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.     

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.     

青藏高原东缘缅萨洼金矿成矿流体地质地球化学特征

缅萨洼金矿位于中国中轴构造带的中南段,青藏高原的东缘,赋存于金河-箐河断裂带次级断裂羊坪子韧性剪切带中本文根据对该矿床硫化物流体包裹体的氦氩同位素、硫化物的硫同位素以及与硫化物共生的石英的流体包裹体特征、成分以及氢氧同位素组成的测定,讨论了缅萨洼金矿的成矿流体来源及其矿床成因。结果显示,该矿床硫化物流体包裹体中的3He/4He变化较小,为0.69-0.82,显示了地幔流体参与成矿作用的可能性。而4He的含量变化范围较大,一般在2.19-10.62×10-6cm3STP/g(方铅矿除外)与3He/4He相比,40Ar/36Ar的比值则变化较小,一般为251-509。而硫化物的δ34S同位素变化范围在-1.8-2.2‰,平均值为0.5‰,说明硫的地幔来源。与硫化物共生的石英的流体包裹体的类型主要有富液相的盐水溶液包裹体、富气相的盐水溶液包裹体、三相CO2包裹体、纯液相CO2包裹体以及有机流体包裹体。成矿流体的氢氧同位素则显示成矿流体来源于岩浆水(或地幔流体)与大气降水的混合流体,本文认为,缅萨洼金矿的成矿流体为地幔流体与大气降水的混合流体,是渐新世印度大陆与亚洲大陆碰撞之后,该地区大规模走滑与剪切作用过程中,局部伸展作用的产物。     

CCSD在线流体监测捕获的气体地球化学异常与2004年9．3级苏门答腊地震可能的超远程关系

中国大陆科学钻探工程在线流体地球化学监测在2004年12月10至2005年1月10日之间捕获到一段重要的气体地球化学异常。该异常从2004年12月24日晚上11点半开始到12月29日晚上7点半结束,其中在12月26日早上7点半到29日晚7点半这段异常非常特殊,表现出流体地球化学的剧烈变化。具体表现为流体组分从基本上不含Ar、He及N2跳跃到富含Ar、但亏损He和N2。该异常发生在2004年9.3级苏门答腊地震前1个半小时。由于CCSD现场离苏门答腊地震震中距离大于4170公里,大于该地震破裂长度1200公理的3倍,该地震在CCSD现场产生的静态应力变化微乎其微,不足以导致CCSD现场深部岩石或封闭破裂的岩石物理性质剧烈变化,因而可以排除静态激发效应的作用。在我国的云南和广东等地所观测到的地震异常和地下水位变化等表明2004年苏门答腊地震的动态激发效应主要沿东北方向,这和大地震的动态激发具有方向性一致。而CCSD现场就位于该方向上。我们推测2004年苏门答腊地震所产生的面波在CCSD现场激发的动态效应,导致库仑型失稳,增进深部岩石或破裂带的渗透率,释放富含Ar但亏损He和N2的流体,产生CCSD所观测到的气体异常。     

西北地区不同类型云的时空分布及其与降水的关系

利用1983年7月～2001年9月国际卫星云气候计划ISCCP D2的月平均资料，对西北不同区域不同类型云的云量和云水路径的时空分布及其与降水的关系进行了研究。结果表明:高原气候区是各种云出现最多的地区，特别是积状云的云量明显高于其他两区，但这些云的云水路径值低；西北地区大多数云云量的高值区出现在天山山区、北疆地区、陕西东南部和青藏高原的部分地区。高云和部分中云云量空间分布特征与降水有着较好的一致性:沿着天山—昆仑山—祁连山一带以及陕南和／或陇南地区是高值区，低值区在塔里木盆地—内蒙古西部戈壁沙漠—黄土高原西北部一带；绝大多数云类春夏季节云量维持较高，秋冬季节云量较少。云水路径值较大的层状云类的云量多寡与降水多寡相一致；积状云类和层积云类云量多少与降水没有一定的关系，在降水偏少时，这类云的云量大多与降水正常时相近，有些云的云量甚至比降水偏多时还要多。     

西北地区空中云水资源的时空分布特征

利用1983年7月至1998年12月国际卫星云气候计划ISCCP D2的月平均云资料,对西北地区空中云水资源的时空分布特征进行了系统的研究。结果表明:三个不同区域的月平均总云量、光学厚度和云水路径的区域平均值分别在52.5%~58.3%,2.6~6.6和44.9~77.6 g.m-2之间;西北地区空中云水资源多年平均分布有其沿地形分布的特点,总云量、中云量、总光学厚度和总云水路径的高值区均在天山、昆仑山、祁连山一带,而低值中心一般分布在塔里木盆地—内蒙古西部戈壁沙漠—黄土高原西北部一带。此外,祁连山、青海所在的高原气候区云水资源近年呈上升趋势,特别是总光学厚度和总云水路径15年来呈明显上升趋势,分别约上升了0.8和16.4 g.m-2。     

大别山晓天—磨子潭断裂带石英脉流体包裹体的特征及其构造意义

晓天—磨子潭断裂流体包裹体的均一温度、盐度和捕俘压力研究结果表明:晓天—磨子潭断裂中石英脉中流体主要来自浅部,有多期次流体包裹体,流体包裹体的均一温度分为三个区间:140～180℃、190～240℃和270～340℃,反映了至少经历了三次强烈的流体活动。流体包裹体的盐度<10%,捕获压力<1.350×108Pa。总体上越靠近晓天—磨子潭断裂,包裹体的均一温度和盐度越高,捕获压力越大,局部地区的差异,能从断裂对流体控制上得到合理的解释;另外,流体包裹体的均一温度、盐度和捕获压力,在不同的显微构造,围岩性质、构造环境和时空范围中,发生不同的变化。一方面多次构造活动和热事件的驱动流体活动,另一方面流体的活动,降低了岩石脆—韧性变形的温压条件,促进了岩石的变形。     

Strike-slip fault bridge fluid pumping mechanism: insights from field-based palaeostress analysis and numerical modelling

We present a finite-element study of stress perturbation in evolving compressive and extensional strike-slip fault bridges. The results are compared with a fracture study of a compressive bridge at St Donats, UK. Horizontally interbedded calcareous mudstone and bioclastic calcilutite at St Donats have a distinct vertical permeability anisotropy. This sedimentary sequence behaves as a set of horizontal aquifers. The fluid flow in these aquifers is sensitive to mean stress gradients. Paleostress analysis of field fracture data, verified by finite-element modelling, indicates a rotation of σ₁ towards parallelism with boundary faults inside the growing compressive bridge. Boundary faults and bridge faults recorded numerous fluid flow events. The modelled mean stress pattern shows a regional maximum within the bridge and local maxima/minima pairs at boundary fault tips.Finite-element modelling of an extensional bridge indicates that σ₃ rotates towards parallelism with boundary faults. The mean stress pattern is similar to the pattern in compressive bridge but with maxima and minima locations interchanged. The stress patterns are reestablished by each stress build-up preceding the rupturation of the boundary faults throughout the development stages of strike-slip fault bridges. Mean stress gradients developed pre-failure control the fluid flow in fractures of the strike-slip fault system at and after the end of each stress build-up and the fluid flow in boundary faults post-failure. Fracture reactivation and new fracture generation within an evolving bridge is a process consisting of multiple successive events that retain the storage capacity of the bridge. Rupture and sealing of the main bounding-faults is a step-wise process that opens and closes fluid conduits between areas with different pressures.