The structure and dynamics of 2-dimensional fluids in swelling clays

The interlayer pores of swelling 2:1 clays provide an ideal 2-dimensional environment in which to study confined fluids. In this paper we discuss our understanding of the structure and dynamics of interlayer fluid species in expanded clays, based primarily on the outcome of recent molecular modelling and neutron scattering studies. Counterion solvation is compared with that measured in bulk solutions, and at a local level the cation-oxygen coordination is found to be remarkably similar in these two environments. However, for the monovalent ions the contribution to the first coordination shell from the clay surfaces increases with counterion radius. This gives rise to inner-sphere (surface) complexes in the case of potassium and caesium. In this context, the location of the negative clay surface charge (i.e. arising from octahedral or tetrahedral substitution) is also found to be of major importance. Divalent cations, such as calcium, eagerly solvate to form outer-sphere complexes. These complexes are able to pin adjacent clay layers together, and thereby prevent colloidal swelling. Confined water molecules form hydrogen bonds to each other and to the clays' surfaces. In this way their local environment relaxes to close to the bulk water structure within two molecular layers of the clay surface. Finally, we discuss the way in which the simple organic molecules methane, methanol and ethylene glycol behave in the interlayer region of hydrated clays. Quasi-elastic neutron scattering of isotopically labelled interlayer CH₃OD and (CH₂OD)₂ in deuterated clay allows us to measure the diffusion of the CH₃- and CH₂-groups in both clay and liquid environments. We find that in both the one-layer methanol solvates and the two-layer glycol solvates the diffusion of the most mobile organic molecules is close to that in the bulk solution.     

Sulfide evolution in high-temperature to ultrahigh-temperature metamorphic rocks from Lützow–Holm Complex, East Antarctica

The high-temperature (HT) to ultrahigh-temperature (UHT) metamorphic rocks from Lützow–Holm Complex, East Antarctica show a systematic difference between sulfide assemblages in the rock matrix and those found as inclusions in the silicates stable in high-temperatures. Matrix sulfides are commonly pyrite with or without pentlandite and chalcopyrite. On the other hand, inclusion sulfides are pyrrhotite with or without pentlandite and chalcopyrite lamellae. When recalculated into integrated single-phase sulfide compositions, inclusion sulfides from the UHT region showed a wider range of solid–solution composition than the inclusion sulfides from the HT region. The host minerals of the sulfides with extreme solid–solution compositions are those stable at the peak of metamorphism such as orthopyroxene and garnet. One of the most extreme ones is included in orthopyroxene coexisting with sillimanite ± quartz, which is the diagnostic mineral assemblage of UHT metamorphism. These observations suggest that sulfide inclusions preserve their peak metamorphic compositions. Pyrrhotite did not revert to pyrite because of the closed system behavior of sulfur in inclusion sulfides. On the other hand, in the rock matrix where the open system behavior of sulfur is permitted, original sulfides were partly to completely altered by the later fluid activity.     

Mineral and fluid inclusions in zircon of UHP metamorphic rocks from the CCSD-main drill hole: A record of metamorphism and fluid activity

The Chinese Continental Scientific Drilling (CCSD) main drill hole (0–3000 m) in Donghai, southern Sulu orogen, consists of eclogite, paragneiss, orthogneiss, schist and garnet peridotite. Detailed investigations of Raman, cathodoluminescence, and microprobe analyses show that zircons from most eclogites, gneisses and schists have oscillatory zoned magmatic cores with low-pressure mineral inclusions of Qtz, Pl, Kf and Ap, and a metamorphic rim with relatively uniform luminescence and eclogite-facies mineral inclusions of Grt, Omp, Phn, Coe and Rt. The chemical compositions of the UHP metamorphic mineral inclusions in zircon are similar to those from the matrix of the host rocks. Similar UHP metamorphic P–T conditions of about 770 °C and 32 kbar were estimated from coexisting minerals in zircon and in the matrix. These observations suggest that all investigated lithologies experienced a joint in situ UHP metamorphism during continental deep subduction. In rare cases, magmatic cores of zircon contain coesite and omphacite inclusions and show patchy and irregular luminescence, implying that the cores have been largely altered possibly by fluid–mineral interaction during UHP metamorphism.

Abundant H₂O–CO₂, H₂O- or CO₂-dominated fluid inclusions with low to medium salinities occur isolated or clustered in the magmatic cores of some zircons, coexisting with low-P mineral inclusions. These fluid inclusions should have been trapped during magmatic crystallization and thus as primary. Only few H₂O- and/or CO₂-dominated fluid inclusions were found to occur together with UHP mineral inclusions in zircons of metamorphic origin, indicating that UHP metamorphism occurred under relatively dry conditions. The diversity in fluid inclusion populations in UHP rocks from different depths suggests a closed fluid system, without large-scale fluid migration during subduction and exhumation.     

Correct nomenclature for the Angadimogar pluton, Kerala, southwestern India

The proper usage of modal composition and geochemical classification of granitoids is discussed for assigning a proper nomenclature for the Angadimogar pluton, Kerala, southwestern India. This discussion is mainly aimed at addressing questions concerning the nomenclature of Angadimogar pluton (syenitevs. granite). Modal composition and whole-rock XRD data clearly show that the pluton exposed near Angadimogar is a quartz-syenite and its geochemistry is typical of a ferroan, metaluminous, alkali (A-type) granitoid     

Secular variations of the upper crust composition: Implication of geochemical data on the Upper Precambrian shales from the Southern Urals western flank and Uchur-Maya region

In the mid-1980s, it was concluded based on geochemical study that Th, Sc, La concentrations and ratios Th/Sc, La/Sc and Eu/Eu* did not wary significantly in the post-Archean time. It was impossible to judge about compositional variations of upper crust during the Riphean and Vendian, because data of that time characterized a limited number of samples from the post-Archean basins of Australia, New Zealand, and Antarctic. Considered in this work are variations of Eu/Eu*, LREE/HREE, Th/Sc, and La/Sc ratios in Upper Precambrian fine-grained siliciclastic rock of the Southern Urals western flank (Bashkirian meganticlinorium) and Uchur-Maya region (Uchur-Maya plate and Yudoma-Maya belt). As is established, only the Eu anomaly in the studied siliciclastic rocks is practically identical to this parameter of the average post-Archean shale. Three other parameters plot on the Riphean-Vendian variation curves with positive and negative excursions of diverse magnitude, which do not coincide always in time. It is assumed that these excursions likely mark stages of local geodynamic activity, destruction of pre-Riphean cratons, and progressing recycling of sedimentary material during the Riphean.     

Origin of the Nchanga copper–cobalt deposits of the Zambian Copperbelt

The Zambian Copperbelt forms the southeastern part of the 900-km-long Neoproterozoic Lufilian Arc and contains one of the world’s largest accumulations of sediment-hosted stratiform copper mineralization. The Nchanga deposit is one of the most significant ore systems in the Zambian Copperbelt and contains two major economic concentrations of copper and cobalt, hosted within the Lower Roan Group of the Katangan Supergroup. A Lower Orebody (copper only) and Upper Orebody (copper and cobalt) occur towards the top of arkosic units and within the base of overlying shales. The sulfide mineralogy includes pyrite, bornite, chalcopyrite, and chalcocite, although in the Lower Orebody, sulfide phases are partially or completely replaced by malachite and copper oxides. Carrollite is the major cobalt-bearing phase and is restricted to fault-propagation fold zones within a feldspathic arenite. Hydrothermal alteration minerals include dolomite, phlogophite, sericite, rutile, quartz, tourmaline, and chlorite. Quartz veins from the mine sequence show halite-saturated fluid inclusions, ranging from ~31 to 38 wt% equivalent NaCl, with homogenisation temperatures (Th_TOT) ranging between 140 and 180°C. Diagenetic pyrites in the lower orebody show distinct, relatively low δ ³⁴S, ranging from −1 to −17‰ whereas arenite- and shale-hosted copper and cobalt sulfides reveal distinctly different δ ³⁴S from −1 to +12‰ for the Lower Orebody and +5 to +18‰ for the Upper Orebody. There is also a clear distinction between the δ ³⁴S mean of +12.1±3.3‰ (n=65) for the Upper Orebody compared with +5.2±3.6‰ (n=23) for the Lower Orebody. The δ ¹³C of dolomites from units above the Upper Orebody give δ ¹³C values of +1.4 to +2.5‰ consistent with marine carbon. However, dolomite from the shear-zones and the alteration assemblages within the Upper Orebody show more negative δ ¹³C values: −2.9 to −4.0‰ and −5.6 to −8.3‰, respectively. Similarly, shear zone and Upper Orebody dolomites give a δ ¹⁸O of +11.7 to +16.9‰ compared to Lower Roan Dolomites, which show δ ¹⁸O of +22.4 to +23.0‰_. Two distinct structural regimes are recognized in the Nchanga area: a weakly deformed zone consisting of basement and overlying footwall siliciclastics, and a moderate to tightly folded zone of meta-sediments of the Katangan succession. The fold geometry of the Lower Roan package is controlled by internal thrust fault-propagation folds, which detach at the top of the lowermost arkose or within the base of the overlying stratigraphy and show vergence towards the NE. Faulting and folding are considered to be synchronous, as folding predominantly occurred at the tips of propagating thrust faults, with local thrust breakthrough. The data from Nchanga suggests a strong link between ore formation and the development of structures during basin inversion as part of the Lufilian Orogeny. Sulfides tend to be concentrated within arenites or coarser-grained layers within shale units, suggesting that host-rock porosity and possibly permeability played a role in ore formation. However, sulfides are also commonly orientated along, but not deformed by, a tectonic fabric or hosted within small fractures that suggest a significant role for deformation in the development of the mineralization. The ore mineralogy, hydrothermal alteration, and stable isotope data lend support to models consistent with the thermochemical reduction of a sulfate- (and metal) enriched hydrothermal fluid, at the site of mineralization. There is no evidence at Nchanga for a contribution of bacteriogenic sulfide, produced during sedimentation or early diagenesis, to the ores.Electronic Supplementary Material Supplementary material is available for this article at and is accessible for authorized users.Editorial handling: H. Frimmel     

3D numerical modelling of fluid flow in the Val-d’Or orogenic gold district: major crustal shear zones drain fluids from overpressured vein fields

Fluid flow patterns have been determined using oxygen isotope isopleths in the Val-d’Or orogenic gold district. 3D numerical modelling of fluid flow and oxygen isotope exchange in the vein field shows that the fluid flow patterns can be reproduced if the lower boundary of the model is permeable, which represents middle or lower crustal rocks that are infiltrated by a metamorphic fluid generated at deeper levels. This boundary condition implies that the major crustal faults so conspicuous in vein fields do not act as the only major channel for upward fluid flow. The upper model boundary is impermeable except along the trace of major crustal faults where fluids are allowed to drain out of the vein field. This upper impermeable boundary condition represents a low-permeability layer in the crust that separates the overpressured fluid from the overlying hydrostatic fluid pressure regime. We propose that the role of major crustal faults in overpressured vein fields, independent of tectonic setting, is to drain hydrothermal fluids out of the vein field along a breach across an impermeable layer higher in the crust and above the vein field. This breach is crucial to allow flow out of the vein field and accumulation of metals in the fractures, and this breach has major implications for exploration for mineral resources. We propose that tectonic events that cause episodic metamorphic dehydration create a short-lived pulse of metamorphic fluid to rise along zones of transient permeability. This results in a fluid wave that propagates upward carrying metals to the mineralized area. Earthquakes along crustal shear zones cause dilation near jogs that draw fluids and deposit metals in an interconnected network of subsidiary shear zones. Fluid flow is arrested by an impermeable barrier separating the hydrostatic and lithostatic fluid pressure regimes. Fluids flow through the evolving and interconnected network of shear zones and by advection through the rock matrix. Episodic breaches in the impermeable barrier along the crustal shear zones allow fluid flow out of the vein field.     

Superdense CO2 inclusions in Cretaceous quartz–stibnite veins hosted in low-grade Variscan basement of the Western Carpathians, Slovakia

CO₂ inclusions with density up to 1,197 kg m⁻³ occur in quartz–stibnite veins hosted in the low-grade Palaeozoic basement of the Gemericum tectonic unit in the Western Carpathians. Raman microanalysis corroborated CO₂ as dominant gas species accompanied by small amounts of nitrogen (<7.3 mol%) and methane (<2.5 mol%). The superdense CO₂ phase exsolved from an aqueous bulk fluid at temperatures of 183–237°C and pressures between 1.6 and 3.5 kbar, possibly up to 4.5 kbar. Low thermal gradients (∼12–13°C km⁻¹) and the CO₂–CH₄–N₂ fluid composition rule out a genetic link with the subjacent Permian granites and indicate an external, either metamorphogenic (oxidation of siderite, dedolomitization) or lower crustal/mantle, source of the ore-forming fluids.According to microprobe U–Pb–Th dating of monazite, the stibnite-bearing veins formed during early Cretaceous thrusting of the Gemeric basement over the adjacent Veporic unit. The 15- to 18-km depth of burial estimated from the fluid inclusion trapping PT parameters indicates a 8- to 11-km-thick Upper Palaeozoic–Jurassic accretionary complex overlying the Gemeric basement and its Permo-Triassic autochthonous cover.     

黔西南高砷煤的元素地球化学特征

通过分析黔西南高砷煤的元素地球化学特征,探索高砷煤中微量元素、稀土元素的地球化学行为,从而揭示了高砷煤的形成机理。分析表明,高砷煤与非高砷煤在微量元素含量方面存在较大差异,金、汞、铊矿石与龙潭煤系中的砷具有同源性,龙潭煤系页岩与峨眉山玄武岩在稀土元素组成上具有继承性。     

基于MAPGIS建立地球化学图形-数据库

将建立地球化学图形-数据库过程分为已建立常规地球化学数据库和未建立常规地球化学数据库,其主要区别是采样点位是否具有地理位置坐标。以未建立常规地球化学数据库的情况为例,介绍了利用MAPGIS软件建立和管理地球化学图形-数据库的思路、过程和方法,并简单介绍了利用建立的图形数据库进行检索和地球化学专题图件制作的方法。