Heavy metal and sulfur transport during subcritical and supercritical hydrothermal alteration of basalt: Influence of fluid pressure and basalt composition and crystallinity

Crystalline basalt, diabase and basalt glass have been reacted with a Na-Ca-K-Cl fluid of seawater ionic strength at 350–425°C, 375–400 bars pressure and fluid/rock mass ratios of 0.5–1.0, to assess the role of temperature, basalt/diabase chemistry and texture on heavy metal and sulfur mobility during hydrothermal alteration.Alteration of basalt/diabase is characterized by cation fixation and hydrolysis reactions which show increased reaction progress with increasing temperature at constant pressure. Correspondingly, pH in a series of 400 bar experiments ranges from 4.8 to 2.7 at 350 and 425°C, respectively and is typically lower for alteration of a SiO₂-rich crystalline basalt than for other rock types, due, in part, to relatively high SiO₂ concentrations in solution. High SiO₂ concentrations stabilize hydrous Na- and Ca-rich alteration phases, causing pH to decrease according to reactions such as: 3.0 CaAl₂Si₂O₈ + 1.0 Ca⁺⁺ + 2.0 H₂O = 2.0 Ca₂Al₃Si₃O₁₂(OH) + 2.0 H⁺Phases experimentally produced include: mixed layer chlorite/smectite, Ca-rich amphibole and clinozoisite. Clinozoisite was identified as a replacement product of plagioclase from diabase-solution interaction experiments.In direct response to H⁺ production, dissolved Fe, Mn and H₂S concentrations increase dramatically. For early-stage reaction, H₂S typically exceeds Fe and Mn. However, at 425°C and after long-term reaction at 400°C, H₂S is lost from solution, apparently in response to pyrite replacement of oxide and silicate phases.Pyrrhotite formed at temperatures ≤ 375°C, whereas magnetite was identified in all run products, except from basalt glass alteration.Cu and Zn concentrations in solution are not simple functions of pH. These metals achieve greatest solubility in fluids from experiments at 375–400°C, except when basalt glass is used as a reactant. The relatively low concentrations of these species in solution during basalt glass reaction may be due to adsorption by fine grained alteration phases.     

Magmatic and hydrothermal inclusions in carbonatite of the Magnet Cove Complex,Arkansas

The carbonatite at Magnet Cove, Arkansas, USA contains a great variety and abundance of magmatic and hydrothermal inclusions that provide an informative, though fragmentary, record of the original carbonatite melt and of late hydrothermal solutions which permeated the complex in postmagmatic time. These inclusions were studied by optical and scanning electron microscopy. Primary magmatic inclusions in monticellite indicate that the original carbonatite melt contained approximately 49.7 wt% CaO, 16.7% CO₂, 15.7% SiO₂, 11.4% H₂O, 4.4% FeO+Fe₂O₃, 1.1% P₂O₅ and 1.0% MgO. The melt was richer in SiO₂ and iron oxides than the carbonatite as now exposed; this is attributed to crystal settling and relative enrichment of calcite at shallower levels. The density of the carbonatite melt as revealed by the magmatic inclusions was approximately 2.2–2.3 g/cc. Such a light melt should separate rapidly from any denser parent material and could be driven forcibly into overlying crustal rocks by buoyant forces alone. Fluid inclusions in apatite suggest that a separate (immiscible) phase composed of supercritical CO₂ fluid of low density coexisted with the carbonatite magma, but the inclusion record in this mineral is inconclusive with respect to the nature of any other coexisting fluids. Maximum total pressure during CO₂ entrapment was about 450 bars, suggesting depths of 1.5 km or less for apatite crystallization and supporting earlier proposals of a shallow, subvolcanic setting for the complex. Numerous secondary inclusions in the Magnet Cove calcite contain an intriguing variety of daughter minerals including some 19 alkali, alkaline earth and rare earth carbonates, sulfates and chlorides few of which are known as macroscopic phases in the complex. The exotic fluids from which the daughter minerals formed are inferred to have cooled and diluted through time by progressive mixing with local groundwaters. These fluids may be responsible for certain late veins and elemental enrichments associated with the complex.     

Direct physical evidence of dolomite recrystallization

The possibility of recrystallization is a long‐standing barrier to deciphering the genetic origin of dolomites. There is often uncertainty regarding whether or not characteristics of ancient dolomites are primary or the consequence of later recrystallization unrelated to the original dolomitization event. Results from 65 new high‐temperature dolomite synthesis experiments (1 m , 1·0 Mg/Ca ratio solutions at 218°C) demonstrate dolomite recrystallization affecting stoichiometry, cation ordering and nanometre‐scale surface texture. The data support a model of dolomitization that proceeds by a series of four unique phases of replacement and recrystallization, which occur by various dissolution–precipitation reactions. During the first phase (induction period), no dolomite forms despite favourable conditions. The second phase (replacement period) occurs when Ca‐rich dolomite products, with a low degree of cation ordering, rapidly replace calcite reactants. During the replacement period, dolomite stoichiometry and the degree of cation ordering remain constant, and all dolomite crystal surfaces are covered by nanometre‐scale growth mounds. The third phase (primary recrystallization period), which occurs in the experiments between 97% and 100% dolomite, is characterized by a reduced replacement rate but concurrent increases in dolomite stoichiometry and cation ordering. The end of the primary recrystallization period is marked by dolomite crystal growth surfaces that are covered by flat, laterally extensive layers. The fourth phase of the reaction (secondary recrystallization period) occurs when all calcite is consumed and is characterized by stoichiometric dolomite with layers as well as a continued increase in the degree of cation ordering with time. Inferences of recrystallization, in natural dolomite, based on cation order or stoichiometry of dolomite, usually depend on assumptions about the precursor dolomite subjected to recrystallization. If it is assumed that the experimental evidence presented here is applicable to natural, low‐temperature dolomites, then the presence of mounds is direct evidence of a lack of recrystallization and the presence of layers is direct evidence of recrystallization.     

Composition, sources, and mechanism of continental crust growth in the Lake zone of the Central Asian Caledonides: I. Geological and geochronological data

Data on the composition, inner structure, and age of volcanic and siliceous-terrigenous complexes and granitoids occurring in association with them in the Caledonian Lake zone in Central Asia are discussed in the context of major relations and trends in the growth of the Caledonian continental crust in the Central Asian Foldbelt (CAFB). The folded structures of the Lake zone host basalt, basalt-andesite, and andesite complexes of volcanic rocks that were formed in distinct geodynamic environments. The volcanic rocks of the basalt complex are noted for high concentrations of TiO₂ and alkalis, occur in association with fine-grained siliceous siltstone and siliceous-carbonate rocks, are thus close to oceanic-island complexes, and were likely formed in relation to a mantle hotspot activity far away from erosion regions supplying terrigenous material. The rocks of the basalt-andesite and andesite complexes have lower TiO₂ concentrations and moderate concentrations of alkalis and contain rock-forming amphibole. These rocks are accompanied by rudaceous terrigenous sediments, which suggests their origin in island-arc environments, including arcs with a significantly dissected topography. These complexes are accompanied by siliceous-terrigenous sedimentary sequences whose inner structure is close to those of sediments in accretionary wedges. The folded Caledonides of the Lake zone passed through the following evolutionary phases. The island arcs started to develop at 570 Ma, their evolution was associated with the emplacement of layered gabbroids and tonalitetrondhjemite massifs, and continued until the onset of accretion at 515–480 Ma. The accretion was accompanied by the emplacement of large massifs of the tonalite-granodiorite-plagiogranite series. The postaccretionary evolutionary phase at 470–440 Ma of the Caledonides was marked by intrusive subalkaline and alkaline magmatism. The Caledonides are characterized by within-plate magmatic activity throughout their whole evolutionary history, a fact explained by the accretion of Vendian-Cambrian oceanic structures (island arcs, oceanic islands, and back-arc basins) above a mantle hotspot. Indicators of within-plate magmatic activity are subalkaline high-Ti basalts, alkaline-ultrabasic complexes with carbonatites and massifs of subalkaline and alkaline gabbroids, nepheline syenites, alkaline granites, subalkaline granites, and granosyenites. The mantle hotspot likely continued to affect the character of the lithospheric magmatism even after the Caledonian folded terrane was formed.     

The assemblage quartz — Sillimanite — Garnet — Cordierite as an indicator of metamorphic conditions in the Daly Bay Complex,N.W.T.

If cordierite is treated as an anhydrous mineral, the composition of garnet and cordierite, coexisting with quartz and silliminate, depends on total pressure and temperature. Phase relations may be deduced by combining some available experimental work with several approximations. Assuming ideal ionic solution in garnet and cordierite, analyses of coexisting garnet and cordierite permit the determination of total pressure and temperature. Five rocks from the Daly Bay Complex, N. W. T., collected from locations up to 35 miles apart, indicate a range of 610–760 and 5.3–6.6 kb.     

Fluid inclusion studies of the Abawso gold prospect,near the Ashanti Belt,Ghana

The major Ghanaian lode gold deposits are preferentially aligned along the western and eastern contacts of the Kumasi Basin with the Ashanti and Sefwi Belts, respectively. The investigated area of the Abawso small-scale concession, covering the workings of the old Ettadom mine, is situated 3 km west of the lithological contact of the Birimian metavolcanic rocks of the Akropong Belt in the east with the Birimian metasedimentary rocks of the Kumasi Basin in the west. The rocks of the Abawso concession represent a steeply NW-dipping limb of a SE-verging anticline with an axis plunging to the SW. Quartz veining occurs predominantly in the form of en échelon dilatational veins along NNE–SSW-striking shear zones of a few metres width and shows evidence of brittle and ductile deformation. Also stockwork-style quartz veining occurs in the vicinity of the main shaft of the old Ettadom mine. Hydrothermal alteration includes sericitisation, sulphidation and locally carbonatisation. The auriferous quartz veins mainly follow the trend of brittle to ductile deformed quartz veins; however, some occur in stockwork. Fluid inclusion studies reveal a large number of H₂O inclusions along intragranular trails in auriferous quartz vein samples, as well as an overall dominance of H₂O and H₂O-CO₂ inclusions over CO₂ inclusions. Textural observations and physico-chemical fluid inclusion properties indicate post-entrapment modifications for all quartz vein samples due to grain boundary migration recrystallisation. This process is interpreted to be responsible for the generation of the CO₂ inclusions from a H₂O-CO₂ parent fluid. In comparison with mineralisation at the Ashanti and Prestea deposits, which are characterised by CO₂±N₂ inclusions, the observed inclusion assemblage may be due to a shallower crustal level of mineralisation, or different degrees and styles of recrystallisation, or a less pronounced development of laminated quartz veins due to comparably restricted pressure fluctuations. Furthermore, the microthermometric observations allow the reconstruction of a possible retrograde P-T path, depicting near-isothermal decompression in the P-T range of the brittle/ductile transition.Editorial handling: E. Frimmel     

矿物学文献中未定名矿物的编码系统:国际矿物学协会新矿物与命名和分类委员会“未定名矿物”小组报告

国际矿物学协会新矿物与命名和分类委员会(IMA-CNMMN)的未定名矿物小组(SUM),开发了一个编码系统,对已经发表但尚未定名的矿物进行编码。在文献中存在两类未定名矿物。一是"有效"未定名矿物,是指未定名矿物没有对应的已知矿物种,但如果它们有其他产地或能够在其他样品中被发现,那么已发表的相关矿物描述允许得到认可。二是"无效"未定名矿物,是指未定名矿物已经有对应的已知矿物种;或者相关矿物描述不足以获得认可。未定名矿物的名单是由IMA保管。该编码系统提供了一个永久的UM号码。中国的矿物学文献的数量和重要性有必要用中文阐述未定名矿物的编码系统。     

Diagenesis of Ordovician carbonates from the north-east Michigan Basin, Manitoulin Island area, Ontario: evidence from petrography, stable isotopes and fluid inclusions

Middle to Late Ordovician subtidal carbonates in the Manitoulin Island area of Ontario are predominantly limestone in composition, but non-ferroan and ferroan dolomite is a common cement as well as a selective or locally pervasive replacement phase. Integration of field, petrographic, geochemical (δ¹³C, δ¹⁸O) and fluid inclusion data indicates that lithification of these carbonates occurred during burial diagenesis, with much of the alteration controlled by regional fracturing and hydrothermal influences. Aqueous (type 1) fluid inclusions in early calcite (pre-dolomite) and dolomite are saline (> 29 wt% NaCl eq.) solutions with Ca and/or Mg in excess of Na and display homogenization temperatures with modes of 95 and 101°C, respectively. These temperatures can be explained by significantly more burial than can be accounted for either by the available stratigraphic information or by an unusually high palaeogeothermal gradient, which also is not well supported. The fluid inclusion temperatures are interpreted to have resulted from hydrothermal fluids which circulated during the burial diagenesis of these strata. Type 1 inclusions in late (post-dolomite) calcite are less saline (<19 wt% NaCl eq.) and have a bimodal distribution of homogenization temperatures with a relatively well defined low temperature peak similar to those in early calcite and dolomite and a broad higher temperature grouping with a mode at 183°C. A small proportion of methane and light hydrocarbon-bearing fluid inclusions (type 2) are present in all stages of carbonate. Dolomitizing fluids were derived from burial compaction of argillaceous sediments in the more central parts of the Michigan Basin and the updip migration of these brines along fractures to the basin margin where the carbonates of the Manitoulin Island area were dolomitized. Alternatively, migration of dolomitizing brines downward from the overlying pervasively dolomitized Silurian sequence into fractures in the Ordovician carbonates may have occurred. Integration of the aqueous fluid inclusion data into the diagenetic history of these carbonates remains equivocal because most of the inclusions are secondary or indeterminate in origin. Nevertheless, high salinities resulting from interaction with evaporitic strata and hydrothermal effects are clearly implicated although the origin of the latter remains unclear. The alteration styles of the Ordovician carbonates in the Manitoulin area are similar to those of Ordovician hydrocarbon reservoirs described from other parts of the Michigan Basin. They indicate that fracture-related diagenesis occurred on a basin-wide scale and that hydrothermal effects were important.     

Natrolite,part I: Refinement of high-order data,separation of internal and external vibrational amplitudes from displacement parameters

A single crystal of natrolite, Na₂Al₂Si₃O₁₀·2H₂O, was studied by X-ray diffraction methods at room temperature. The intensities were measured with MoKα radiation (λ = 0.7107 Å) in a complete sphere of reflection up to sin θ/λ = 0.903 Å^?1. The structure was refined in the orthorhombic space group Fdd2 with a = 18.2929 (7) Å, b = 18.6407(9) Å, c = 6.5871(6) Å, V = 2246 ų, Z = 8. A refinement of high-order diffraction data yielded reliability factors of R(F) = 0.9%, R _w(F) = 0.8%, GoF = 1.40 for 1856 high-angle reflections (0.7 ?in θ/λ <0.903 Å^?1) and R(F) = 1.0%, R _W(F) = 1.2%, GoF = 3.07 for all 3471 independent reflections in the complete sphere of reflection. The T-O distances as well as the T-O-T angles were found to be strongly influenced by the different bond strengths received by the individual oxygen atoms. The T O distances calculated using Baur's extended valence rule agree on average within 0.003 Å with the observed values. An analysis of the mean square displacement amplitudes allowed a separation of the external and internal vibrational amplitudes along the T-O bonds as well as along the Na O and H₂O-O bond directions and the calculation of force constants. The internal vibrational amplitudes (ΔU) of the T-O vibrations are in the range of 5 to 11 × 10^-4 Ų, that is about one order of magnitude smaller than the mean square displacement amplitudes of the external vibrations. The corresponding force constants are F = 354 to 824 Nm^?1. The values of the force constants of the motion of the Na-ion and the water molecule against the framework oxygen atoms lie in the range between F = 57 and 293 Nm^?1. This is the first instance where displacement amplitudes from a zeolite structure refinement could be apportioned between contributions from internal and external vibrations for individual bonds.     

The Catoca kimberlite pipe, Republic of Angola: A paleovolcanological model

The Catoca kimberlite pipe is among the world’s largest primary diamond deposits. The Catoca volcanic edifice is only slightly eroded. Kimberlitic rocks of various facies compose a crater of about 1 km in diameter and a diatreme. The structure of the pipe and mining conditions of the deposit are complicated by intense intrapipe tectonic processes related to large-amplitude subsidence. Based on geological data, we propose a structural model of the deposit and a paleovolcanological model of the Catoca pipe formed during a full cycle beginning with a stage of active volcanism and completed by stages of gradually waning volcanic activity and sedimentation. It is suggested that the banded tuffisitic kimberlite of the crater zone was deposited at the stage of active volcanic eruption from specific pyroclastic suspension as a low-viscosity mixture of crystals and aqueous sol rich in serpentine.