Magnetite whiskers and platelets in the ALH84001 Martian meteorite: evidence of vapor phase growth

Nanometer-sized magnetite crystals associated with carbonates in fracture zones within Martian meteorite ALH84001 have been examined using analytical transmission electron microscopy. Some of the the crystals exhibit distinctive morphologies: filamentary rods and ribbons, and platelets. The rods and ribbons are elongated along the crystallographic [100] and [111] directions. Some of the rods contain microstructural defects indicating that they grew by spiral growth about screw dislocations. Platelets are flattened along the [100] and [110] directions. These unique morphologies and microstructures constrain the growth conditions of magnetite. The whiskers and platelets most likely formed in the temperature range 500–800°C by direct condensation from a vapor or precipitation from a supercritical fluid, and their properties are inconsistent with a biogenic origin.     

滇西老王寨金矿床黄铁矿形貌特征与化学组成

老王寨金矿床是三江特提斯成矿域中已探明规模最大的造山型金矿床,黄铁矿是其最主要的载金矿物,依据矿(化)脉切割关系、矿石结构构造及矿物共生组合,该矿床成岩-成矿期共发育5个世代黄铁矿。沉积-成岩期草莓状黄铁矿含Pb、Zn、Mn、Co、Ni和Bi。热液金成矿期可划分为:Ⅰ石英-绢云母-黄铁矿、Ⅱ石英-多金属硫化物、Ⅲ方解石-石英-毒砂-黄铁矿和Ⅳ方解石-石英-辉锑矿-黄铁矿四个阶段,其黄铁矿分别以粗粒他形、立方体、五角十二面体和立方体为主,总体继承了沉积-成岩期黄铁矿含Pb、Zn、Mn、Co、Ni和Bi的特征,Au、As、Sb和Cu也有不同程度富集,显示成矿流体成分复杂。Ⅲ阶段为金的主成矿阶段,以发育五角十二面体黄铁矿为特征,富集Au、As、Sb、Pb、Zn、Cu、Co、Ni和Bi,其中,Au与As构成 [Au, As]^2-和[Au(As, S₃)]^2-等络合物以类质同象的形式替代[S²]^2-而进入到黄铁矿中,两者呈正相关,成矿系统处于中-低温、流体过饱和度(硫逸度)高,且缓慢冷却,矿质来源充足的环境。     

Morphology and geochemistry of different pyrite types from the Upper Witwatersrand System of the Klerksdorp Goldfield,South Africa

The morphology of pyrites from the Proterozoic, auriferous and uraniferous conglomerates of the Upper Witwatersrand System of the Klerksdorp Goldfield (South Africa) was studied by means of scanning electron microscopy (SEM). The pyrite particles were recovered by hydrofluoric acid leaching, thus making a three-dimensional SEM examination possible. According to morphological criteria the pyrites were classified into three types. Trace-element analysis by atomic absorption spetrophotometry (Au, Co, Ni, Cu, Zn, Pb, Mn, As) and the statistical evaluation of the results confirmed the morphological classification:

Type 1: Authigenic, idiomorphic to hypidiomorphic pyrites or pyrite accumulations, which were formed in the conglomerates during diagenesis or metamorphism.

Type 2: Allogenic, rounded, compact pyrites. This type was eroded from primary deposits in the hinterland of the Witwatersrand basin and deposited with the Witwatersrand sediments. It shows the closest trace-element affinity to pyrites from the Barberton Mountain Land, the source area model for the Witwatersrand sediments. The recognition of this pyrite type from the Klerksdorp Goldfield is in agreement with observations on detrital compact pyrites described from other goldfields of the Witwatersrand.

Type 3: Allogenic, rounded, porous pyrites. These were formed from pyritic muds and iron sulfide gels existing on the surface of the alluvial fan, and later were reworked as mud balls or fragments and deposited with the conglomerates. Indentations with radial fracture patterns point to transport partly in a plastic state. The occurrence of colloform pyrites among this type supports the postulation of pyritic muds or iron sulfide gels. Only in this type of pyrite various inclusions such as gold, quartz, silicates, brannerite, copper- and titanium-bearing minerals were found. It is suggested that these inclusions were trapped as dust-like particles in the pyritic muds or iron sulfide gels on the surface of the alluvial fan. Only the presence of the allogenic, porous pyrites could be correlated with high gold values in the conglomerates.

The three-dimensional SEM examination of the pyrites has shown that the pyrite types described by previous authors from the Witwatersrand System can be classified into the three types of pyrite given here.     

Coupled trace element and SIMS sulfur isotope geochemistry of sedimentary pyrite:Implications on pyrite growth of Caixiashan Pb-Zn deposit

Colloform pyrite with core-rim texture is commonly deposited in carbonate platforms associated with the sulfide ores such as the Caixiashan Pb-Zn deposit.However,the genesis of colloform pyrite in Pb-Zn deposits,its growth controls and their geological implication are insufficiently understood.Integration of in-situ trace element and SIMS sulfur isotopes has revealed geochemical variations among these pyrite layers.These colloform pyrite occur as residual phases of core-rim aggregates,the cores are made up of very fine-grained anhedral pyrite particles,with some rims being made up of fine-grained and poorlycrystallized pyrite,while the other rims were featured with euhedral cubic pyrite.which are cemented by fine-grained calcite and/or dolomite with minor quartz.Sulfur isotope analysis shows that some wellpreserved rims have negative δ~(34)S values(-28.12‰to-0.49‰),whereas most of the cores and rims have positive δ~(34)S values(0 to+44.28‰;peak at+14.91‰).Integrating with the methane and sulfate were observed in previous fluid inclusion study,we suggest that the ~(34)S depleted rims were initially formed by bacteria sulfate reduction(BSR),whereas the positive δ~(34)S values were resulted from the sulfate reduction driven by anaerobic methane oxidation(AOM).The well-developed authigenic pyrite and calcite may also support the reaction of AOM.Combined with petrographic observations,trace element composition of the colloform pyrite reveals the incorporation and precipitation behavior of those high abundance elements in the pyrite:Pb and Zn were present as mineral inclusion and likely precipitated before Fe,as supported by the time-resolved Pb-Zn signal spikes in most of the analyzed pyrite grains.Other metals,such as Hg,Co and Ni,may have migrated as chloride complexes and entered the pyrite lattice.Arsenic and Sb,generally influenced by complex-forming reactions rather than substitution ones,could also enter the pyrite lattice,or slightly predate the precipitation of colloform pyrite as mineral inclusions,which are controlled by their hydrolysis constant in the ore fluids.The colloform pyrite may have grown inward from the rims.The successive BSR reaction process would enrich H_2~(32)S in the overlying water column but reduce the metal content,the nucleation of these pyrite rims was featured by strongly negative sulfur isotopes.The following AOM process should be activated by deformation like the turbidity sediment of the mudstone as the sulfide deposition are associated with fault activities that caused the emission of methane migration upward and simultaneously replenishing the metal in the column.The higher AOM reaction rate and the higher metal supply(not only Fe.but with minor other metals such as Pb and Zn) caused by sediment movement enhanced the metal concentration within the pyrite lattice.     

Theoretical growth of framboidal and sunflower pyrite using the R-package frambgrowth

Mineralogy and Petrology - Framboids and sunflowers are the most ubiquitous shapes of sedimentary pyrite. Framboids are spherical aggregates of nanocrystals, while sunflowers are formed by...     

Multi-stage growth and invisible gold distribution in pyrite from the Kundarkocha sediment-hosted gold deposit,eastern India

Gold mineralization at Kundarkocha, India, is hosted in sheared gray quartz veins that were emplaced in carbonaceous pyritic phyllite. Gold occurs as enclosed grains within sulfides and free grains in quartz. Based on characteristic textural and chemical features, documented by X-ray element imaging, electron probe microanalysis and laser-ablation inductively-coupled plasma mass spectrometry analyses, four pyrite types were identified in carbonaceous phyllites and auriferous veins. Rock-hosted fine-grained syn-sedimentary to early diagenetic pyrite framboids (PyI) have lower contents of Co and As but consistently high gold values. Pyrite of the next generation (PyII) has numerous silicate and rare sulfide inclusions; lower contents of Co and Ni, moderate As values; the highest mean value of invisible gold and maximum concentrations of trace elements such as Li, Ti, Zn, Rb, Sr, Y, Zr, Nb, La, Ce, Ta, Th, U and Cr. Pyrite of the third generation (PyIII) shows evidence of overgrowth over PyII, contains both silicate and sulfide inclusions, and are characterized by moderate contents of Co, high Ni and low Au values and higher concentrations of large ion lithophile elements, but lesser amount of high field strength elements. Pyrites of the latest type (PyIV) occur as polycrystalline aggregates that contain inclusions of gold, sulfides and rare silicates, show oscillatory zoning of Co and As and the lowest concentrations of all other trace elements. Successive decrease in contents of majority of trace elements from PyII to PyIV is attributed to fluid-assisted recrystallization during diagenesis and low grade metamorphism.Later generation pyrites (PyII through PyIV) exhibit higher Au contents regardless of their As values, indicating occurrence of invisible gold mostly as nanoparticles, at times reaching up to 500 ppm. Unlike the majority of trace elements that underwent large-scale remobilizations, gold was somehow locked up in pyrite resulting in a rather lean deposit at Kundarkocha.     

The effect of As, Co, and Ni impurities on pyrite oxidation kinetics: An electrochemical study of synthetic pyrite

Synthetic pyrite crystals doped with As, Co, or Ni, undoped pyrite, and natural arsenian pyrite from Leadville, Colorado were investigated with electrochemical techniques and solid-state measurements of semiconducting properties to determine the effect of impurity content on pyrite’s oxidation behavior. Potential step experiments, cyclic voltammetry, and AC voltammetry were performed in a standard three-electrode electrochemical cell setup. A pH 1.78 sulfuric acid solution containing 1 mM ferric iron, open to atmospheric oxygen, was chosen to approximate water affected by acid drainage. Van der Pauw/Hall effect measurements determined resistivity, carrier concentration and carrier mobility.The anodic dissolution of pyrite and the reduction of ferric iron half-reactions are taken as proxies for natural pyrite oxidation. Pyrite containing no impurities is least reactive. Pyrite with As is more reactive than pyrite with either Ni or Co despite lower dopant concentration. As, Co, and Ni impurities introduce bulk defect states at different energy levels within the band gap. Higher reactivity of impure pyrite suggests that introduced defect levels lead to higher density of occupied surface states at the solid-solution interface and increased metallic behavior. The current density generated from potential step experiments increased with increasing As concentration. The higher reactivity of As-doped pyrite may be related to p-type conductivity and corrosion by holes. The results of this study suggest that considering the impurity content of pyrite in mining waste may lead to more accurate risk assessment of acid producing potential.     

The effect of As, Co, and Ni impurities on pyrite oxidation kinetics: Batch and flow-through reactor experiments with synthetic pyrite

Pyrite samples synthesized with As, Co, or Ni impurities and without added impurities were oxidized in batch and mixed flow-through reactors in the presence of 1 mM ferric iron, at pH 2. Six samples from each dopant population were used to provide a statistically robust comparison; two natural samples from Leadville, CO (major impurities Pb, As, Bi, Ag, Zn) and Elba, Italy (Co, As) were also included. In each experiment, three reaction progress variables were monitored: ferric iron, ferrous iron, and sulfate. The pyrite samples with impurities have average oxidation rates that are faster than the undoped samples, with As- and Co-doped pyrite having the highest rates. As, Co, and Ni were released to solution in accordance with their concentrations in the solid samples. As concentrations in the batch reactor experiments tended to remain constant, in contrast to Co and Ni, which increased over time. Initial rates, calculated from the batch reactor experiments, were faster than the steady-state rates calculated from the mixed flow-through reactor experiments. Apparent rates calculated using sulfate were faster than apparent rates calculated using ferric and ferrous iron, reflecting oxidation of ferrous iron in solution by dissolved oxygen. The results imply that impurities in pyrite do contribute to its reactivity, in agreement with studies using electrochemical methods. Oxidation rate differences among pyrite samples with different impurities are probably too small to warrant explicit consideration in environmental modeling applications, but are important to understanding pyrite oxidation mechanisms and semiconducting properties.     

Hydrogeologic and environmental impact of amjhore pyrite mines,India

Drainage from active and inactive pyrite mines has produced chemical and physical pollution of both ground- and surface water in Amjhore region. In the present case, chemical pollution is caused by exposing pyrite minerals to oxidation or leaching, resulting in undesirable concentrations of dissolved materials. Pyrite mining suddenly exposed large quantities of sulfides to direct contact with oxygen, and oxidation proceeds rapidly, resulting in acidity and release of metal (Fe) and sulfates to the water system, eventually resulting in water pollution in the region. The magnitude and impact of the problem is just being recognized and, as the present and the future projected demand for clean water is of top priority, the present studies were undertaken.Mine drainage includes water flowing from the surface and underground mines and runoff or seepage from the pyrite mines. This article describes the various hydrologic factors that control acid water formation and its transport. The mine drainage is obviously a continuing source of pollution and, therefore, remedial measures mainly consisting of a double-stage limestone-lime treatment technique have been suggested. The present results will be used to develop an alternative and more effective abatement technology to mitigate acid production at the source, namely, the technique of revegetation of the soil cover applied to the waste mine dump material.Water quality change is discussed in detail, with emphasis on acidity formed from exposed pyrite material and on increase in dissolved solids. Preventive and treatment measures are recommended.     

The impact of pyrite variability, dispersive transport and precipitation of secondary phases on the sulphate release due to pyrite weathering

The objective of this study was to investigate the impact of flow, transport and geochemical parameters in the unsaturated and saturated zones on the release of SO₄ from overburden lignite spoil piles into the adjacent lake. A vertical one-dimensional model was set up using the reactive transport simulator SULFIDOX in order to account for the unsaturated zone. The SULFIDOX model was calibrated for effective diffusion using measured O₂ in the gas phase and SO₄ concentrations in the liquid phase from the unsaturated zone of the heap. The results show high sensitivity to O₂ supply and initially present gypsum, but the inclusion of secondary mineral precipitation in equilibrium is of minor importance for the results. To account for the transport of released SO₄ from the saturated zone into the surface water, scenarios were performed by using SULFIDOX results as input concentration for a two-dimensional vertical model set up with PROCESSING MODFLOW and MT3D. These scenarios indicate a rising discharge of SO₄ into the adjacent lake due to continued pyrite weathering for 80 a. Results are highly sensitive to dispersivity, whereas the spatial variability of pyrite distribution did not show any influence on the results. The consideration of initially present gypsum shows a major effect on the modelled SO₄ release.     

The behaviour of platelets in natural diamonds and the development of a new mantle thermometer

Platelets are one of the most common defects occurring in natural diamonds but their behaviour has not previously been well understood. Recent technical advances, and a much improved understanding of the correct interpretation of the main infrared (IR) feature associated with platelets (Speich et al. 2017), facilitated a systematic study of platelets in 40 natural diamonds. Three different types of platelet behaviour were identified here. Regular diamonds show linear correlations between both B-centre concentrations and platelet density and also between platelet size and platelet density. Irregular diamonds display reduced platelet density due to platelet breakdown, anomalously large or small platelets and a larger platelet size distribution. These features are indicative of high mantle storage temperatures. Finally, a previously unreported category of subregular diamonds is defined. These diamonds experienced low mantle residence temperatures and show smaller than expected platelets. Combining the systematic variation in platelet density with temperatures of mantle storage, determined by nitrogen aggregation, we can demonstrate that platelet degradation proceeds at a predictable rate. Thus, in platelet-bearing diamonds where N aggregation is complete, an estimate of annealing temperature can now be made for the first time.     

Morphology and growth of aragonite crystals in hot-spring travertines at Lake Bogoria, Kenya Rift Valley

Pseudohexagonal aragonite crystals are common components in some hot-spring travertines at Chemurkeu on the western shore of Lake Bogoria, Kenya. Beds, lenses and pods of aragonite crystals are intercalated with beds of white non-crystallographic calcite dendrites. The pseudohexagonal aragonite crystals, which are up to 4 cm long and 4 mm wide, are formed of nested skeletal crystals. Each skeletal crystal is formed of cyclical twinned crystals that are constructed of stacked subcrystals. The latter are inclined at a consistent angle of 40° to the long axis of the pseudohexagonal aragonite crystal. Intense competition for space during growth modified the crystal morphology with the result that many of the pseudohexagonal crystals are distorted. Intercrystalline and intracrystalline pores are filled or partly filled by epitaxial aragonite overgrowths and/or reticulate microbial coatings that have a high concentration of Si and Mg. In places, this extracellular mucus induced etching of the underlying aragonite crystal. Today the hot (T>95 °C) Na-HCO₃-Cl spring waters at Chemurkeu have a salinity of 5–6 g L^?1 TDS, a pH of 8·1–9·1, Ca²⁺ concentrations of <2 mg L^?1 and Mg²⁺ concentrations of <0·7 mg L^?1, The springs of the Lake Bogoria Geothermal Field are fed by a shallow aquifer (T～100 °C) and a deeper aquifer (T～170 °C). Springs at Chemurkeu derive from meteoric groundwater, lake water and condensed steam, and are fed mainly from the shallow thermal aquifer. Much of the aragonite may have formed when the spring waters contained more dissolved Ca²⁺ than today, possibly under more humid conditions during the Holocene.     

Equation of state, elasticity, and shear strength of pyrite under high pressure

 Physical properties including the equation of state, elasticity, and shear strength of pyrite have been measured by a series of X-ray diffraction in diamond-anvil cells at pressures up to 50 GPa. A Birch–Murnaghan equation of state fit to the quasihydrostatic pressure–volume data obtained from laboratory X-ray source/film techniques yields a quasihydrostatic bulk modulus K _0T =133.5 (±5.2) GPa and bulk modulus first pressure derivative K ^′ _0T =5.73 (±0.58). The apparent equation of state is found to be strongly dependent on the stress conditions in the sample. The stress dependency of the high-pressure properties is examined with anisotropic elasticity theory from subsequent measurements of energy-dispersive radial diffraction experiments in the diamond-anvil cell. The calculated values of K _0T depend largely upon the angle ψ between the diffracting plane normal and the maximum stress axis. The uniaxial stress component in the sample, t=σ₃−σ₁, varies with pressure as t=−3.11+0.43P between 10 and 30 GPa. The pressure derivatives of the elastic moduli dC ₁₁/dP=5.76 (±0.15), dC ₁₂/dP=1.41 (±0.11) and dC ₄₄/dP=1.92 (±0.06) are obtained from the diffraction data assuming previously reported zero-pressure ultrasonic data (C ₁₁=382 GPa, C ₁₂=31 GPa, and C ₄₄=109 GPa). Received: 21 December 2000 / Accepted: 11 July 2001     

Syndepositional and diagenetic features in the pyrite ores of Amjhore,Bihar, India

The sedimentary pyrite deposit of Amjhore, Bihar associated with the Bijaigarh Shale of the Upper Vindhyan Group (Proterozoic age) exhibits characteristic syndepositional features suggestive of both calm and disturbed conditions of deposition. The pyrite ores also show typical diagenetic features.     

Morphology and formation mechanism of pyrite induced by the anaerobic oxidation of methane from the continental slope of the NE South China Sea

In order to understand the response of authigenic pyrite to gas hydrate geo-systems, pyrite tubes or rods at the sulfate–methane transition (SMT) zone of core GC10 from the northern continental slope of the South China Sea (SCS) were investigated. In situ X-ray diffraction (XRD) results show that the pyrite tube consists of pyrite micro-crystals with trace amount of graphite in the inner tube. Scanning electron microscope (SEM) observations of pyrite tubes indicate various aggregations in the form of framboidal, euhedral, and colloidal pyrite microcrystals. Typical framboidal pyrite is considered as packing of octahedral microcrystals. Interestingly, many framboids in the tubes consist of round or irregular microcrystals and have an outer crust that consists of secondary pyrite. The size of the framboids in the inner wall of the tube is larger than that in the middle wall or foraminifer-filled pyrite. High-resolution transmission electron microscopic (HRTEM) images show marcasite lamellae defects in the spherulitic pyrite crystals, which reveal different solution conditions during the pyrite precipitation. Nano-foil-like graphitic carbon was observed to be closely associated with the pyrite spherules. The occurrence of both marcasite layers and nano-foil-like graphitic carbon suggest that the migration of methane from deep sediment. It is suggested that the formation of pyrite serves as a catalyst during the reaction from methane to elemental carbon under the anaerobic oxidation of methane. Meanwhile, this reaction results in local acidification of the solution inside the pyrite tubes, which favors marcasite lamellae growth on the host pyrite substrate.     

Diagenetic pyrite from the lead-zinc deposits of Zawar,India

Pyrite from the Precambrian lead-zinc deposits of Zawar, West India, shows excellent sedimentary features, viz., composite bedding, lenticular bedding, flame structure etc. which are attributed to turbidites. Early diagenetic pyrite occurs as framboids and isolated euhedral as well as subhedral grains. Most of the isolated grains are probably derived from the breaking of unconsolidated framboids. Diagenetic crystallization of pyrite became operative during an early stage of deposition and continued to modify the initial sedimentary fabrics.