Pyrite framboids and their development: a new conceptual mechanism

It has been suggested that the two morphologies of sedimentary pyrite, framboids and euhedra, may reflect two distinct pathways of pyrite formation. Framboids form indirectly via iron monosulphides, whereas euhedra form from direct precipitation from solution. A third pathway which is bridging these two forms is proposed here, namely the continuous growth from a monosulphide globule through framboids to a euhedral single crystal. It is also suggested that framboids probably occur over a range of three orders of magnitude, from the least complex microframboids through framboids to polyframboids.Dedicated to Professors G. C. Amstutz and L. G. Love for their unrivalled contribution to the knowledge of pyrite framboids     

Sulfide minerals in Coal Bed V,minnehaha mine,Sullivan County,Indiana

Polished and thin section examinations of samples from Indiana Coal Bed V (Springfield) have shown three sulfides to be present; namely pyrite, marcasite and sphalerite. Pyrite and marcasite are dominant forms whereas sphalerite is very minor. These sulfides appear to have formed in four distinct stages as judged on the basis of mineralogy and mineral texture. Pyrite occurs as framboids throughout the coal seam, as fibrous crystals in two horizons of the coal and in massive form as cleat fillings and cell fillings in fusinite and semi-fusinite. Marcasite occurs in spherical polycrystalline and twinned grains, as polycrystalline overgrowths on framboids, as cementing material for clusters of framboids, as blocky polycrystalline grains and with pyrite as cell fillings in fusinite and semi-fusinite. Sphalerite occurs exclusively as cell fillings in semi-fusinite. The paragenetic sequence indicates fluctuations in the overall coal bed chemistry. Individual sections display evidence of chemical variation on the micro scale.     

遗迹化石Rhizocorallium中莓状黄铁矿对古环境古生态的指示--以豫西南上泥盆统为例

豫西南淅川上泥盆统王冠组地层中发育大量与层面平行且具有蹼纹的U形遗迹化石Rhizocorallium。利用环境扫描电镜对Rhizocorallium进行微观观察,发现在其边缘管和蹼纹内部发育大量不同形态的莓状黄铁矿及莓状铁氧化物（单晶为五角十二面体,八面体,立方体和近球形）,与之对应的围岩中仅见少量黄铁矿单晶颗粒。表面具有覆盖膜的莓状黄铁矿大多存在于潜穴内部,其中边缘管中莓状黄铁矿的单晶直径（0.672~1.603 μm,平均直径1.063 μm）较之蹼纹中部的（0.376~0.877 μm,平均直径0.5 μm）的大。上述特征显示出潜穴中莓状黄铁矿的存在可能与硫酸盐类还原菌有关。Rhizocorallium边缘管和蹼纹中高丰度莓状黄铁矿的发现表明:遗迹化石Rhizocorallium可能是造迹者精心构筑的觅食-花园。由于食物供应和氧化还原条件的不同,Rhizocorallium造迹者在其潜穴内部培植不同的微生物,形成一个互利共生的群落。     

Formation process of pyrite polyframboid based on the heavy-metal analysis by micro-PIXE

Pyrite framboid in sedimentary rocks could be concerned with arsenic contamination in groundwater of acidic environment and has been studied for the formation process of its unique morphology. However, not much has been discussed about the formation process based on the heavy-metal distribution in pyrite framboids and their aggregates. To reveal the formation process of pyrite framboids and their aggregates, mudstone from the Late Cretaceous Hakobuchi Group, central Hokkaido, Japan, are investigated for mode, petrographical, mineralogical, and micro-PIXE (particle-induced X-ray emission) analysis in this study. Spherical and sub-spherical pyrite framboids observed in polyframboids can be divided into two types based on the diameter of framboids (D) and the average diameter of microcrystals (d) within framboids: type 1, ranging from 2 to 9 μm and from 0.4 to 0.9 μm, respectively, and type 2, ranging from 8 to 50 μm and from 0.5 to 1.8 μm, respectively. Based on the quantitative traverse analyses and 2-D elemental mapping results by micro-PIXE, heterogeneities in the concentrations of heavy metals within the analyzed aggregations of pyrite are exhibited. On the basis of the As and Pb zoning patterns, the time range and chronological stages of pyrite-aggregation growth are revealed.     

Syngenetic sulphide minerals in a copper-rich bog

Heavy mineral separates of peat from a mineralotrophic bog contain sulphide minerals with distinctive textures. Pyrite framboids, consisting of spherical aggregates of subhedral pyrite crystals, are surrounded by a thin rim of chalcopyrite or a layer of massive marcasite. Clusters of framboids are cemented by covellite which also occurs as small idiomorphic grains, with rectangular or hexagonal outlines, surrounded by chalcopyrite. The sulphides appear to have resulted from discharge of groundwaters, enriched in copper from weathering of primary sulphides in bedrock and in iron by reduction of the till underlying the peat, into the hydrogen sulphide charged bog.     

草莓状黄铁矿的形成机制探讨及其对古氧化-还原环境的反演

【研究目的】草莓状黄铁矿广泛存在于现代沉积物和沉积岩中,其成因机制总体上分为有机成因和无机成因两种,尽管两种机制均有理论与实验的支撑,但尚未建立一种具有普遍意义的形成机制。【研究方法】本文对目前草莓状黄铁矿的形成机理、氧化还原环境的应用及后期环境变化的影响进行了系统的综合研究。【研究结果】不同氧化-还原环境下形成的草莓状黄铁矿在粒径、形态以及硫同位素之间均存在较大的差异,可做为反演古氧化-还原环境的指标。草莓状黄铁矿的微晶尽管与粒径具有一定的正相关性,但是两者在形态演化序列、生长模式、聚集因素等方面与古氧化-还原环境的关系尚不清楚。仅凭草莓状黄铁矿粒径与铬还原法测定的硫同位素反演古氧化-还原环境存在一定的局限性,需要其他指标综合判定,尚需进一步开展草莓状黄铁矿原位硫同位素值与粒径对古氧化-还原环境反演的研究。后期氧化可使草莓状黄铁矿表面化学成分发生变化,但粒径分布依然具有古氧化-还原环境的指示意义。【结论】草莓状黄铁矿的实验模拟、理论体系和多学科交叉的研究中仍存在一些问题,尚需进一步研究。     

草莓状黄铁矿微晶形态和成分的地质意义——以栖霞组含泥灰岩为例

在湖北省京山县雁门口地区二叠世栖霞组上部的含泥灰岩中发现棘皮动物化石,其腔被不同形态微晶的草莓状黄铁矿充填,有正四面体、正六面体、五角十二面体和近球体。溶解氧与草莓状黄铁矿的形成过程有关,其浓度决定微晶的S/Fe。统计显示,黄铁矿的S/Fe平均值随微晶的边数增加而增加,所以,棘皮动物腔内草莓状黄铁矿形成由早及晚的次序为：近球体微晶,五角十二面体微晶,正六面体微晶,正四面体微晶的草莓状黄铁矿。同一环境中,黄铁矿微晶的S/Fe可用来指示形成次序。     

Nannobacteria and the formation of framboidal pyrite: Textural evidence

Study of sedimentary pyrite in the form of framboids, euhedral crystals or metasomatic masses has revealed that their surfaces are commonly covered with spheroids of about 50 nm. This applies to all the examples studied, from modern to Proterozoic. These spheroids are interpreted as the pyritized corpses of nannobacterial cells; if correct, this indicates that precipitation of iron sulfide was performed by these dwarf forms of bacteria, often associated with decaying organic matter.     

原始黄铁矿莓体的发现与研究

用扫描电子显微镜研究晋东南太原组下部黄铁矿矿石和煤岩中的黄铁矿,发现许多原始莓体保留着形成时的特征。这些特征反映出原始莓体大多数为硫磺细菌化石,少数由胶体形成。本文对莓体的成因、特征、形成环境等进行了论述。     

广西宁明组植物化石中黄铁矿及其沉积意义

对化石中的黄铁矿进行研究,有助于明确生物的化石化过程以及期间的沉积微环境。利用光学显微镜和扫描电镜,对广西宁明组植物化石中保存的黄铁矿进行了分析,发现离散型单晶和成群的莓状体共同保存。单晶绝大多数为无规则至球状体,晶棱不明显,表面可见凹点;少数为八面体,晶棱明显,表面光滑;单晶直径为0.79~1.58 μm;莓状体为圆球状,粒径为7.23~14.95 μm,S/Fe原子个数比的均值为1.54。莓状体的粒径大小和变化幅度均处于低值段,其S/Fe原子个数比值小于2,结果均说明当时植物体上、下表皮间为一种贫氧的水体环境,并在短时间内形成了莓状体。植物化石上、下表皮间由于未保存组织结构,而被大量的、近似层状分布的黄铁矿单晶和莓状体充填,结果支持了化石内莓状体形成与有机质降解之间存在着必然联系。     

北大西洋Logatchev热液区多形貌黄铁矿特征及其意义

北大西洋Logatchev热液区产出的黄铁矿形貌丰富、成分各异,极具特殊性和代表性.运用扫描电镜和电子探针系统观测黄铁矿矿物学特征,发现粒状黄铁矿粒径不一,具高Fe、S,低微量元素的特点;草莓状黄铁矿见有松散莓体、球形-次球形莓体和自形结构莓体,其Cu含量总体较高,不同晶体特征的莓体成分存在差异;胶状黄铁矿见有多层环带,内核到环带由纳微米晶体聚合生成,由内到外成分具有S/Fe比、Zn含量减小,As含量增大的趋势.分析认为早期粒状黄铁矿是在较高温度下的热液体系中直接形成,随热液作用衰减,生成的粒状黄铁矿多呈纳-微米晶产出;草莓状黄铁矿是由松散纳-微米晶逐步聚集形成,受溶液过饱和度影响,莓体粒度和聚集程度存在差异;胶状黄铁矿多晶聚集环带生长方向是由内向外的,聚集程度差异指示沉积环境的反复交替.研究区多形貌黄铁矿具有由分散的微晶→多晶聚合体→自形单晶的完整演化系列特征,对于解读现代海底热液活动的方式和特点,揭示纳米晶体-宏观晶体的演化过程有积极意义.      

沉积地层中草莓状黄铁矿分析方法及其在古海洋学上的应用

草莓状黄铁矿是黄铁矿的特殊形态,其定义为由相近大小、相似形态的黄铁矿微晶颗粒组成的球形、亚球形聚合体。草莓状黄铁矿粒径分析已广泛应用于各个地质历史时期的古海洋环境恢复研究中,但其形成机理、判别标准与实验方法仍存在分歧。因此对沉积地层中草莓状黄铁矿的形成机理、在古海洋环境恢复中的指示意义及判别标准、实验与数据分析方法等进行总结阐述,有助于理解草莓状黄铁矿的粒径大小与形态对氧化还原条件的指示意义。草莓状黄铁矿在不同氧化还原环境下的形成机理存在差异,其粒径大小、数量以及分布范围可综合反映沉积时水体的氧化还原条件;而草莓状黄铁矿微晶几何形态及整体形貌特征也与古海洋氧化还原环境密切相关。此外,虽然有学者指出该方法可能存在一些问题,但只要在分析过程中结合沉积特征、古生态特征、地球化学指标等多方面证据对环境进行综合判别,甄别特殊条件下沉积的草莓状黄铁矿,则可有效避免这些问题。最后,针对后期氧化作用对草莓状黄铁矿粒径分布的影响进行了评价,结果显示经过后期氧化作用的草莓状黄铁矿粒径变化很小,不会对其在恢复古海洋氧化还原环境的应用上产生影响。     

沉积地层中的黄铁矿形态及同位素特征初探——以华南埃迪卡拉纪深水相地层为例

地质历史时期新元古代大气氧含量普遍较低。在硫酸盐还原细菌作用下,作为海洋重要的氧化性离子,陆源硫酸根离子有效促进了深层海水的氧化进程。在此过程中,硫元素在硫酸根和黄铁矿之间发生显著同位素分馏,其分馏程度可反推当时古海洋的氧化还原状态。沉积地层中的黄铁矿普遍具有多种形态,不同形态黄铁矿的形成环境多有不同。如草莓状黄铁矿多形成于底层缺氧水体或沉积物的浅表面,而大颗粒单晶黄铁矿或脉状黄铁矿则多沉积于成岩早期的沉积物孔隙或形成于成岩后期的热液改造。与草莓状黄铁矿不同,大颗粒单晶或脉状黄铁矿的硫同位素组成并不能反映沉积时期的古海洋氧化还原条件。判定沉积地层中不同形态的黄铁矿及形成过程,是获得有效反映海洋沉积环境硫同位素组成特征的基本前提。简要总结了地质历史时期沉积地层中的黄铁矿类型及矿物形成过程,并以华南埃迪卡拉纪蓝田组岩芯样品为例,识别出各个样品中的黄铁矿形态组成特征,对比分析了全岩黄铁矿与样品中大颗粒黄铁矿硫同位素组成差异。研究结果表明:不同岩性样品中黄铁矿的形态种类及含量均存在差异。页岩样品保存有更好形态的自形晶以及草莓状黄铁矿;碳酸盐岩样品中具有较多自形晶以及他形晶黄铁矿,并且其中的少量草莓状黄铁矿遭受后期成岩作用而发生不同程度的晶体蚀变。样品中大颗粒黄铁矿的硫同位素值（δ34S_L-pyr）通常显著高于全岩黄铁矿的硫同位素值（δ34S_T-pyr）,最大差值可达48.5‰。在利用黄铁矿的硫同位素组成来反推当时古海洋环境时,需要区分不同形态黄铁矿,仔细剔除大颗粒黄铁矿,降低成岩期黄铁矿对样品中硫同位素组成的影响。更细致的微区黄铁矿硫同位素分析工作将依赖于SIMS分析测试手段进行。     

Simulating experiment on the hydrothermal superimposing metallogenesis of the Dongguashan strata-bound copper deposit

Series of sedimentary hydrothermal-diplogenetic copper deposits have been found scattering in the region along the middle-lower reaches of the Yangtze River, and their metallogenetic mechanism is still in hot debate. In order to reveal the ore-forming kinetics of sedimentary process and hydrothermal superimposition, and evaluate the role of sedimentary pyrite in the enrichment and precipitation of copper, a set of simulating experiments on the reaction between pyrite and CuCl2 solution were conducted. According to the physicochemical characteristics of the ore-forming fluid of the Dongguashan copper deposit, Anhui Province, 100 MPa was selected as the experimental pressure, and the experimental temperatures were set at 450, 350, 250 and 150°C, respectively. The reactions between pyrite grains isolated from the Shimenkou strata-bound pyrite deposit and the solution with 0.2 mol/L CuCl2 and 1.0 mol/L NaCl were experimentally simulated. Then, variations in surface topography and surface chemistry of the experimental pyrite grains were documented using scanning electronic microscopy (SEM), atomic force microscopy (AFM), Auger electron spectrometry (AES) and X-ray photoelectron spectroscopy (XPS), and the solution and newly formed minerals were analyzed using inductively coupled plasma (ICP-AES) and X-ray diffraction (XRD) techniques. Desulphurization of pyrite surface was observed and new copper minerals were detected. It is proposed that pyrite can act as a geochemical barrier for the enrichment and precipitation of copper from the solution under the experimental conditions. Furthermore, the ore-forming mechanism of sedimentary hydrothermal-diplogenetic copper deposits was discussed.     

有孔虫壳体内草莓状黄铁矿成因及其地质意义——以湖北雁门口地区栖霞组有孔虫化石为例

在湖北省京山县雁门口地区栖霞组上部的含泥灰岩中存在丰富的节房虫科底栖有孔虫化石,主要有节房虫属、厚壁虫属和郎格虫属,壳体均被草莓状黄铁矿充填。对其系统的显微镜、扫描电镜观察和黄铁矿的能谱分析结果发现,黄铁矿草莓体直径最大为15 μm,平均约10 μm,硫铁原子比值（S/Fe）为1.90±0.10,表明在黄铁矿形成过程中,有孔虫壳体空腔内呈轻度- 中度贫氧的微环境。在分析该类黄铁矿成因的基础上,认为有孔虫壳体内的黄铁矿在指示沉积环境和保存环境方面具有局限性。     

Arsenic in framboidal pyrite from recent sediments of a shallow water lagoon of the Baltic Sea

Arsenic is a redox‐sensitive element of environmental relevance and often enriched in iron sulphides. Because sediments from the Achterwasser lagoon, a part of the estuarine system of the river Oder, south‐west Baltic Sea, show unexpectedly high pyrite concentrations of up to 7·5 wt% they were used to investigate the influence of authigenic pyrite on the mobility and burial of As in the coastal environment. Micro‐X‐ray‐fluorescence measurements of 106 micrometre‐sized pyrite framboids from the anoxic sediments show highly variable As concentrations ranging from 6 to 1142 μg g^?1. Even within a 1 cm thick layer, the As concentration of different framboids varies greatly and no clear depth trend is visible throughout the 50 cm long sediment core. Pyrite can account for 9 to 55% (average 22%) of the total As budget of the sediments and the degree of trace metalloid pyritization for As ranges from 26 to 61%, indicating that authigenic pyrite formation is an important process in the geochemical cycling of As in coastal sediments. High‐resolution micro‐X‐ray fluorescence mapping of single pyrite grains shows that As is distributed inhomogeneously within larger framboids, suggesting changing pore water composition during pyrite growth. X‐ray absorption near edge structure spectra indicate that As is usually present as As(‐I) substituting S in the pyrite lattice. However, in samples close to the sediment/water interface a considerable part of As is in higher valence states (+III/+V). This can be explained by frequent re‐suspension of the surficial sediments to the oxic water column due to wave action and subsequent re‐deposition, leading to the adsorption of As oxyanions onto pyrite. Although reduced As(‐I) becomes more important in the deeper samples, reflecting decreasing redox potential and a longer time since deposition, the occurrence of oxidized As species (AsIII/AsV) in pyrite in the anoxic part of the sediment suggests formation under dysoxic conditions.     

Sulfide minerals in Seelyville Coal III,Chinook Mine,Indiana

Sulfide minerals in coal bed III at the Chinook Mine, Indiana, are pyrite, marcasite, and rarely sphalerite. Pyrite occurs as framboids concentrated mainly in exinite, as bands or lenses in vitrinite and clay partings, as cell fillings in fusinite, and in cleats. Marcasite normally occurs in association with clusters of pyrite framboids within micro-organic remains. Sphalerite occurs exclusively in fusinite associated with cleat pyrite. The iron sulfides, which are of authigenic origin, were formed during the biochemical stage of coalification during the accumulation and compaction of peat. The factor that limited their formation in such an environment was the availability and reactivity of iron. Chemical heterogeneity in the peat swamps where the sulfides formed existed even on a microscopic scale. The iron sulfides were commonly precipitated in localized micro-environments that were favorable for their formation. The metamorphic stage of coalification did not affect the iron sulfides significantly, although it may have been responsible for the recrystallization of pyrite framboids and minor deformation of pyrite in fusinite and its local mobilisation.     

Notes on framboidal pyrite from Allandale New South Wales,Australia

Pyrite masses composed of compacted pyrite framboids in chalcedony in weathered andesites at Allandale, New South Wales, Australia, show evidence of colloidal origin and contemporaneous deposition of pyrite and silica. Free framboids and framboidal clusters in the chalcedony show indications of crystallization into pyrite polyhedra and pyrite octahedra.     

Pyrite characteristics and shale gas significance of the Niutitang Formation in Cengong area,Guizhou ProvinceSCIEI北大核心CSCD

黄铁矿特征研究可为页岩沉积环境恢复与页岩气富集保存规律预测提供依据。以贵州岑巩地区岑页1井牛蹄塘组为研究对象,基于岩心、薄片、扫描电镜及微量元素、硫同位素地球化学,确定牛蹄塘组页岩沉积环境及页岩气富集地质条件。研究表明,牛蹄塘组页岩黄铁矿发育为草莓状、自形-半自形及他形(主要为胶状他形)三种形态,不同形态的黄铁矿形成于不同沉积环境,草莓状黄铁矿形成于缺氧还原环境,自形-半自形黄铁矿形成于贫氧环境,胶状他形黄铁矿指示沉积过程有热液活动的参与。测试井牛蹄塘组整体处于较开放的沉积水体,上段为含氧-贫氧环境,硫同位素整体变轻且发生负漂;中段为较缺氧环境,硫同位素跨度大且发生正漂;下段为还原性更强的沉积环境,硫同位素小幅度负漂。黄铁矿含量与有机质富集密切相关,与黄铁矿有关的孔隙为页岩气吸附、保存及运移提供载体,且草莓状黄铁矿指示的缺氧硫化环境更利于有机质保存。研究工作系统梳理了黄铁矿对牛蹄塘组页岩沉积环境及储层页岩气富集的指示作用,为页岩气勘探提供指示。