A geochemical study of the Sweet Home Mine,Colorado Mineral Belt,USA: hydrothermal fluid evolution above a hypothesized granite cupola

Deposition of quartz–molybdenite–pyrite–topaz–muscovite–fluorite and subsequent hübnerite and sulfide–fluorite–rhodochrosite mineralization at the Sweet Home Mine occurred coeval with the final stage of magmatic activity and ore formation at the nearby world-class Climax molybdenum deposit about 26 to 25 m.y. ago. The mineralization occurred at depths of about 3,000 m and is related to at least two major fluid systems: (1) one dominated by magmatic fluids, and (2) another dominated by meteoric water. The sulfur isotopic composition of pyrite, strontium isotopes and REY distribution in fluorite suggest that the early-stage quartz–molybdenite–pyrite–topaz–muscovite–fluorite mineral assemblage was deposited from magmatic fluids under a fluctuating pressure regime at temperatures of about 400°C as indicated by CO₂-bearing, moderately saline (7.5–12.5 wt.% NaCl equiv.) fluid inclusions. LA-ICPMS analyses of fluid inclusions in quartz demonstrate that fluids from the Sweet Home Mine are enriched in incompatible elements but have considerably lower metal contents than those reported from porphyry–Cu–Au–Mo or Climax-type deposits. The ore-forming fluid exsolved from a highly differentiated magma possibly related to the deep-seated Alma Batholith or distal porphyry stock(s). Sulfide mineralization, marking the periphery of Climax-type porphyry systems, with fluorite and rhodochrosite as gangue minerals was deposited under a hydrostatic pressure regime from low-salinity ± CO₂-bearing fluids with low metal content at temperatures below 400°C. The sulfide mineralization is characterized by mostly negative δ³⁴S values for sphalerite, galena, chalcopyrite, and tetrahedrite, highly variable δ¹⁸O values for rhodochrosite, and low REE contents in fluorite. The Pb isotopic composition of galena as well as the highly variable ⁸⁷Sr/⁸⁶Sr ratios of fluorite, rhodochrosite, and apatite indicates that at least part of the Pb and Sr originated from a much more radiogenic source than Climax-type granites. It is suggested that the sulfide mineralization at the Sweet Home Mine formed from magmatic fluids that mixed with variable amounts of externally derived fluids. The migration of the latter fluids, that were major components during late-stage mineralization at the Sweet Home Mine, was probably driven by a buried magmatic intrusion.     

河南省内乡县银洞沟银金多金属矿成矿年龄: 热液锆石LA-MC-ICP-MS U-Pb测年

北秦岭构造带广泛发育与古生代洋壳俯冲和碰撞造山有关的岩浆活动以及与造山过程有关的变质作用,但古生代热液脉型矿床在北秦岭构造带少见报道。银洞沟银金多金属矿为北秦岭构造带东部的一处中型热液脉型矿床,本文通过对该矿床赋矿围岩和含矿石英脉中锆石开展LA- MC- ICP- MS U- Pb测年和锆石成因研究,确定了矿床的形成时代,并探讨了矿床的成矿动力学背景。结果表明赋矿围岩黑云母二长花岗岩的形成时代为431. 4±2. 1 Ma,含矿石英脉中锆石结晶年龄为419. 4±5. 9 Ma,石英脉中锆石的岩相学、锆石中矿物和流体包裹体及锆石微量元素研究表明419. 4 Ma代表矿床的形成时代。结合前人的研究结果,确定银洞沟银金多金属矿为形成于晚志留世的造山型矿床,成矿作用与碰撞期后～420 Ma的变质作用密切相关,成矿流体来源于地层的变质脱水,成矿物质主要来源于秦岭岩群和二郎坪群。     

Natural evidence for rapid abiogenic hydrothermal generation of CH4

Although recent hydrothermal experiments imply that abiogenic methane (CH₄) generation from hydrothermal reduction of CO₂ can occur, evidence from natural systems was still lacking. Based on the chemical and isotopic equilibrium signatures of low-temperature fumarolic gas discharges, we are able to provide hard evidence for its natural occurrence, namely in three subduction-related bi-phase hydrothermal systems of the Mediterranean, whose temperatures range from 260 to 470 °C. The attainment of equilibrium and the time spans of recent volcanic dormancy allowed us to calculate minimum rates for chemical and isotopic equilibration. These are significantly higher than those previously reported and might be due to the presence of a saturated water vapor phase in the investigated systems. The fact that nature provides conditions enabling relatively fast production of hydrocarbons from CO₂ strongly supports the concerns that were recently raised from laboratory experiments. These address the use of the carbon isotope composition of reduced carbon in Archean sediments as a tracer of early life and the occurrence of CH₄ on extraterrestrial planets as a bioindicator. In view of the potential role of abiogenic CH₄ as a precursor of life, we also present an estimate of abiogenic hydrothermal CH₄ fluxes throughout the Archean. It is not expected that these fluxes exceeded 80 Mt/yr during the past 4.0 Ga. This, however, would have been enough to facilitate HCN production on the prebiotic Earth.     

Phosphoinnelite, Ba4Na3Ti3Si4O14(PO4,SO4)2(O,F)3, a new mineral species from peralkaline pegmatite of the Kovdor pluton, Kola Peninsula

Phosphoinnelite, an analogue of innelite with P > S, has been found in a peralkaline pegmatite vein crosscutting calcite carbonatite at the phlogopite deposit, Kovdor pluton, Kola Peninsula. Cancrinite (partly replaced with thomsonite-Ca), orthoclase, aegirine-augite, pectolite, magnesioarfvedsonite, golyshevite, and fluorapatite are associated minerals. Phosphoinnelite occurs as lath-shaped crystals up to 0.2 × 1 × 6 mm in size, which are combined typically in bunch-, sheaf-, and rosettelike segregations. The color is yellow-brown, with vitreous luster on crystal faces and greasy luster on broken surfaces. The mineral is transparent. The streak is pale yellowish. Phosphoinnelite is brittle, with perfect cleavage parallel to the {010} and good cleavage parallel to the {100}; the fracture is stepped. The Mohs hardness is 4.5 to 5. Density is 3.82 g/cm³ (meas.) and 3.92 g/cm³ (calc.). Phosphoinnelite is biaxial (+), α = 1.730, β = 1.745, and γ = 1.764, 2V (meas.) is close to 90°. Optical orientation is Z^c ∼ 5°. Chemical composition determined by electron microprobe is as follows (wt %): 6.06 Na₂O, 0.04 K₂O, 0.15 CaO, 0.99 SrO, 41.60 BaO, 0.64 MgO, 1.07 MnO, 1.55 Fe₂O₃, 0.27 Al₂O₃, 17.83 SiO₂, 16.88 TiO₂, 0.74 Nb₂O₅, 5.93 P₂O₅, 5.29 SO₃, 0.14 F, −O=F₂ = −0.06, total is 99.12. The empirical formula calculated on the basis of (Si,Al)₄O₁₄ is (Ba_3.59Sr_0.13K_0.01)_Σ3.73(Na_2.59Mg_0.21Ca_0.04)_Σ3.04(Ti_2.80Fe _0.26 ³⁺ Nb_0.07)_Σ3.13[(Si_3.93Al_0.07)_Σ4O₁₄(P_1.11S_0.87)_Σ1.98O_7.96](O_2.975F_0.10)_Σ3.075. The simplified formula is Ba₄Na₃Ti₃Si₄O₁₄(PO₄,SO₄)₂(O,F)₃. The mineral is triclinic, space group P or P1. The unit cell dimensions are a = 5.38, b = 7.10, c = 14.76 ?; α = 99.00°, β = 94.94°, γ = 90.14°; and V = 555 ?³, Z = 1. The strongest lines of the X-ray powder pattern [d, ? in (I)(hkl)] are: 14.5(100)(001), 3.455(40)(103), 3.382(35)(0 2), 2.921(35)(005), 2.810(40)(1 4), 2.683(90)(200, 01), 2.133(80)( 2), 2.059(40)(204, 1 3, 221), 1.772(30)(0 1, 1 7, 2 2, 2 3). The infrared spectrum is demonstrated. An admixture of P substituting S has been detected in the innelite samples from the Inagli pluton (South Yakutia, Russia). An innelite-phosphoinnelite series with a variable S/P ratio has been discovered. The type material of phosphoinnelite has been deposited at the Fersman Mineralogical Museum, Russian Academy of Sciences, Moscow. Original Russian Text ? I.V. Pekov, N.V. Chukanov, I.M. Kulikova, D.I. Belakovsky, 2006, published in Zapiski Rossiiskogo Mineralogicheskogo Obshchestva, 2006, No. 3, pp. 52–60. Considered and recommended by the Commission on New Minerals and Mineral Names, Russian Mineralogical Society, May 9, 2005. Approved by the Commission on New Minerals and Mineral Names, International Mineralogical Association, July 4, 2005 (proposal 2005-022).     

青海省同仁县夏布浪铜铅锌矿床安山岩SHRIMP锆石U-Pb定年及其对成矿时代的制约

青海省同仁县夏布浪铜铅锌矿是近年来在秦祁昆结合部新发现的VMS型铜铅锌多金属矿床之一。该矿床为小型铜铅锌矿, 矿体规模变化较大, 呈浸染状、网脉状、条带状赋存于三叠系火山岩中;主要的金属矿物有黄铜矿、黄铁矿、辉锑矿、方铅矿、闪锌矿;围岩蚀变有绿泥石化、碳酸盐化、硅化等, 其中硅化蚀变与成矿作用关系最为密切, 且蚀变带范围随矿体厚度变化而变化。含矿安山岩SHRIMP 锆石U-Pb年龄为240.1±2.4 Ma(MSWD=0.31), 说明夏布浪矿区内安山岩形成时代为中三叠世。结合前人对区域内三叠纪岩浆活动的研究成果, 认为该矿的形成与火山活动密切相关, 其成矿时代与安山岩形成时代一致, 且该矿床形成于古特提斯洋在中三叠世向北俯冲过程中的大陆边缘弧环境。     

A hydrothermal investigation of the system FeO, Fe2O3, TiO2

Phase relations in the system FeO---Fe₂O₃---TiO₂, at temperatures ranging between 300°C and 700°C, have been investigated experimentally with special refference to the reaction Fe₃O₄ + TiO₂ = Fe₂O₃ + FeTiO₃. Pressure was varied between 500 and 2000 bars but its effect was negligible. Magnetite and rutile are the stable assemblage at temperatures above 550 dgC, and hematite and ilmenite are stable for lower temperatures. The equilibrium oxygen fugacity is estimated to be 10^−17.5 bars at equilibrium temperature. It is suggested that intermediate hematite-ilmenite solid solutions are inhomogeneous, consisting of ‘domains’ of hematite and ilmenite. The ‘domains’ are too small to be resolved by X-ray diffraction techniques. The top of the solvus curve in the hematite-ilmenite solution corresponds to a temperature of 660°C. Regular solution theory is not applicable to the solid solution.     

C02-CH4流体与金成矿作用：以阿尔泰山南缘和穆龙套金矿为例

造山型金矿的成矿作用与H20-CO2流体有着密切的联系。然而对阿尔泰山南缘和穆龙套金矿的流体包裹体研究表明，无水的CO2-CH4流体在中亚成矿域中一些金矿床中具有同样重要意义。阿尔泰山南缘萨热阔布金矿包裹体的Xch4达0.20～0.23，穆龙套金矿的XCH4为0.07～0.23。CH4扩大了流体不混溶的范围，有利于对Au的富集沉淀。CO2流体在Au成矿中的重要作用至少包括了三方面的意义，即：缓冲流体PH值范围、提高流体中的Au含量并使其维持与还原硫的络合作用进行迁移；扩大超临界流体的温度范围；增加流体不混溶的区域。CH4的加入扩大了流体不混溶的范围，有利于对Au的富集沉淀。     

Geochemistry of high H2 and CH4 vent fluids issuing from ultramafic rocks at the Rainbow hydrothermal field (36°14′N, MAR)

The Flores diving cruise was part of the MAST III-AMORES (1995-1998) program funded by the European Union. One of the major achievements of the Flores cruise was the discovery of the Rainbow hydrothermal field hosted in ultramafic rocks south of the Amar segment on the Mid-Atlantic ridge (MAR). The Rainbow hydrothermal fluids exhibit temperatures of 365 °C, pH of 2.8, high chlorinity (750 mmol/kg), and low silica (6.9 mmol/kg). The uniformity in endmember major, minor, trace element concentrations and gas contents suggests that all Rainbow fluids originate from the same deep source. Although H₂S content is relatively low (1.20 mmol/kg), all vent fluids show extraordinary high H₂ (16 mmol/kg), CH₄ (2.5 mmol/kg) and CO (5 μmol/kg) endmember concentrations compared to fluids collected from other vent sites along the MAR. Hydrogen represents more than 40% of the total gas volume extracted from the fluids. At Rainbow, H₂ production is likely associated with alteration of olivine and orthopyroxene minerals during serpentinization. Given that exposures of ultramafic rock may be common, particularly along slow-spreading ridges, the production of H₂ may have important implications for microbial activity at and beneath the seafloor.     

“东川式“层状铜矿40Ar-39Ar成矿年龄测定

本文采用40Ar-39真空击碎技术和阶段加热技术,测定了采自落雪矿的"东川式"层状铜矿之两个石英样品的年龄,获得了810～770 Ma的40Ar-39Ar等时线年龄,这些年龄与我们从前获得的脉状铜矿石英的年龄范围一致,再次表明晋宁-澄江期是东川铜矿的主要成矿期.     

Ar/Ar dating of hydrothermal activity, biota and gold mineralization in the Rhynie hot-spring system, Aberdeenshire, Scotland

This study presents a new high-precision ⁴⁰Ar/³⁹Ar age for the Devonian hot-spring system at Rhynie. Hydrothermal K-feldspar sampled from two veins that represent feeder conduits and a hydrothermally altered andesite wall rock, date the hydrothermal activity, the fossilised biota, and syn - K-feldspar gold mineralization at 403.9 ± 2.1 Ma (2σ). Oxygen isotope data for the parent fluid (−4‰ to 2‰) show that the K-feldspar was precipitated from a dominantly meteoric fluid, which mixed with magmatic fluids from a degassing magma chamber.The ⁴⁰Ar/³⁹Ar age (403.9 ± 2.1 Ma [2σ]) when recalculated (407.1 ± 2.2 Ma [2σ]) with respect to the astronomically tuned age for Fish Canyon sanidine (28.201 ± 0.023 Ma [1σ]), also provides a robust marker for the polygonalis-emsiensis Spore Assemblage Biozone within the Pragian-?earliest Emsian. Furthermore, the age identifies the Devonian pull-apart volcano-sedimentary basins of the British and Irish Caledonides (and their root zones), as specific targets for future gold exploration.     

Actinide crystal-liquid partitioning for clinopyroxene and Ca3(PO4)2

Using fission and alpha track radiography techniques, we have measured partition coefficients (D) for the actinide elements Th, U and Pu between diopsidic clinopyroxene, whitlockite [β-Ca₃ (PO₄)₂] and silicate liquid at 20kbar. Equilibrium partitioning at the crystal-liquid interface is assumed, and corrections for actinide zoning have been applied to the measured D values. Reproducibility for both actinide and minor element D values is carefully examined as a criterion for crystal-liquid interface equilibrium. The data are mostly compatible with interface equilibrium except for experiments at high cooling rates ( ? 30 deg/hr). Partition coefficients for Th/U/Pu of about 0.002/0.002/0.06 are measured for clinopyroxene and 1.2/0.5/3.4 for whitlockite. At an oxygen fugacity of 10^?8.5, Pu is much more readily incorporated into the crystalline phases than is U or Th because of the importance of trivalent Pu. The D_Pu(cpx) is similar to D(cpx) of the light rare earths supporting the concept of Pu/(rare earth) dating.     

Solubility of Fe-ettringite (Ca6[Fe(OH)6]2(SO4)3 · 26H2O)

The solubility of Fe-ettringite (Ca₆[Fe(OH)₆]₂(SO₄)₃ · 26H₂O) was measured in a series of precipitation and dissolution experiments at 20 °C and at pH-values between 11.0 and 14.0 using synthesised material. A time-series study showed that equilibrium was reached within 180 days of ageing. After equilibrating, the solid phases were analysed by XRD and TGA while the aqueous solutions were analysed by ICP-OES (calcium, sulphur) and ICP-MS (iron). Fe-ettringite was found to be stable up to pH 13.0. At higher pH-values Fe-monosulphate (Ca₄[Fe(OH)₆]₂(SO₄) · 6H₂O) and Fe-monocarbonate (Ca₄[Fe(OH)₆]₂(CO₃) · 6H₂O) are formed. The solubilities of these hydrates at 25 °C are:      

Solubility of pyromorphite Pb5(PO4)3Cl-mimetite Pb5(AsO4)3Cl solid solution series

Pyromorphite Pb₅(PO₄)₃Cl and mimetite Pb₅(AsO₄)₃Cl are isostructural minerals with apatite. Due to their high environmental stability, they have gained considerable attention as metals sequestration agents in water treatment and contaminated soil remediation. Pyromorphite and mimetite can form a continuous solid solution series in near-Earth surface environments. Precipitation of the end members and intermediate members of the series is likely to occur in the areas where the cost-effective in situ immobilization reclamation method, based on phosphate amendments, is applied. In contrast to the widely studied thermodynamic parameters of pyromorphite and mimetite, knowledge of the thermodynamics of their solid solutions is sparse. To supplement the data, a number of compounds from the pyromorphite-mimetite series were synthesized at room temperature using a method to simulate the conditions in the near-Earth surface environments. Afterwards, batch dissolution and dissolution-recrystallization experiments of seven synthesized precipitates were conducted at 25 °C, pH = 2 and in a 0.05 M KNO₃ background electrolyte. The experiments were carried out for a period of 6 (dissolution) and 14 (dissolution-recrystallization) months. A plateau in the [Pb] evolution patterns was used to determine equilibrium. All seven dissolutions were congruent, and the ionic activity products (IAP) of the minerals from the pyromorphite-mimetite solid solution series were calculated based on the dissolution reaction: . The IAPs for pyromorphite and mimetite exhibit a significant difference in values over three orders of magnitude between approximately 10⁻⁷⁹ for pyromorphite and approximately 10⁻⁷⁶ for mimetite. The series appeared to be ideal, and Lippmann and Roozboom diagrams were used for better understanding of its thermodynamics. The results indicated a strong tendency of pyromorphite to partition into the solid phase in the series, which explains some of the naturally observed phenomena. The improvement of the lattice stability of the mimetite due to isostructural phosphate substitutions in anionic sites was observed. The thermodynamic data reported in this study supplement existing databases used in geochemical modeling.     

粤北瑶岭钨矿成矿相关花岗岩的锆石SHRIMP年龄与40Ar/39Ar成矿年龄及其地质意义

粤北瑶岭钨矿区存在石英脉型黑钨矿和矽卡岩型白钨矿两种成矿类型,与石英脉型黑钨矿成矿同期形成的白云母的40Ar/39Ar年龄为(149.44±0.73)Ma,与华南中生代燕山期大规模的W、Sn成矿作用的年龄一致,代表石英脉型黑钨矿的成矿年龄.与石英脉型黑钨矿成矿相关的隐伏灰白色黑云母花岗岩的SHRIMP锆石年龄为(158...     

K-H3OFe3(SO4)2(OH)6铁矾的XRD研究

根据X射线衍射(XRD)分析发现: A Fe₃(SO₄)₂(OH)₆(A=K⁺、H₃O⁺)系列铁钒的XRD数据十分相近,难以用XRD区别,需通过能谱(EDS)辅助分析,才能区分此类铁矾。另外,此类铁矾的003和107面网间距d随K⁺含量增大而增大,且呈一元三次方程的关系;而033和220面网间距d随K⁺含量增大而减小,呈一元二次方程的关系。对该现象从铁矾晶体结构方面进行解释:K⁺、H₃O⁺离子位于较大空隙中,且沿着Z轴方向排列,当K⁺、H₃O⁺离子之间相互替换时,会导致该铁矾晶体结构在Z轴方向有较明显的变化。     

Free energy of formation for green rust sodium sulphate (NaFe6Fe3(OH)18(SO4)2(s))

In a recent study, sulphate-bearing green rust (GR_SO4) was shown to incorporate Na⁺ in its structure (NaFe^II₆Fe^III₃(OH)₁₈(SO₄)_2(s); GR_Na,SO4). The compound was synthesised by aerial oxidation of Fe(OH)_2(s) in the presence of NaOH. This paper reports on its free energy of formation .Freshly synthesised GR_Na,SO4 was titrated with 0.5 M H₂SO₄ in an inert atmosphere at 25 °C, producing dissolved Fe²⁺ and magnetite or goethite. Solution concentrations, PHREEQC and the MINTEQ database were used to calculate reaction constants for the reactions:

     

Molecular isotopic heterogeneity of fossil organic matter: implications for δCbiomass and δCpalaeoatmosphere proxies

The degree of isotopic variation in fossil organic matter renders bulk δ¹³C signatures strongly influenced by molecular isotopic heterogeneity. For example, in fossil wood the relative abundance of less depleted ¹³C moieties, i.e. preserved ¹³C enriched polysaccharides versus the relatively ¹³C depleted lignin moieties, can be seen to significantly bias δ¹³C_{fossil wood} values. Moreover the variation in δ¹³C values of specific compounds within fossil material are themselves highly variable and reflect the heterogeneity in isotopic values of different carbon atoms within individual compounds. For studies using δ¹³C values of fossil plant material as proxies (e.g., for δ¹³C_{palaeoatmosphere}, δ¹³C_biomass) it is recommended that the biases introduced through molecular heterogeneity, preservation type and taxonomic status of the fossil material are determined initially. Biases inherent in the bulk signature can then be reduced, rendering this value more robust. Alternatively, compound specific stable carbon isotope measurements of individual moieties preserved through geological time might prove to be an alternative proxy for monitoring changes in the bulk δ¹³C value of the plant and might reveal atmospherically induced trends.