopic compositions of sulfides were analyzed to constrain the origin of the Maozu deposit. δ¹³C_PDB and δ¹⁸O_SMOW values of hydrothermal calcites range from −3.7‰ to −2.0‰ and +13.8‰ to +17.5‰, respectively, and plot near the marine carbonate rocks field in a plot of δ¹³C_PDB vs. δ¹⁸O_SMOW, with a negative correlation. It suggests that CO₂ in the hydrothermal fluids was mainly originated from marine carbonate rocks, with limited influence from sedimentary organic matter. δ³⁴S_CDT values of sulfides range from +9.9‰ to +19.2‰, similar to that of Cambrian to Triassic seawater sulfate (+15‰ to +35‰) and evaporate (+15‰ to +30‰) in the Cambrian to Triassic sedimentary strata. It suggests that reduced sulfur was derived from evaporate in sedimentary strata by thermo chemical sulfate reduction. Sulfides have low radiogenic Pb isotope compositions (²⁰⁶Pb/²⁰⁴Pb = 18.129–18.375, ²⁰⁷Pb/²⁰⁴Pb = 15.640–15.686 and ²⁰⁸Pb/²⁰⁴Pb = 38.220–38.577) that plot in the field between upper crust and the orogenic belt evolution curve in the plot of ²⁰⁷Pb/²⁰⁴Pb vs. ²⁰⁶Pb/²⁰⁴Pb, and similar to that of age corrected Proterozoic basement rocks (Dongchuan and Kunyang Groups). This indicates that ore-forming metals were mainly derived from basement rocks. Hydrothermal calcite yields a Sm–Nd isotopic age of 196 ± 13 Ma, possibly reflecting the timing of Pb–Zn mineralization in the SYG province, younger than the Permian Emeishan mantle plume (∼260 Ma). All data combined suggests that hydrothermal fluids circulated through basement rocks where they picked up metals and migrated to surface, mixed with reduced sulfur-bearing fluids and precipitated metals. Ore genesis of the Maozu deposit is different from known magmatic–hydrothermal, Sedimentary Exhalative or Mississippi Valley-types, which maybe represent a unique ore deposit type, named as the SYG-type.     

Factors Controlling Precipitation of Barite and Witherite and Genesis of the Ankang–Xunyang Barium Deposits, Shaanxi, China

The barium deposits in Ankang and Xunyang counties,Shaanxi Province,China,occur in the northernmost part of the world-class barium metallogenic belt in south Qinling.The deposits are hosted by the Lower Silurian carbonaceous siliceous rocks,with a unique combination of barite and witherite.The homogenization temperatures of fluid inclusions in the barite are mainly concentrated between 135 and 155 ℃,whereas those from the witherite have two peaks of 165-175 ℃,and 215-225℃,respectively.Laser Raman analysis of fluid inclusions indicates that the vapor phase of fluid inclusions in barite is dominated by H_2O,although some contains N_2,H_2S,and CH_4.The compositions of the vapor and liquid phases of fluid inclusions in witherite can be divided into two end-members,one dominated by H_2O without other volatiles,and the other containing CH_4,C_2H_6,C_3H_8,C_2H_4,and C_6H_6 in addition to H_2O.CO_2,H_2S,and some CH_4 are interpreted as products of chemical reactions during mineralization.Organic gases(CH_4,C_2H_6,C_3H_8,C_2H_4,and C_6H_6) in the fluids were critical in the formation of barium sulfate versus carbonate.The δ~(34)S values of barite range from 38.26‰ to54.23‰(CDT),the δ~(34)S values of sulfides coexisting with barium minerals vary from 22.44‰ to25.11‰(CDT),and those in the wall rock from 11.60‰ to 19.06‰(CDT).We propose that the SO_4~(2-)generally experienced bacterial sulfate reduction in seawater before mineralization,and some SO_4~(2-)also experienced thermochemical sulfate reduction in hydrothermal system during mineralization.The δ~(13)C values of witherite range from-27.30‰ to-11.80‰(PDB),suggesting that carbon was sourced from organic substances(like CH_4,C_2H_4,and C_2H_6).The formation of witherite was possibly associated with thermochemical sulfate reduction,which caused the consumption of the organic gases and SO_4~(2-) in the hydrothermal solutions,consequently inhibiting barite formation.The important conditions for forming witherite include high fluid temperatures,high Ba~(2+) concentrations,CO_2 in the fluids,low HS~- concentrations,and the subsequent rapid diffusion of H_2S during thermochemical sulfate reduction of the fluids.     

硼及硼同位素地球化学在地质研究中的应用

总结了硼及硼同位素的地球化学特征：（１）硼是易溶元素,主要赋存在地球表层,尤其是海水、海相沉积物及海水交代岩石中。其同位素组成δ１１Ｂ值按顺序变化,封闭盐湖卤水（＞４０‰）＞海水（３９５‰）＞海相硼矿物（１８２‰～３１７３‰）＞海相沉积物（１３９‰～２５２‰）＞海水交代岩石（４５１‰～１０８５‰）。大陆水及陆相沉积物硼含量及硼同位素组成变化极大,并多以负值为主。海陆过渡构造带则具有过渡的硼丰度值和硼同位素组成。（２）１１Ｂ较１０Ｂ具有更活跃的地球化学性质,因此在水岩作用中具有明显的同位素交换。硅化交代作用中,岩石被硅化交代,释放硼,并优先释放重硼,同位素组成变轻;在脱硅反应中,岩石释放硅吸收硼,并优先吸收重硼,同位素组成变重。在封闭体系中,水溶液淋滤岩石中部分的硼,即可大量富集,并富集１１Ｂ;在开放体系中,岩石硼被大量淋滤流失,δ１１Ｂ值明显降低。由于水岩作用的结果,从新鲜海底玄武岩到正常海水,硼同位素值从－２９５‰到３９５‰逐渐升高。（３）变质脱水反应中硼被大量排出,并优先排出重硼同位素,进入流体相,因此随着变质程度由低到高,岩石中硼含量及同位素组成δ１１Ｂ值由高变低。（４）在成矿研究中?     

Triassic alkaline intrusives in the Yanliao-Yinshan area: their chronology, Sr, Nd and Pb isotopic characteristics and their implication

Dated isotopic ages for 15 alkaline intrusives in the Yanliao-Yinshan area, ranging from 268 to 190 Ma, ten of which are from 250 to 208 Ma, indicate that most of them were formed in the Triassic Epoch. All the E_Nd(t) ratios from - 17.19 to -3.21 averaging -7.09, the E_Sr(t) ratios fmm 11.7 to71.5 averaging 36.63, and the I_sr(t) ratios from 0.705 0 to 0.709 3 averaging 0.706 8, show their characteristics of enrichment. On the E_Nd (t) virus E_Sr(t) correlation diagram, the samples from these intmsives were plotted within the enriched mantle trend lines and just outside, demonstrating their close connection to materials from the enriched mantle reservoir, taking into account the same Pb isotopic composition as that of the mantle.     

Tectonic evolution of the Late Paleozoic Early Mesozoic orogenic belt in the eastern segment of the northern margin of the North China Block: Evidence from meta volcanic rocks of Jianshanzi,northern Liaoning ProvinceSCIEI北大核心CSCD

LA-ICP-MS U-Pb dating, whole -rock geochemistry and Hf isotopic analyses for the Jianshanzi volcanic rocks in the Kaiyuan area are presented to explore the Late Paleozoic -Early Mesozoic tectonic evolution history of the eastern segment of the northern margin of the North China block. The detailed research indicates that the protolith of Jianshanzi metamorphic volcanic rocks includes rhyolite, dacite and andesite, they are calc-alkaline series and metaluminous-weak peraluminous rocks. According to the zircon U-Pb dating, the metamorphic rhyolite and metamorphic andesite formed in the Late Permian (256. 1 +/- 1. 5Ma, 252.4 +/- 1. 7Ma) and the Late Triassic (222. 4 +/- 1. 8Ma, 227. 9 +/- 1. 2Ma), respectively. They are characteristized by enrichment in light rare earth elements and large ion lithophile elements, and depletion of heavy rare earth elements and high field strength elements. Metamorphic rhyolite has an obvious negative Eu anomaly with epsilon(Hf) ( t) values of 10. 83 + 8. 10 and the second -stage model are 698 similar to 1967Ma. They are mainly due to the partial melting of the juvenile basaltic lower crust and the contamination of a small amount of ancient crustal materials. Metamorphic andesite has no obvious Eu anomaly, and the epsilon(Hf)( t) value and the second -stage model are +4.54 similar to + 6. 79 and 825 similar to 968 Ma, which may be the product of partial melting of basic lower crust. There are two periods of magmatism in Jianshanzi volcanic rocks: Late Permian -Early Triassic (247 similar to 256Ma) and Late Triassic (similar to 225Ma). The material composition of the Jianshanzi volcanic rocks is characterized by different times and different tectonic backgrounds. It is comprehensively believed that the eastern segment of the northern margin of the North China block was in an active continental margin tectonic environment during the Permian, and the Palaeo-Asian Ocean subducted in both directions; Mantle -derived magma ascends and emplaces, forming a nascent crust and causing crustal thickening. The Paleo-Asian Ocean finally closed in the early Middle Triassic, and the impact of collisional orogeny may have continued until the early Late Triassic.     

新疆东部金窝子金矿成因讨论：同位素地质年代学证据

金窝子金矿床位于新疆－甘肃交界处,构造上位于西柏利亚,塔里木哈联克斯坦和中朝古 块的交汇部位,是新疆东部地区重要的金矿床。基于９０％左右的矿体以含金石英脉形式集中分布于金窝子花岗闪长岩体内的构造破碎带中,而其余１０％的含金石英网脉散布于邻近岩体的围岩破碎带中,多数者认为该矿床与花岗闪长质岩浆的侵位有直接的成因联系,并主张围岩破碎带中的含金石英网脉的形成时代早于岩体中的含金石英脉。     

四川石棉地区前震旦纪“康定杂岩”的时代探讨

四川石棉地区的前震旦纪基底变质杂岩（“康定杂岩”） 呈断块产出,由中浅（深） 变质岩、变质侵入岩及混合岩组成。在片岩中获蓟县纪—青白口纪球藻类化石;采用锆石ＵＰｂ 法和ＰｂＰｂ 法获得变粒岩的原岩年龄为１０６７Ｍａ,变质砂岩的成岩年龄小于８５３Ｍａ,变质侵入岩的成岩年龄为８７６ ～８２８Ｍａ,混合岩的变成年龄为７１１Ｍａ,结合早震旦世岩体侵蚀混合岩,故将基底变质杂岩的时代确定为蓟县纪—青白口纪。