Mineralogy and geochemistry of a Late Permian coal in the Dafang Coalfield, Guizhou, China: influence from siliceous and iron-rich calcic hydrothermal fluids

This paper describes the influence of siliceous and iron-rich calcic low-temperature hydrothermal fluids (LTHF) on the mineralogy and geochemistry of the Late Permian No. 11 Coal (anthracitic, R_r=2.85%) in the Dafang Coalfield in northwestern Guizhou Province, China. The No. 11 Coal has high contents of vein ankerite (10.2 vol.%) and vein quartz (11.4 vol.%), with formation temperatures of 85 and 180 °C, respectively, indicating that vein ankerite and vein quartz were derived from low-temperature calcic and siliceous hydrothermal fluids in two epigenetic episodes. The vein quartz appears to have formed earlier than vein ankerite did, and at least three distinct stages of ankerite formation with different Ca/Sr and Fe/Mn ratios were observed.The two types of mineral veins are sources of different suites of major and trace metals. Scanning electron microscope and sequential extraction studies show that, in addition to Fe, Mg, and Ca, vein ankerite is the dominant source of Mn, Cu, Ni, Pb, and Zn in the coal, and the contents of these five elements are as high as 0.09% and 74.0, 33.6, 185, and 289 μg/g, respectively. In contrast, vein quartz is the main carrier mineral for platinum-group elements (PGEs) Pd, Pt, and Ir in the coal, and the contents of Pd, Pt, and Ir are 1.57, 0.15, and 0.007 μg/g, respectively. Sequential extraction showed a high PGE content in the silicate fraction, up to 10.4 μg/g Pd, 1.23 μg/g Pt, and 0.05 μg/g Ir, respectively. It is concluded that the formation of ankerite and quartz and the anomalous enrichment of trace elements in the No. 11 Coal in the Dafang Coalfield, Guizhou, result from the influx of calcic and siliceous low-temperature hydrothermal fluids.     

Oxygen and Carbon Isotope Study of Calcite and Dolomite in the Disseminated Au-Ag Telluride Bulawan Deposit, Negros Island, Philippines

Abstract: The disseminated Au‐Ag telluride Bulawan deposit, Negros island, Philippines, is hosted by dacite porphyry breccia pipes which formed in a Middle Miocene dacite porphyry stock. Electrum and Au‐Ag tellurides occur mostly as grains intergrown with or filling voids between sphalerite, pyrite, chalcopyrite, galena and tennantite. Calcite, quartz and rare dolomite are the principal gangue minerals. Four types of alteration were recognized in the deposit, namely; propylitic, K‐feldspar‐sericitic, sericitic and carbonate alteration. Carbonate alteration is correlatable to the gold deposition stage and occurs mostly along fault zones. The δ¹⁸O and δ¹³C compositions of calcite and dolomite in propylite zone and ore‐stage dacite porphyry breccia were determined. The δ¹⁸O values of calcite in propylitized andesite range from +12.2 to +14.7%, and their δ¹³C values range from ‐6.1 to ‐1.0%. The δ¹⁸O values of calcite and dolomite in sericite‐ and carbonate‐altered, mineralized dacite porphyry breccia and dacite porphyry rocks range from +15.1 to +23.1%, and the δ¹³C values of calcite and dolomite range from ‐3.9 to +0.9%. The δ¹⁸O and δ¹³C values of the hydrothermal fluids were estimated from inferred temperatures of formation on the basis of fluid inclusion microthermometry. The δ¹⁸O values of hydrothermal fluid for the propylitic alteration were calculated to be +8.5 ‐ +9.5%, assuming 375°C. On the other hand, the δ¹⁸O values of ore solutions for base metal and Au mineralization were computed to be +13.6 ‐ +14.6%, assuming 270°C. The hydrothermal fluids that formed the Bulawan deposit are dilute and ¹⁸O‐enriched fluids which reacted with ¹⁸O‐ and ¹³C‐rich wallrocks such as limestone.     

可可西里盆地东部五道梁群热水湖相成因新认识

五道梁地区位于青藏高原北部可可西里盆地东部,其中新世发育一系列古湖泊,保存有大套碳酸盐沉积。本文通过对五道梁北山含叠层石剖面和南部剖面进行矿物学、元素地球化学研究,发现叠层石剖面主要矿物为方解石和少量石英,而南侧剖面则含有铁白云石、方解石、石英和钠长石。铁白云石和钠长石次生加大边的发现说明该区曾受热水活动的影响。元素分析结果也显示As、Sb、Ba、Fe等热水沉积标志元素含量较高,且Ni/Co、Mn/Sr、V/Cr、V/Sc等比值也较高;加之稀土元素配分模式和碳氧同位素特征均表明该地区为热水湖相沉积。另外叠层藻的出现也反映当时湖水温度至少为20~30℃。综合各种分析结果说明五道梁群为热水湖相成因,该区中新世发育有大量火山岩,因此可作为下一步寻找火山沉积型硼矿床重要线索。     

白云凹陷第三系储层中铁白云石的成因机理及与CO2活动的关系

白云凹陷第三系储层中发育大量的铁白云石,受研究区热流背景的影响,铁白云石主要见于高地温梯度地区埋深1000～3000m、地层温度60～130℃的浅—中部地层中及CO_2热流体活动区域。铁白云石的δ~(13)C值(-2.83‰～-1.83‰)具有无机成因的特征,与研究区气藏中幔源岩浆成因CO_2的δ~(13)C值较为一致,铁白云石的δ~(18)O值(-9.45‰～-5.37‰)和~(87)Sr/~(86)Sr值(0.7101～0.7161)也反映了其沉淀受到深部热流体活动的影响。以两口典型CO_2气井为例,储层中流体包裹体均一温度及蒙脱石向伊利石的演化特征证明储层经历了热流体侵入;CO_2热流体活动区域不仅是铁白云石集中分布地带,并出现片钠铝石+铁白云石+菱铁矿等示踪CO_2运移、聚集的自生矿物组合。地层中铁白云石、高岭石含量与气藏中CO_2的含量呈正相关关系,绿泥石含量与CO_2、铁白云石含量呈反消长关系。高地温梯度地区丰富的CO_2热流体活动是该地区储层中铁白云石沉淀与含量高的重要原因,无机岩浆成因CO_2是铁白云石沉淀的主要碳源,CO_2热流体充注造成绿泥石等黏土矿物异常转化,为铁白云石沉淀提供了所需的Fe~(2+)、Mg~(2+)离子。     

Secondary Ion Mass Spectrometry Bias on Isotope Ratios in Dolomite–Ankerite,Part II: δ13C Matrix Effects

This study is Part II of a series that documents the development of a suite of calibration reference materials for in situ SIMS analysis of stable isotope ratios in Ca‐Mg‐Fe carbonates. Part I explored the effects of Fe²⁺ substitution on SIMS δ¹⁸O bias measured from the dolomite–ankerite solid solution series [CaMg(CO₃)₂–CaFe(CO₃)₂], whereas this complementary work explores the compositional dependence of SIMS δ¹³C bias (calibrated range: Fe# = 0.004–0.789, where Fe# = molar Fe/(Mg+Fe)). Under routine operating conditions for carbonate δ¹³C analysis at WiscSIMS (CAMECA IMS 1280), the magnitude of instrumental bias increased exponentially by 2.5–5.5‰ (session‐specific) with increasing Fe‐content in the dolomite structure, but appeared insensitive to minor Mn substitution [< 2.6 mole % Mn/(Ca+Mg+Fe+Mn)]. The compositional dependence of bias (i.e., the matrix effect) was expressed using the Hill equation, yielding calibration residual values ≤ 0.3‰ relative to CRM NBS‐19 for eleven carbonate reference materials (6‐μm‐diameter spot size measurements). Based on the spot‐to‐spot repeatability of a drift monitor material that ‘bracketed’ each set of ten sample‐spot analyses, the analytical precision was ± 0.6–1.2‰ (2s, standard deviations). The analytical uncertainty for individual sample analyses was approximated by combining the precision and calibration residual values (propagated in quadrature), suggesting an uncertainty of ± 1.0–1.5‰ (2s).     

河北小营盘石英—碳酸盐型金矿床成矿作用

石英—碳酸盐型金矿床是金的主要来源之一,在绿岩带金矿中占有重要地位。绿岩带金矿成矿时代古老(2.5—2.9 Ga),规模巨大,矿物成分简单而且稳定,发育石英、铁白云石或铁菱镁矿、绢云母、黄铁矿等围岩蚀变。而且铁白云石化蚀变在绿岩带金矿成矿中起重要作用,与韧性剪切带关系密切,铁白云石δ~(13)C值为-4±2‰,可能是地幔来源的标志。本项研究发现,小营盘金矿的铁白云石蚀变作用,携带了大量金等成矿物质沿着SN向张扭性断裂交代早期含金石英脉和糜棱岩,共同构成金的富矿体;含金铁白云石蚀变岩的δ~(13)C值平均为—4.13‰,Pb—Pb等时线年龄为2711±238 Ma。结合矿床产出的构造背景和成矿特征,可以初步确定小营盘金矿属于高级变质的绿岩带金矿,这是我国金矿地质学研究的一项新进展,希望有助于华北陆台与绿岩带有关矿产的研究和找矿及国际对比。     

黔东南石英脉型金矿床中铁白云石流体包裹体研究

铁白云石是黔东南石英脉型金矿主成矿阶段的主要脉石矿物之一,与金的矿化关系十分密切,在金的运移、沉淀等方面起着重要作用,其流体包裹体特征可以反映成矿流体性质。通过对铁白云石开展系统的流体包裹体岩相学观察、均一法测温和冰点测定,计算出包裹体盐度和密度等数据。结果表明: 铁白云石包裹体较为发育,以含CO₂的包裹体为主; 均一温度集中在240~300 ℃范围内,平均均一温度为267.21 ℃; 成矿流体的盐度为7.31%~21.40%(NaCl),平均为15.31%(NaCl); 成矿流体的密度介于0.72~0.97 g/cm³之间,平均为0.89 g/cm³。认为黔东南石英脉型金矿床属于低盐度、高密度的中温热液矿床。     

蒙古国塔木察格盆地塔南凹陷铜钵庙组火山碎屑岩中片钠铝石胶结物的成因

塔木察格盆地塔南凹陷铜钵庙组火山碎屑岩中发育大量的片钠铝石自生矿物。通过偏光显微镜、扫描电镜及X射线衍射分析等,查明了火山碎屑岩中的胶结物与自生矿物类型和成岩共生序列。含片钠铝石火山碎屑岩的成岩共生序列为粘土包壳-方解石-一期微晶石英-一期高岭石-二期微晶石英、二期高岭石、片钠铝石-铁白云石;通过MAT253稳定同位素质谱仪确定了片钠铝石和铁白云石的稳定同位素组成为片钠铝石的δ¹³C_PDB为-8.15‰~-2.81‰,与片钠铝石平衡的CO₂的δ¹³C_CO2为-12.91‰~-7.55‰,通过与海拉尔盆地及BGS盆地系碳氧同位素数据的类比,表明片钠铝石中的碳主要为幔源岩浆来源,形成片钠铝石的钠和铝主要来源于安山岩岩屑、长石晶屑碎屑、玻屑和火山灰等;铁白云石的δ¹³C_PDB为-6.76‰~-2.65‰,与片钠铝石的碳氧同位素数据相似,结合相关地质实例及地球化学模拟实验,可以推断铁白云石中的碳也是幔源岩浆来源,铁白云石中的铁离子主要来源于安山岩岩屑、玻屑、火山灰和蒙脱石等矿物。     

Secondary Ion Mass Spectrometry Bias on Isotope Ratios in Dolomite–Ankerite,Part I: δ18O Matrix Effects

We document the development of a suite of carbonate mineral reference materials for calibrating SIMS determinations of δ¹⁸O in samples with compositions along the dolomite–ankerite solid solution series [CaMg(CO₃)₂–CaFe(CO₃)₂]. Under routine operating conditions for the analysis of carbonates for δ¹⁸O with a CAMECA IMS 1280 instrument (at WiscSIMS, University of Wisconsin‐Madison), the magnitude of instrumental bias along the dolomite–ankerite series decreased exponentially by ~ 10‰ with increasing Fe content in the dolomite structure, but appeared insensitive to minor Mn substitution [< 2.6 mol% Mn/(Ca+Mg+Fe+Mn)]. The compositional dependence of bias (i.e., the sample matrix effect) was calibrated using the Hill equation, which relates bias to the Fe# of dolomite–ankerite [i.e., molar Fe/(Mg+Fe)] for thirteen reference materials (Fe# = 0.004–0.789); for calibrations employing either 10 or 3 μm diameter spot size measurements, this yielded residual values ≤ 0.3–0.4‰ relative to CRM NBS 19 for most reference materials in the suite. Analytical precision was ± 0.3‰ (2s, standard deviations) for 10‐μm spots and ± 0.7‰ (2s) for 3‐μm spots, based on the spot‐to‐spot repeatability of a drift monitor material that ‘bracketed’ each set of ten sample‐spot analyses. Analytical uncertainty for individual sample analyses was approximated by a combination of precision and calibration residual values (propagated in quadrature), suggesting an uncertainty of ± 0.5‰ (2s) for 10‐μm spots and ± 1‰ (2s) for 3‐μm spots.     

热水沉积铁白云石微斜长石岩的发现及其找矿意义

铁白云石微斜长石岩作为一种特殊岩石类型,在辽东元古宙裂谷块状硫化物矿床中与成矿关系密切。岩石呈韵律层状,富含Ｋ、Ｂ、Ｓｉ,在Ａｌ２Ｏ３—ＳｉＯ２—（ＣａＯ＋ＭｇＯ）和Ｆｅ—Ｍｎ—（Ｃｕ＋Ｎｉ＋Ｃｏ）三角图上均落入热水沉积岩区。稀土元素具有铈负异常、轻稀土元素富集等特征。硅同位素地球化学显示该岩石为热水沉积成因。此类岩石做为一种热水沉积岩具有重要的找矿意义,依据这一标志在老矿山外围已经找到了硫化物矿体。