花岗质岩石中黑云母成分区域性变化对深部物质示踪及成矿的约束：以秦岭地区为例

秦岭造山带早中生代花岗质岩浆及成矿作用非常发育, 是探讨地壳深部物质组成及成矿关系的重要地区之一, 学者已从岩石学、矿床学和地球化学等角度开展了众多研究, 但对成矿作用与花岗岩和地壳深部物质组成的认识仍不太清楚。黑云母是中酸性岩中常见的暗色矿物, 也是指示成矿可能性的重要矿物之一。因此, 本文对秦岭该期花岗质岩石中黑云母成分开展研究, 为解决该问题探索新途径。对秦岭早中生代花岗质岩石中黑云母成分的研究结果显示, 北秦岭和南秦岭两个构造单元中黑云母成分和形成物理条件存在系统差异, 揭示其岩浆物源有别, 进而制约了其成矿种类特征。北秦岭早中生代花岗质岩石中黑云母的成分和形成条件变化范围小, 以MgO(8%~13%)、TiO₂(3%~5%)和Cl(0.02%~0.6%)含量较高, F(0.2%~0.4%)含量较低, 以及较高的氧逸度(logfO₂值为-16.96~-14.62)和温度(682~771℃)为特征; 而南秦岭的成分和形成条件总体变化范围较大, 具有MgO(3%~15%)、TiO₂(2%~4.5%)、Cl(0.01%~0.18%)含量较低, F(0.1%~1.6%)含量较高, 以及较低的氧逸度(logfO₂值为-20.88~-15.08)和温度(536~754℃)。此外, 研究还显示, 黑云母的形成压力与岩浆演化程度和矿物组合相关, 当岩石中出现黑云母+白云母±石榴子石组合时, 压力较高。秦岭两个构造单元中黑云母成分和形成条件的差异, 特别是氧逸度和Cl含量的明显不同, 揭示各自的成矿种类和成矿潜力不同, 如北秦岭较高的氧逸度和Cl含量, 形成铜矿的潜力比南秦岭大。同时, 两个构造单元中黑云母的成分差异, 还揭示了岩浆物源及深部物质组成的不同, 即北秦岭比南秦岭具有更为年轻的地壳, 这与区域同位素填图示踪的深部物质组成差异基本一致。由此可见, 对区域上同时代花岗质岩石中黑云母成分的研究, 不仅可以揭示岩浆演化、岩浆结晶过程物理化学条件等, 还可示踪深部物质组成的空间变化与差异及成矿种类和潜力, 有望成为探测深部物质组成的新方法和了解区域成矿背景和潜力的新途径。

     

Wall-Rock alteration of biotite hornfels at the Tyrnyauz deposit,Russia

A new zonation type of W–Mo-bearing altered biotite hornfels at the Tyrnyauz deposit is reported. The review of zonation indicates a subsequent transition into the mobile state of CaO, MgO, FeO, and Al₂O₃ and retention of volume owing to dissolution or deposition of quartz as an excess mobile mineral. The main features of zonation are similar to those in acid leaching columns; the input of strong CaO base into the outer zone is unusual.     

Evolution of 2:1 layered silicates in low-grade metamorphosed Liassic shales of Central Switzerland

White mica from the Liassic black shales and slates in Central Switzerland was analysed by transmission electron microscopy (TEM) and electron microprobe to determine its textural and compositional evolution during very low-grade prograde metamorphism. Samples were studied from the diagenetic zone, anchizone and epizone (T ≈100°–450 °C). Phyllosilicate minerals analysed include illite/smectite (I/S), phengite, muscovite, brammallite, paragonite, margarite and glauconite. Textural evolution primarily is towards larger, more defect-free grains with compositions that approach those of their respective end-members. The smectite-to-illite transformation reduced the amounts of the exchange components SiK_?1Al_?1, MgSiAl_?2, and Fe³⁺Al_?1. These trends continue to a lesser degree in the anchizone and epizone. Correlations between the proportion of smectite in I/S and the composition of I/S indicate that smectite layers may contain a high layer charge. Illite in I/S bears a compositional resemblance to macrocrystalline phengite in some samples, but is different in others. Paragonite first appears in the upper diagenetic zone or lower anchizone as an interlayer-deficient brammallite, and it may be mixed with muscovite on the nanometre scale. Owing to the small calculated structure factor for paragonite-muscovite superstructures, conventional X-ray powder diffraction cannot distinguish between mixed-layer structures and a homogeneous compositionally intermediate solid solutions. However, indirect TEM evidence shows that irregularly shaped domains of Na- and K-rich mica exist below 10 nm. Subsequent coarsening of domains at higher grades produced discrete paragonite grains at the margins of muscovite crystals or in laths parallel to the basal plane of the host muscovite. Margarite appears in the epizone and follows a textural evolution similar to paragonite in that mixtures of margarite, paragonite, and muscovite may initially occur on the nanometre scale. However, no evidence of interlayer-poor margarite has been found.     

Formation of corrensite, chlorite and chlorite-mica stacks by replacement of detrital biotite in low-grade pelitic rocks

Transmission and scanning electron microscopy were utilized to investigate the nature and mechanisms of alteration of abundant detrital biotite of volcanic origin and progressive modification of phyllosilicate aggregates in a prograde sequence of pelitic rocks (illite crystallinity index = 0.19–0.58λ2θ) from the Gaspé Peninsula in Quebec.
Detrital biotite has been diagenetically altered to form corrensite and chlorite through two mechanisms; (1) layer-by-layer replacement gave rise to interstratification of packets of layers and complex mixed layering via several kinds of layer transitions between biotite and chlorite, corrensite or smectite; (2) dissolution-transport-precipitation resulted in the formation of relatively coarse-grained aggregates of randomly orientated, corrensite-rich flakes and fine-grained corrensite intergrown with chlorite and illite in the matrix.
The data show that stacks consisting of alternating packets of trioctahedral and dioctahedral phyllosilicates originated during early diagenesis when lenticular fissures in strained altering biotite were filled by dioctahedral clays. Subsequent prograde evolution of dioctahedral clays occurred through deformation, dissolution and crystallization, and overgrowth. Illite evolved to muscovite, with K in part provided through biotite alteration, and corrensite/chlorite to homogeneous chlorite. The alteration of detrital biotite is closely related to the formation of titanite and magnetite in diagenetic rocks, and pyrite, calcite and anatase or rutile in the higher grade rocks.
The observations demonstrate that detrital biotite of volcanic origin may be the principal precursor of chlorite in chlorite-rich metapelites originating in marginal basins. The mineral parageneses suggest that the transitions from corrensite to chlorite and illite to muscovite may be a function of local chemistry and time.     

Mineralogical and geochemical alteration of low-grade metamorphic black slates due to oxidative weathering

Low-grade metamorphic black slates of Silurian and Lower Devonian ages (from the Thüringisches Schiefergebirge in Germany) were investigated to identify mineralogical and geochemical alterations that occur during the oxidative weathering black slates.The slates exhibit an intense total organic carbon decrease (>90 wt%) due to oxidative weathering. The organic matter in black slate consists mainly of non-pyrolysable material with only minor portions of pyrolysable material. In contrast to the non-pyrolysable organic matter, the concentration of pyrolysable organic matter is not decreased during weathering. Heating experiments have yielded information about a potential protection of pyrolysable organic matter against weathering, which is probably caused by a structural configuration or the intergrowth of organic matter and illite.The slates consist mainly of illite. Iron oxide (goethite) and phosphate encrustations were formed on slate surfaces as a result of oxidative and acid weathering of both iron sulfide and monazite. Kaolinite often occurs as an older encrustation beneath the iron oxide encrustations. Encrustations of iron oxide and phosphate are major sinks for trace elements, released during oxidative weathering.     

Comparison of crude oils and their alteration products

A simple method is proposed for using gas Chromatographic data on the high molecular weight saturated fractions of crude oils to make comparisons of source materials, migration mechanisms and, in particular, alteration processes within reservoirs. The preferential loss of normal alkanes by bacterial attack on a light crude is one of several processes readily followed using this scheme.     

Derivatives of silicic acids as model compounds for silicates

Silicon-29 chemical shifts of methyl, ethyl, chloro and trimethylsilyl derivatives of silicic acids are compared to those of silicic acid anions found in aqueous solutions. Although the chemical shifts of the silicate anions vary with pH and concentration, a good correlation is obtained for the chloro and alkoxi derivatives. The chemical shifts of the trimethylsilyl esters are of limited comparability to the data of the silicates only.     

Lead and strontium isotopes as monitors of experimental granitoid mineral dissolution

Flow-through dissolution experiments were carried out on crushed granitoid rock (the Elat Granite) and three mineral separates (plagioclase, perthite, and biotite + chlorite) from this rock at pH 1 and 25°C. Major element concentrations were combined with Pb and Sr isotopic analyses of starting materials and output solutions and together enabled us to elucidate several important mechanisms related to granitoid rock weathering. We observed an initial stage of rock dissolution (<200 hours of reaction) that was characterized by elemental release from traces of calcite and/or apatite and to a lesser extent from the interlayer sites of biotite. Dissolution in the interval of 200 to 400 h was dominated by the release of elements from the interlayer sites of biotite, and at 400 to 1000 h of reaction the chemistry of output solutions was dominated by the release of elements from tetrahedral and octahedral sites of biotite as well as from plagioclase. After 1000 h, the dissolution of plagioclase, and to a lesser extent biotite, dominated the composition of elements released by the rock. We demonstrate that Pb and Sr isotope ratios in the output solutions can be used to identify each of these stages of dissolution. By comparing our experimental results on the release of Pb and Sr isotopes with field measurements of Pb and Sr isotopes in soil chronosequences from the Wind River and the Sierra Nevada Mountains (USA), we are able to show that similar isotopic patterns appear in both the pH 1 experiments and in soils formed under natural conditions at higher pH. By combining these experimental results with previous field studies, we are able to estimate the duration of most of these stages of granitoid weathering under natural conditions in temperate climates. In soils older than a few hundred years and younger than 10,000 yr the release of elements from interlayer sites of biotite controls the weathering flux. Soils between 10,000 and 100,000 yr old are dominated by biotite and plagioclase weathering, with biotite weathering controlling the first part of this period and plagioclase dominating the later part. After more than 100,000 yr, plagioclase, and to a lesser degree biotite, dominate the weathering flux within these granitoid soils.     

Natural alteration products of sulphide mattes from primary lead smelting

The natural alteration products developed on mattes from lead metallurgy were determined: oxides and hydroxides (HFO, Cu(OH)₂), sulphates (thenardite, gypsum), hydroxysulphates (jarosite, beaverite, brochantite) and carbonates (cerussite, malachite, NaOH·2 PbCO₃). The large range of stability of newly formed phases confirms a significant variety of E_h–pH conditions of natural weathering of matte. Jarosite is stable at pH<3, but some hydroxides and carbonates typically form in neutral and alkaline environments. Consequently, the best dumping conditions for metallurgical mattes are difficult to determine. Such materials can have severe environmental effects and should be dumped in controlled waste-disposal sites. To cite this article: V. Ettler et al., C. R. Geoscience 335 (2003).     

Spectroscopic evidence for aqueous alteration products on the surfaces of low-albedo asteroids

High-resolution IR spectra (0.9–2.5 μm) and narrowband photometry (3.0–3.5 μm) are presented for asteroids 1 Ceres, 2 Pallas and 324 Bamberga. Laboratory experiments with hydrated minerals indicate that the 3 μm absorption feature observed on asteroids is largely due to interlayer water molecules in clay minerals, with a possible contribution from water molecules bound to salts. The depth of the 3 μm band as a function of 2.2 μm albedo is a useful measure of the amount of hydrated mineral present on these asteroids. 1 Ceres must consist mostly of a clay mineral like that in CM chondrites, with some contribution to the strength of the 3 μm band by hydrated salts. These salts, which are products of aqueous alteration, may also be responsible for Ceres' high albedo relative to other C-type asteroids. 2 Pallas must have a low abundance of hydrated minerals relative to 1 Ceres, with the bulk of its composition being spectrally featureless minerals such as the iron-free silicates in CM chondrules. 324 Bamberga probably contains clay minerals, but their abundance cannot be determined at present. The spectrum of Bamberga below 2.5 μm shows evidence for abundant magnetite, which can be a product of aqueous alteration. The presence of magnetite on Bamberga and possibly other C-type asteroids may be responsible for their low albedos. The spectra of C-type asteroids may be reconcilable with those of carbonaceous chondrites if the asteroids surfaces have undergone alteration by aqueous or other analogous processes.     

Garnet compositions and their use as indicators of peraluminous granitoid petrogenesis — southeastern Arabian Shield

Garnet, an uncommon accessory mineral in igneous rocks, occurs in seven small peraluminous granitoid plutons in the southeastern Arabian Shield; textural equilibrium between garnet and other host granitoid minerals indicates that the garnets crystallized from their host magmas. Compositions of the garnets form three groups that reflect host-granitoid compositions, which in turn reflect source compositions and tectonic regimes in which the host magmas were generated. Garnets from the seven plutons have almandine-rich cores and spessartine-rich rims. This reverse zoning depicts host magma compositional evolution; i.e. rimward spessartine enrichment resulted from progressive, host-magma manganese enrichment. The garnets are heavy rare-earth element enriched; (Lu/La) _N ranges from 13 to 355 and one of the garnets contains spectacularly elevated abundances of Y, Ta, Th, U, Zn, Zr, Hf, Sn, and Nb. Involvement of garnets with these trace element characteristics in magma genesis or evolution can have dramatic effects on trace element signatures of the resulting magmas. Other researchers suggest that Mn-enriched magmas are most conducive to garnet nucleation. Although the garnetiferous granitoids discussed here are slightly Mn enriched, other genetically similar peraluminous Arabian granitoids lack garnet; Mn enrichment alone does not guarantee garnet nucleation. The presence of excess alumina in the magma may be a prerequisite for garnet nucleation.     

Examination of chloritization of biotite as a tool for reconstructing the physicochemical parameters of mineralization and associated alteration in the Zafarghand porphyry copper system,Ardestan, Central Iran: mineral-chemistry and stable isotope analyses

Mineralogy and Petrology - The chloritization of biotite and stable isotopes of silicate have been studied for the Zafarghand porphyry copper deposit, Ardestan, Iran. The studied area, in the...     

Typochemistry of rinkite and products of its alteration in the Khibiny Alkaline pluton,Kola Peninsula

The occurrence, morphology, and composition of rinkite are considered against the background of zoning in the Khibiny pluton. Accessory rinkite is mostly characteristic of foyaite in the outer part of pluton, occurs somewhat less frequently in foyaite and rischorrite in the central part of pluton, even more sparsely in foidolites and apatite–nepheline rocks, and sporadically in fenitized xenoliths of the Lovozero Formation. The largest, up to economic, accumulations of rinkite are related to the pegmatite and hydrothermal veins, which occur in nepheline syenite on both sides of the Main foidolite ring. The composition of rinkite varies throughout the pluton. The Ca, Na, and F contents in accessory rinkite and amorphous products of its alteration progressively increase from foyaite and fenitized basalt of the Lovozero Formation to foidolite, rischorrite, apatite–nepheline rocks, and pegmatite–hydrothermal veins.     

Clumped isotope thermometry of carbonatites as an indicator of diagenetic alteration

We measure the clumped isotopic signature of carbonatites to assess the integrity of the clumped isotope paleothermometer over long timescales (10⁷-10⁹ years) and the susceptibility of the proxy to closed system re-equilibration of isotopes during burial diagenesis. We find pristine carbonatites that have primary oxygen isotope signatures, along with a Carrara marble standard, do not record clumped isotope signatures lighter than 0.31‰ suggesting atoms of carbon and oxygen freely exchange within the carbonate lattice at temperatures above 250-300 °C. There is no systematic trend in the clumped isotope signature of pristine carbonatites with age, although partial re-equilibration to lower temperatures can occur if a carbonatite has been exposed to burial temperatures for long periods of time. We conclude that the solid-state re-ordering of carbon and oxygen atoms is sufficiently slow to enable the use of clumped isotope paleothermometry on timescales of 10⁸ years, but that diagenetic resetting can still occur, even without bulk recrystallization. In addition to the carbonatite data, an inorganic calibration of the clumped isotope paleothermometer for low temperature carbonates (7.5-77 °C) is presented and highlights the need for further inter-lab standardization.     

Quantification of Ar recoil ejection from GA1550 biotite during neutron irradiation as a function of grain dimensions

This study presents the first measurement of ³⁹Ar recoil ejection loss from individual, dimensionally characterized mineral grains due to neutron irradiation, and reveals the extent to which this recoil loss is problematic for ⁴⁰Ar/³⁹Ar dating. Using the well-characterized biotite standard GA1550, known to have between grain reproducibility of ⁴⁰Ar*/³⁹Ar_K of order 0.1%, we measured the thicknesses (3-210 μm) and surface areas (0.07-0.90 mm²) of 159 grains selected to span the dimensional range represented in the aliquot. Thinner grains with high surface area/volume (SA/V) reveal elevated ⁴⁰Ar/³⁹Ar, as much as 26% higher than thicker grains expected to suffer proportionately negligible depletion. Although the thinner grains yield intrinsically less precise measurements due to small ³⁹Ar ion beams, a regular decrease in net recoil loss with increasing biotite grain thickness is clear for grains thinner than ca. 50 μm. Grains thicker than 50 μm reveal essentially no ³⁹Ar loss within analytical uncertainties. The measured ³⁹Ar loss spectrum is significantly higher than predicted by previous modeling approaches. These results suggest a practical threshold of ca. 50 μm grain thickness for biotites, and probably other phyllosilicates, irradiated with ²³⁵U fission spectrum neutrons in order to avoid recoil artifacts. Poor agreement between our data and simulation results indicates that recoil displacement models should be revisited in order to resolve the discrepancy. Further empirical work to determine the recoil loss of ³⁹Ar in other minerals is important not only for routine age measurements, but also to shed more light on the role of recoil in multi-diffusion domain theory and other thermochronologic applications exploiting variable diffusion radii and/or grain size effects.     

The electrical conductivity of some hydrous and anhydrous molten silicates as a function of temperature and pressure

Electrical conductivity of the following molten silicate systems (in mol%): 60SiO₂-40Na₂O; 65SiO₂-35Na₂O; 75SiO₂-25Na₂O; 78SiO₂-22Na₂O; 72SiO₂-24Na₂O-4CaO; 66SiO₂-19Na₂O-15H₂O; and an anhydrous and hydrous (4 wt% H₂O) Mt. Erebus lava, have been measured as a function of temperature (to 1000°C) and pressure (to 1.3 kbar). The anhydrous soda-rich melts have a positive pressure coefficient of conductivity to ~200 bars and beyond this pressure the pressure coefficient is small and negative. Addition of water lowers the conductivity and gives rise to a negative pressure coefficient at the highest temperatures. The conductivity of hydrous Mt. Erebus lava passed through a maximum with increasing temperature at constant pressure. These phenomena are interpreted in terms of explanations of similar phenomena found in molten salt and aqueous electrolyte solutions.     

Problem of the gold and tin metallogenic specialization of granitoid fluid-magma systems as exemplified by the Russian Far East

The formation of large accumulations of Au and Sn and independent metallogenic provinces, zones, and clusters is based on both the heterogeneous structure of the Earth’s crust and the upper mantle, which results in the diversity of the sources of magmas and ore-forming elements, and the differences in the geochemical properties of these elements. During the transport of Au and Sn by fluid-magma columns, the mobility of the metals is affected and polarized by their different affinity to the silicate-forming clusters of melt, oxygen, and other strong oxidizers. This influence promoted the divergence of the migration paths of these elements to ore concentration levels. By the moment of the release of the ore-forming fluids, the metallogenic characteristics of the melts with contrasting redox potentials were usually already established, which is supported by the preferential association of the tin and gold mineralization with ilmenite-and magnetiteseries granitoids, respectively. Combined concentrations of the metals could potentially be produced by fluid-magma systems with transitional degrees of the melt oxidation. However, even in such cases, the simultaneous concentration of tin and gold was hampered by the opposing redox reactions of the formation of the most common minerals of these metals: the main tin migration species — Sn²⁺— had to be oxidized with the formation of cassiterite, whereas the mobile gold species — Au⁺ or Au³⁺ — had to be reduced with the formation of native gold. Perhaps, this is why the combined concentrations of tin and gold are characterized by the dominance of one of the metals with a tendency for their accumulation in mineral complexes of different stages. The redox state of the melts controlling the migration activity of the metals depended on the duration of the movement of the fluid-magma columns toward the levels of ore concentrations. This parameter is a function of the depths of their generation and their movement velocity, which were controlled by the geodynamic conditions.     

Arsenic mobility in alteration products of sulfide-rich, arsenopyrite-bearing mine wastes, Snow Lake, Manitoba, Canada

The Arsenopyrite Residue Stockpile (ARS) in Snow Lake, Manitoba contains approximately 250,000 tons of cyanide treated, refractory arsenopyrite ore concentrate. The residue was deposited between 1950 and 1959 in an open waste rock impoundment, and remained exposed until 2000, when the pile was capped with layers of waste rock and clay. During the time when the ARS was exposed to the atmosphere, arsenopyrite, pyrrhotite, pyrite and chalcopyrite were oxidized producing scorodite, jarosite and two generations of amorphous Fe sulfo-arsenates (AISA). These secondary phases attenuated some of the As released to pore water during oxidation in the upper layers of the ARS. The imposition of the cap prevented further oxidation. The secondary As minerals are not stable in the reduced environment that currently dominates the pile. Therefore, As currently is being released into the groundwater. Water in an adjacent monitoring well has concentrations of >20 mg/L total As with relative predominance of As(III).