Kinetic model of carbonate dissolution in Martian meteorite ALH84001

The magnetites and sulfides located in the rims of carbonate globules in the Martian meteorite ALH84001 have been claimed as evidence of past life on Mars. Here, we consider the possibility that the rims were formed by dissolution and reprecipitation of the primary carbonate by the action of water. To estimate the rate of these solution-precipitation reactions, a kinetic model of magnesite-siderite carbonate dissolution was applied and used to examine the physicochemical conditions under which these rims might have formed. The results indicate that the formation of the rims could have taken place in < 50 yr of exposure to small amounts of aqueous fluids at ambient temperatures. Plausible conditions pertaining to reactions under a hypothetical ancient Martian atmosphere (1 bar CO₂), the modern Martian atmosphere (8 mbar CO₂), and the present terrestrial atmosphere (0.35 mbar CO₂) were explored to constrain the site of the process. The results indicated that such reactions likely occurred under the latter two conditions. The possibility of Antarctic weathering must be entertained, which, if correct, would imply that the plausibly biogenic minerals (single-domain magnetite of characteristic morphology and sulfide) reported from the rims may be the products of terrestrial microbial activity. This model is discussed in terms of the available isotope data and found to be compatible with the formation of ALH84001 rims. Particularly, anticorrelated variations of radiocarbon with δ¹³C indicate that carbonate in ALH84001 was affected by solution-precipitation reactions immediately after its initial fall (∼13,000 yr ago) and then again during its recent exposure prior to collection.     

Microscale carbon isotope variability in ALH84001 carbonates and a discussion of possible formation environments

The carbonates in martian meteorite ALH84001 preserve a record of aqueous processes on Mars at 3.9 Ga, and have been suggested to contain signatures of ancient martian life. The conditions of the carbonate formation environment are critical for understanding possible evidence for life on Mars, the history of water on Mars, and the evolution of the martian atmosphere. Despite numerous studies of petrographic relationships, microscale oxygen isotope compositions, microscale chemical compositions, and other minerals associated with the carbonates, formation models remain relatively unconstrained. Microscale carbon isotope analyses of ALH84001 carbonates reveal variable δ¹³C values ranging from +27 to +64‰. The isotopic compositions are correlated with chemical composition and extent of crystallization such that the Mg-poor, early-formed carbonates are relatively ¹³C depleted and the Mg-rich, later forming carbonates, are ¹³C enriched. These data are inconsistent with many of the previously proposed environments for carbonate formation, and a new set of hypotheses are proposed. Specifically, two new models that account for the data involve low temperature (<100°C) aqueous processes: (1) the carbonates formed during mixing of two fluids derived from separate chemical and isotopic reservoirs; or (2) the carbonates formed from high pH fluids that are exposed to a CO₂-rich atmosphere and precipitate carbonate, similar to high pH springs on Earth.     

An Evaporation Model for Formation of Carbonates in the ALH84001 Martian Meteorite

Small, discoid globules and networks of magnesium-iron-calcium carbonates occur within impact-produced fracture zones in the ALH84001 Martian meteorite. Because these carbonates contain or are associated with the hydrocarbons, single-domain magnetite and iron-sulfide grains, and purported microfossils that collectively have been cited as evidence for ancient Martian life, it is critically important to understand their formation. Previous hypotheses for the origin of the carbonates involve either alteration of the rock by hydrothermal fluids at relatively low temperatures, or formation from a CO₂-rich vapor at high temperatures. This paper explores an alternative mechanism–direct precipitation from a ponded evaporating brine infiltrating into fractures in the floor of an impact crater. Such a model can be reconciled with the observed carbonate compositional zoning and extreme stable-isotopic fractionations. If the carbonates formed in this manner, this removes a possible obstacle to the proposed existence of microbial remains in ALH84001; however, the cited evidence for life can be better explained by inorganic processes expected from brines in an evaporating alkaline lake, with an overprint of shock metamorphism and subsequent contamination by organic matter after falling to Earth.     

Elongated prismatic magnetite crystals in ALH84001 carbonate globules: potential Martian magnetofossils.

Using transmission electron microscopy (TEM), we have analyzed magnetite (Fe3O4) crystals acid-extracted from carbonate globules in Martian meteorite ALH84001. We studied 594 magnetites from ALH84001 and grouped them into three populations on the basis of morphology: 389 were irregularly shaped, 164 were elongated prisms, and 41 were whisker-like. As a possible terrestrial analog for the ALH84001 elongated prisms, we compared these magnetites with those produced by the terrestrial magnetotactic bacteria strain MV-1. By TEM again, we examined 206 magnetites recovered from strain MV-1 cells. Natural (Darwinian) selection in terrestrial magnetotactic bacteria appears to have resulted in the formation of intracellular magnetite crystals having the physical and chemical properties that optimize their magnetic moment. In this study, we describe six properties of magnetite produced by biologically controlled mechanisms (e.g., magnetotactic bacteria), properties that, collectively, are not observed in any known population of inorganic magnetites. These criteria can be used to distinguish one of the modes of origin for magnetites from samples with complex or unknown histories. Of the ALH84001 magnetites that we have examined, the elongated prismatic magnetite particles (similar to 27% of the total) are indistinguishable from the MV-1 magnetites in five of these six characteristics observed for biogenically controlled mineralization of magnetite crystals.     

A Comparative Analysis of Evaporate Sediments on Earth and Mars：Implications for the Climate Change on Mars

The knowledge of Martian salts has gone through substantial changes during the past decades. In the 70th of last century, Viking landers have noticed the existence of salts on Mars. Several salt species have been suggested from then on, such as sulfates and chlorides. However, their origin was a mystery due to the lack of observations. The recent explorations and related studies at the beginning of this century revealed that the crustal composition of Mars is similar to that of Earth, and it was hypothesized that almost one third of Martian surface was covered by oceans and lakes in the early stage of Mars. The huge water bodies may have dissolved a large quantity of ions from Martian primary rocks during the whole Noachian and Hesperian epoch. After the enormous drought event happened during the late Hesperian and the early Amazonian, these dissolved ions have formed huge salts deposits and most of them were preserved on Mars until today. To date, carbonates, sulfates, chlorides have all been detected by orbital remote sensing and by landers and rovers. However, the salt mineral assemblages on Mars seems to have some differences from those on Earth, e.g., rich in sulfates and lack of massive carbonates. To explain this difference, we propose that most of the surface carbonates precipitated from the ancient oceans may have been dissolved by the later ubiquitous acidic fluids originated from the global volcanism in the Hesperian era, and formed the enormous sulfate deposits as detected, and this hypothesis seems to be supported by the evidence that most of the sulfate deposits distribute around the Tharsis volcanic province while the survived carbonates located far from it. This process can release most of the carbon on Mars to the atmosphere in the form of CO2 and then be erased by the late heavy bombardments, which might have profound influence on the climate change happened in the Hesperian age. The positive correlation between the GRS results of the potassium distributions and the distribution of chlorides on Mars, together with the high Br concentration measured from the evaporate sediments at two Mars exploration rover landing sites, indicate that the brines in the regions where the chlorides deposited may have reached the stage for potassium salts deposition, thus we propose for the first time that potassium salts deposits might be prevalent in these regions.     

火星生命研究的进展与前景

关于火星是否存在或曾经存在生命的争论由来已久。有人以ALH84001火星陨石新鲜破裂面上的大量碳酸盐小球体和多环芳香烃（PAHs）为主要依据，推论火星至少在13～36亿 aBP前很可能有生命形态存在。然而，很多人认为ALH84001陨石的各种特性可以是非生物成因的。由于地球上的生物在超过115℃的温度下很难存活（火星可与之类比），争论的焦点逐渐集中在碳酸盐球体的形成温度上。也有研究者关注该陨石上有机物质的来源问题。对ALH84001陨石的综合学科研究提出了互相矛盾的证据。综述了自1996年以来在国外各种主要期刊上发表的关于 ALH84001陨石与火星生命的研究成果（也包括了一些对其他火星陨石的研究），认为目前尚不能断言火星生命存在与否。对火星继续深入探索以获取进一步的证据是十分必要的。以美国国家航空和宇航局（NASA）Odys sey宇宙飞船起始的火星探测计划将引发新一轮火星生命研究的热潮。     

Petrography and bulk chemistry of Martian orthopyroxenite ALH84001: implications for the origin of secondary carbonates

New petrologic and bulk geochemical data for the SNC-related (Martian) meteorite ALH84001 suggest a relatively simple igneous history overprinted by complex shock and hydrothermal processes. ALH84001 is an igneous orthopyroxene cumulate containing penetrative shock deformation textures and a few percent secondary extraterrestrial carbonates. Rare earth element (REE) patterns for several splits of the meteorite reveal substantial heterogeneity in REE abundances and significant fractionation of the REEs between crushed and uncrushed domains within the meteorite. Complex zoning in carbonates indicates nonequilibrium processes were involved in their formation, suggesting that CO2-rich fluids of variable composition infiltrated the rock while on Mars. We interpret petrographic textures to be consistent with an inorganic origin for the carbonate involving dissolution-replacement reactions between CO2-charged fluids and feldspathic glass in the meteorite. Carbonate formation clearly postdated processes that last redistributed the REE in the meteorite.     

西藏列廷冈铁多金属矿床磁铁矿元素地球化学特征及地质意义

西藏列廷冈矿床是林周盆地Fe-Mo-Cu-Pb-Zn矿集区内近年来新发现不久、规模较大的矽卡岩型铁多金属矿床。矿区磁铁矿发育,主要包括块状、浸染状和脉状3种类型。基于详细的野外地质调查和室内矿相学研究,将矿床成矿期划分为矽卡岩期和热液期2期,进而划分为5个成矿阶段:早期矽卡岩阶段、退化蚀变阶段、早期热液阶段、石英-硫化物阶段和碳酸盐阶段,其中,块状磁铁矿主要形成于退化蚀变阶段,浸染状和脉状磁铁矿主要形成于早期热液阶段。以磁铁矿为主要研究对象,采用电子探针(EPMA)和单矿物微量稀土元素ICP-MS分析实验,重点对磁铁矿元素地球化学特征、成因矿物学进行系统研究。研究结果表明,3种不同类型磁铁矿内均含Ti、Si、Ca等次要元素以及Na、K、Cr、Ni、Co、Pb、Ba、Sn、Sr、Sb、Cu等多种可检测到的微量元素,且矿物内主要发生了Al、Mg、Mn等元素的类质同像置换,综合TiO_2-Al_2O_3-MgO、TiO_2-Al_2O_3-(MgO+Mn O)和(Ca+Al+Mn)-(Ti+V)、Ni/(Cr+Mn)-(Ti+V)等多种磁铁矿成因判别图解投图结果及矿体野外宏观地质特征,表明矿区磁铁矿均为热液成因。块状磁铁矿具明显的Eu正异常,浸染状和脉状磁铁矿具Eu负异常,均无明显Ce异常特征,表明富Eu成矿流体在矽卡岩期的高温氧化环境下形成了矽卡岩型块状磁铁矿体,在热液期则逐渐转变为低温还原环境,形成浸染状和脉状磁铁矿及多种金属硫化物,且铁的物质来源主要与矿区花岗闪长岩和花岗斑岩紧密相关。     

Modeling aqueous ferrous iron chemistry at low temperatures with application to Mars

Major uncertainties exist with respect to the aqueous geochemical evolution of the Martian surface. Considering the prevailing cryogenic climates and the abundance of salts and iron minerals on Mars, any attempt at comprehensive modeling of Martian aqueous chemistry should include iron chemistry and be valid at low temperatures and high solution concentrations. The objectives of this paper were to (1) estimate ferrous iron Pitzer-equation parameters and iron mineral solubility products at low temperatures (from < 0 °C to 25 °C), (2) incorporate these parameters and solubility products into the FREZCHEM model, and (3) use the model to simulate the surficial aqueous geochemical evolution of Mars.Ferrous iron Pitzer-equation parameters were derived in this work or taken from the literature. Six new iron minerals [FeCl₂·4H₂O, FeCl₂·6H₂O, FeSO₄·H₂O, FeSO₄·7H₂O, FeCO₃, and Fe(OH)₃] were added to the FREZCHEM model bringing the total solid phases to 56. Agreement between model predictions and experimental data are fair to excellent for the ferrous systems: Fe-Cl, Fe-SO₄, Fe-HCO₃, H-Fe-Cl, and H-Fe-SO₄.We quantified a conceptual model for the aqueous geochemical evolution of the Martian surface. The five stages of the conceptual model are: (1) carbonic acid weathering of primary ferromagnesian minerals to form an initial magnesium-iron-bicarbonate-rich solution; (2) evaporation and precipitation of carbonates, including siderite (FeCO₃), with evolution of the brine to a concentrated NaCl solution; (3) ferrous/ferric iron oxidation; (4) either evaporation or freezing of the brine to dryness; and (5) surface acidification.What began as a dilute Mg-Fe-HCO₃ dominated leachate representing ferromagnesian weathering evolved into an Earth-like seawater composition dominated by NaCl, and finally into a hypersaline Mg-Na-SO₄-Cl brine. Weathering appears to have taken place initially under conditions that allowed solution of ferrous iron [low O₂(g)], but later caused oxidation of iron [high O₂(g)]. Surface acidification and/or sediment burial can account for the minor amounts of Martian surface carbonates. This model rests on a large number of assumptions and is therefore speculative. Nevertheless, the model is consistent with current understanding concerning surficial salts and minerals based on Martian meteorites, Mars lander data, and remotely-sensed spectral analyses.     

火星陨石和火星表面泥岩中蚀变过程对比研究

火星次生含水蚀变矿物是火星地质历史时期水环境和气候演变历史的真实记录,一直以来都是火星探测、火星陨石研究的重点,是认识火星环境特征和气候演化的重要研究对象。文中对比研究了表土角砾岩NWA7034、火成堆晶岩MIL03346等两块最富蚀变矿物火星陨石,以及Gale撞击坑出露的Sheepbed泥岩3种岩石类型的蚀变程度及其蚀变矿物类型和组合,分析了层状硅酸盐、铁氧化物/氢氧化物、钙硫酸盐等蚀变矿物的成因及环境指示意义。发现这3类岩石的蚀变作用各不相同。火星陨石NWA7034的蚀变作用以氧化和加热作用为主,无蒸发盐类矿物。火星陨石MIL03346的蚀变程度最低,为后期水溶液进入缝隙而引发的,蚀变作用以橄榄石的伊利石化、裂隙和缝隙中填充次生矿物细脉为主。而火星Sheepbed泥岩经历了后期的等化学风化过程(isochemical weathering),次生过程包括成岩蚀变和成岩后蚀变两个阶段。其中,成岩过程中的蚀变以橄榄石蚀变为铁氧化物和蒙皂石矿物为主,成岩后以形成蒸发盐类矿物硫酸钙为主。以上3种岩石蚀变矿物组成差异反映了火星上不同地质背景中、不同气候条件下蚀变过程的复杂性。文中对火星含水矿物及部分典型矿物的形成条件和过程进行系统总结,这对于理解未来火星探测任务、识别含水矿物的形成、揭示火星水环境和地质历史具有重要指导意义。     

The role of vaterite and aragonite in the formation of pseudo-biogenic carbonate structures: implications for Martian exobiology.

A simple synthesis of various forms of calcium carbonate with spherical and 'floral' morphologies is reported. Vaterite formation occurs at approximately 25 degrees C, aragonite at approximately 70 degrees C and calcite at about approximately 80 degrees C. These are produced when CO2 is reacted with an aqueous solution of calcium chloride in the presence of ammonia. These conditions may have existed at the surface of Mars in the past, leading us to conclude that such mineral formations may be common there. Although the initial phases are modified over time with changing temperature and pressure conditions, they still influence the final morphology of the carbonates observed. A comparison of these structures with those found in the Martian meteorite ALH84001 suggests, but does not confirm, a non-biogenic origin for the ALH84001 carbonates.     

Chemical composition of magnetite in Martian meteorite ALH 84001: Revised appraisal from thermochemistry of phases in Fe-Mg-C-O

Martian meteorite Allan Hills (ALH) 84001 contains sub-micron magnetite grains, suggested to be of biogenic origin, in its globules of Fe-Mg carbonate mineral. There is disagreement on whether the low Mg content of the magnetite could only arise from biological metabolism ( [Treiman, 2003] and [Thomas-Keprta et al., 2009]). However, constraints on the magnetite’s biogenicity are far less certain than had been inferred. The thermochemical bases for the equilibrium calculations are reviewed in detail; there are inconsistencies and gaps in fundamental data for siderite, macromolecular carbons, and magnesioferrite. The calculations of Treiman (2003), assuming formation of magnetite via “siderite = magnetite + CO₂ + CO”, are incorrect because of a flaw in the computer code used. The corrected location of this equilibrium (Thomas-Keprta et al., 2009) is no longer crucial, because of recent finds that the magnetite grains are associated with macromolecular carbon; this implies that the dominant magnetite-forming reaction was “siderite = magnetite + CO₂ + C”. From the location of this equilibrium, using the corrected computer code and best available thermochemical data, the Mg-poor magnetite grains (and macromolecular carbon) in carbonates in ALH 84001 could have formed by decomposition of the carbonates at geologically reasonable pressures and temperatures. The low-Mg compositions of the magnetite grains remain consistent with an abiotic origin within the known geological history of ALH 84001.     

地外有机化合物

球粒陨石中的有机化合物起源于星际介质,是构成太阳星云的初始组分,并与其他物质一起吸积形成小行星和行星。在小行星内,有机质经历了不同程度的水蚀变和热变质作用。球粒陨石中的有机化合物尽管是非生命成因,但组成极为复杂,主要是类似于干酪根的大分子物质,以及少量可溶性有机物。大部分可溶有机分子也发现于地球生物圈,但前者可具有完全不同的H、C、N等同位素组成,这也是它们来源于地球之外的重要证据。星云中宇宙线和紫外线（UV）的辐射、小行星的热变质和水蚀变,是地外有机质演化的主要过程。球粒陨石中的有机质是地球生命起源的物质基础,是生命起源不可或缺的重要环节。同样重要的是,大量的火星探测表明,火星历史上有过满足生命存在的基本条件,而在火星陨石中还发现了一些生物活动相关的线索。未来很可能首先在火星上发现地外生命存在的证据。     

On the in situ aqueous alteration of soils on Mars

Early (>3 Gy) wetter climate conditions on Mars have been proposed, and it is thus likely that pedogenic processes have occurred there at some point in the past. Soil and rock chemistry of the Martian landing sites were evaluated to test the hypothesis that in situ aqueous alteration and downward movement of solutes have been among the processes that have transformed these portions of the Mars regolith. A geochemical mass balance shows that Martian soils at three landing sites have lost significant quantities of major rock-forming elements and have gained elements that are likely present as soluble ions. The loss of elements is interpreted to have occurred during an earlier stage(s) of weathering that may have been accompanied by the downward transport of weathering products, and the salts are interpreted to be emplaced later in a drier Mars history. Chemical differences exist among the sites, indicating regional differences in soil composition. Shallow soil profile excavations at Gusev crater are consistent with late stage downward migration of salts, implying the presence of small amounts of liquid water even in relatively recent Martian history. While the mechanisms for chemical weathering and salt additions on Mars remain unclear, the soil chemistry appears to record a decline in leaching efficiency. A deep sedimentary exposure at Endurance crater contains complex depth profiles of SO₄, Cl, and Br, trends generally consistent with downward aqueous transport accompanied by drying. While no model for the origin of Martian soils can be fully constrained with the currently available data, a pedogenic origin is consistent with observed Martian geology and geochemistry, and provides a testable hypothesis that can be evaluated with present and future data from the Mars surface.     

Experimental study of the hydrothermal reactivity of organic acids and acid anions: II. Acetic acid, acetate, and valeric acid

Organic acids and acid anions occur in substantial concentrations in many aqueous geologic fluids and are thought to take part in a variety of geochemical processes ranging from the transport of metals in ore-forming fluids to the formation of natural gas to serving as a metabolic energy source for microbes in subsurface habitats. The widespread occurrence of organic acids and their potential role in diverse geologic processes has led to numerous experimental studies of their thermal stability, yet there remain substantial gaps in our knowledge of the factors that control the rates and reaction pathways for the decomposition of these compounds under geologic conditions. In order to address some of these uncertainties, a series of laboratory experiments were conducted to examine the behavior of organic acids and acid anions under hydrothermal conditions in the presence of minerals. Reported here are results of experiments where aqueous solutions of acetic acid, sodium acetate, or valeric acid (n-pentanoic acid) were heated at 325°C, 350 bars in the presence of the mineral assemblages hematite + magnetite + pyrite, pyrite + pyrrhotite + magnetite, and hematite + magnetite. The results indicate that aqueous acetic acid and acetate decompose by a combination of two reaction pathways: decarboxylation and oxidation. Both reactions are promoted by minerals, with hematite catalyzing the oxidation reaction while magnetite catalyzes decarboxylation. The oxidation reaction is much faster, so that oxidation dominates the decomposition of acetic acid and acetate when hematite is present. In contrast to previous reports that acetate decomposed more slowly than acetic acid, we found that acetate decomposed at slightly faster rates than the acid in the presence of minerals. Although longer-chain monocarboxylic acids are generally thought to decompose by decarboxylation, valeric acid appeared to decompose primarily by “deformylation” to 1-butene plus formic acid. Subsequent decomposition of 1-butene and formic acid generated a variety of short-chain (≤C₄) hydrocarbons and moncarboxylic acids as well as CO₂. Valeric acid decomposition proceeded more rapidly (by a factor of 2) in the presence of hematite-magnetite-pyrite than with the other mineral assemblages, with the greater reaction rate apparently attributable to the effects of fluid chemistry. Valeric acid was observed to decompose at a substantially faster rate than acetic acid under similar conditions. The results suggest that decomposition of aqueous monocarboxylic acids may make a significant contribution to the conversion of petroleum to light hydrocarbons in natural gas and thermal fluids.     

莱芜张家洼铁矿磁铁矿LA-ICP-MS微量元素特征及其对成矿过程的制约

莱芜张家洼铁矿位于华北克拉通东缘的鲁西地区,矿石成因类型为夕卡岩型铁矿。矿体赋存在早白垩世高镁闪长岩与奥陶系马家沟组灰岩及白云岩接触带附近。本文通过对莱芜岩浆和热液磁铁矿电子探针(EPMA)以及激光剥蚀电感耦合等离子体质谱(LA ICP MS)分析,探讨磁铁矿微量元素组成及变化规律对成岩和成矿作用的指示,为揭示张家洼铁矿的矿床成因及其成矿流体演化过程提供重要制约。分析结果表明,莱芜岩浆磁铁矿与热液磁铁矿相比明显富集Ti、V、Cr等亲铁元素,相对富集Nb、Ta、Zr、Hf等高场强元素以及Sn、Ga、Ge、Sc等中等相容元素,Mg、Al、Mn、Zn、Co显著富集于热液磁铁矿中。Ti、V、Cr以及Mg、Al、Mn、Zn在岩浆和热液中具有不同的地球化学行为,Ti、V、Cr从熔体中进入磁铁矿主要受温度、分配系数以及fO2控制。Mg、Al、Mn、Zn主要受控于水岩反应和后期绿泥石+碳酸盐脉的交代,这些元素通过类质同象替换富集于热液磁铁矿中。Co在热液磁铁矿中除了受水岩相互作用和后期流体交代的影响外,硫化物的出现会导致Co含量急剧降低。Si、Ca、Na及Sr、Ba在岩浆和热液磁铁矿中的地球化学行为非常一致。Ti Ni/Cr图能够用于区分岩浆和热液磁铁矿,莱芜岩浆磁铁矿中Ti含量较高且Ni/Cr比值≤1,热液磁铁矿Ti含量较低且绝大多数Ni/Cr比值≥1。张家洼热液磁铁矿可分为早、晚两个阶段：早期阶段包括(1)早期原生粒状磁铁矿和(2)早期次生磁铁矿;晚期阶段包括(3)晚期原生磁铁矿和(4)晚期次生磁铁矿。原生磁铁矿具有典型的三联点结构特征;次生磁铁矿受后期热液交代影响表现为多空隙,通常呈不规则状、树枝状、骸晶以及交代残余结构。磁铁矿微量元素生动记录了成矿流体演化过程,从早期到晚期、从原生到次生都显示Mg、Al、Mn、Zn包括Co含量持续升高,表明成矿流体可能朝着富集这些微量元素的方向演化。后期流体的交代导致绿泥石蚀变为磁铁矿,连续水岩相互作用和后期流体的交代以及绿泥石直接蚀变是导致热液磁铁矿富集Mg、Al、Mn、Zn等元素的主要原因。热液磁铁矿晚期孔隙较为发育,孔隙度的增加促使更多的流体和磁铁矿发生反应。热液磁铁矿的微量元素不仅能够反映矿床形成的物理化学条件,而且可以反映围岩性质以及水岩相互作用过程。     

BIF-hosted iron mineral system: A review

The BIF-hosted iron ore system represents the world's largest and highest grade iron ore districts and deposits. BIF, the precursor to low- and high-grade BIF hosted iron ore, consists of Archean and Paleoproterozoic Algoma-type BIF (e.g., Serra Norte iron ore district in the Carajás Mineral Province), Proterozoic Lake Superior-type BIF (e.g., deposits in the Hamersley Province and craton), and Neoproterozoic Rapitan-type BIF (e.g., the Urucum iron ore district).The BIF-hosted iron ore system is structurally controlled, mostly via km-scale normal and strike-slips fault systems, which allow large volumes of ascending and descending hydrothermal fluids to circulate during Archean or Proterozoic deformation or early extensional events. Structures are also (passively) accessed via downward flowing supergene fluids during Cenozoic times.At the depositional site the transformation of BIF to low- and high-grade iron ore is controlled by: (1) structural permeability, (2) hypogene alteration caused by ascending deep fluids (largely magmatic or basinal brines), and descending ancient meteoric water, and (3) supergene enrichment via weathering processes. Hematite- and magnetite-based iron ores include a combination of microplaty hematite–martite, microplaty hematite with little or no goethite, martite–goethite, granoblastic hematite, specular hematite and magnetite, magnetite–martite, magnetite-specular hematite and magnetite–amphibole, respectively. Goethite ores with variable amounts of hematite and magnetite are mainly encountered in the weathering zone.In most large deposits, three major hypogene and one supergene ore stages are observed: (1) silica leaching and formation of magnetite and locally carbonate, (2) oxidation of magnetite to hematite (martitisation), further dissolution of quartz and formation of carbonate, (3) further martitisation, replacement of Fe silicates by hematite, new microplaty hematite and specular hematite formation and dissolution of carbonates, and (4) replacement of magnetite and any remaining carbonate by goethite and magnetite and formation of fibrous quartz and clay minerals.Hypogene alteration of BIF and surrounding country rocks is characterised by: (1) changes in the oxide mineralogy and textures, (2) development of distinct vertical and lateral distal, intermediate and proximal alteration zones defined by distinct oxide–silicate–carbonate assemblages, and (3) mass negative reactions such as de-silicification and de-carbonatisation, which significantly increase the porosity of high-grade iron ore, or lead to volume reduction by textural collapse or layer-compaction. Supergene alteration, up to depths of 200 m, is characterised by leaching of hypogene silica and carbonates, and dissolution precipitation of the iron oxyhydroxides.Carbonates in ore stages 2 and 3 are sourced from external fluids with respect to BIF. In the case of basin-related deposits, carbon is interpreted to be derived from deposits underlying carbonate sequences, whereas in the case of greenstone belt deposits carbonate is interpreted to be of magmatic origin. There is only limited mass balance analyses conducted, but those provide evidence for variable mobilization of Fe and depletion of SiO₂. In the high-grade ore zone a volume reduction of up to 25% is observed.Mass balance calculations for proximal alteration zones in mafic wall rocks relative to least altered examples at Beebyn display enrichment in LOI, F, MgO, Ni, Fe₂O_3total, C, Zn, Cr and P₂O₅ and depletions of CaO, S, K₂O, Rb, Ba, Sr and Na₂O. The Y/Ho and Sm/Yb ratios of mineralised BIF at Windarling and Koolyanobbing reflect distinct carbonate generations derived from substantial fluid–rock reactions between hydrothermal fluids and igneous country rocks, and a chemical carbonate-inheritance preserved in supergene goethite.Hypogene and supergene fluids are paramount for the formation of high-grade BIF-hosted iron ore because of the enormous amount of: (1) warm (100–200 °C) silica-undersaturated alkaline fluids necessary to dissolve quartz in BIF, (2) oxidized fluids that cause the oxidation of magnetite to hematite, (3) weakly acid (with moderate CO₂ content) to alkaline fluids that are necessary to form widespread metasomatic carbonate, (4) carbonate-undersaturated fluids that dissolve the diagenetic and metasomatic carbonates, and (5) oxidized fluids to form hematite species in the hypogene- and supergene-enriched zone and hydroxides in the supergene zone.Four discrete end-member models for Archean and Proterozoic hypogene and supergene-only BIF hosted iron ore are proposed: (1) granite–greenstone belt hosted, strike-slip fault zone controlled Carajás-type model, sourced by early magmatic (± metamorphic) fluids and ancient “warm” meteoric water; (2) sedimentary basin, normal fault zone controlled Hamersley-type model, sourced by early basinal (± evaporitic) brines and ancient “warm” meteoric water. A variation of the latter is the metamorphosed basin model, where BIF (ore) is significantly metamorphosed and deformed during distinct orogenic events (e.g., deposits in the Quadrilátero Ferrífero and Simandou Range). It is during the orogenic event that the upgrade of BIF to medium- and high-grade hypogene iron took place; (3) sedimentary basin hosted, early graben structure controlled Urucum-type model, where glaciomarine BIF and subsequent diagenesis to very low-grade metamorphism is responsible for variable gangue leaching and hematite mineralisation. All of these hypogene iron ore models do not preclude a stage of supergene modification, including iron hydroxide mineralisation, phosphorous, and additional gangue leaching during substantial weathering in ancient or Recent times; and (4) supergene enriched BIF Capanema-type model, which comprises goethitic iron ore deposits with no evidence for deep hypogene roots. A variation of this model is ancient supergene iron ores of the Sishen-type, where blocks of BIF slumped into underlying karstic carbonate units and subsequently experienced Fe upgrade during deep lateritic weathering.     

地球同火星蒸发岩沉积的对比

迄今为止,人类已经通过火星轨道探测器、火星着陆器及火星漫游车在火星上发现了碳酸盐、硫酸盐及氯化物等一 系列的盐类矿物,尽管整体上火星盐类矿物组合与地球上基本一致,但在许多细节方面还是和地球上有所不同。文中首先 对于火星盐类认知的现状作了简要综述;基于地球火星蒸发盐沉积及成盐作用规律的对比,预测火星表面及次表面可能存 在着广泛分布的钾盐;此外,发现火星轨道伽玛光谱仪所获的火星表面 K 的分布与火星表面已探测到的氯化物的分布有比 较强的相关性,喻示火星表面氯化物沉积地区的卤水浓度已经接近或达到钾盐形成的条件,同时指出这些地区存在钾盐的 可能性很大。     

Negative δO values in Allan Hills 84001 carbonate: Possible evidence for water precipitation on mars

The Martian meteorite ALH84001 contains ∼1% by weight of carbonate formed by secondary processes on the Martian surface or in the shallow subsurface. The major form of this carbonate is chemically and isotopically zoned rosettes which have been well documented elsewhere. This study concentrates upon carbonate regions ∼200 μm across which possess previously unobserved magnesium rich inner cores, interpreted here as rosette fragments, surrounded by a later stage cement containing rare Ca-rich carbonates (up to Ca₈₁Mg₀₇Fe₀₄Mn₀₇) intimately associated with feldspar. High spatial resolution ion probe analyses of Ca-rich carbonate surrounding rosette fragments have δ¹⁸O_V-SMOW values as low as −10‰. These values are not compatible with deposition from a global Martian atmosphere invoked to explain ALH84001 rosettes. The range of δ¹⁸O values are also incompatible with a fluid that has equilibrated with the Martian crust at high temperature or from remobilisation of carbonate of rosette isotopic composition. At Martian atmospheric temperatures, the small CO₂(gas)-CO₂(ice) fractionation makes meteoric CO₂ an unlikely source for −10‰ carbonates. In contrast, closed system Rayleigh fractionation of H₂O can generate δ¹⁸O_H2O −30‰, as observed at high latitudes on Earth. We suggest that atmospheric transport and precipitation of H₂O in a similar fashion to that on Earth provides a source of suitably ¹⁸O depleted water for generation of carbonate with δ¹⁸O_V-SMOW = −10‰.     

异地碳酸盐岩块体与碳酸盐岩重力流沉积研究及展望

异地碳酸盐岩块体是指已固结或半固结的、经过一定距离搬运再沉积而产于正常沉积地层中规模 较大的碳酸盐岩块,它和碳酸盐岩重力流沉积均属于再沉积碳酸盐岩。文章分析了岩崩、岩屑崩坍、海底滑坡、 滑塌和碎屑流沉积的过程,讨论了异地碳酸盐岩块体的沉积机制;归纳了异地碳酸盐岩块体形成的主要地质背 景,认为异地碳酸盐岩块体可见于活动大陆边缘、被动大陆边缘、海山和前陆盆地等地质环境中;着重介绍了 异地碳酸盐岩块体和碳酸盐岩重力流沉积的研究进展,即线源式的碳酸盐岩裙沉积和点源式的碳酸盐岩海底扇 沉积;最后,阐释了滑来岩块、滑塌堆积和碎屑流沉积的区别与联系,总结了孤立碳酸盐岩块体的搬运沉积机 制,对比区分了碳酸盐岩裙沉积和碳酸盐岩海底扇的沉积特征,认为它们在斜坡环境、沉积物类型和沉积特征 等方面存在诸多不同。