Geochemical evidence for the manufacture,logistics and supply‐chain management of Emperor Qin Shihuang's Terracotta Army,China

Non‐invasive materials characterisation of reconstructed statues of Emperor Qin Shihuang's Terracotta Army has revealed distinct micro‐geochemical patterning within the clay paste used in their manufacture. The significance of this is explored in terms of the production sequence, logistics and supply‐chain management involved in the construction of this enormous funerary assemblage. Of particular interest is a compositional distinction between figures marked with the names ‘Gong’ (宫) and ‘Xianyang’ (咸阳). These seem to represent the products of two workshops involved in the supply of ceramic objects for this ambitious, large‐scale building project undertaken by the Qin Empire during the third century bce .     

The inclusion record of fluid evolution,crack healing and trapping from a heterogeneous system during rapid cooling of pegmatitic veins (Dronning Maud Land; Antarctica)

Granitoid (pegmatite and aplite) veins in metamorphic rocks and intrusive syenites of central Dronning Maud Land, Antarctica, are flanked by conspicuous light‐coloured alteration halos, which represent the damage zone of fracture propagation. The damage zone is characterized by a high density of sealed or healed microcracks, about 1 order of magnitude above background. Fluid inclusions along healed microcracks in quartz of both pegmatite and alteration halos are inspected by optical and scanning electron microscopy, and their composition is analysed by microthermometry and quadrupole mass spectrometry. The similar inclusion record in the granitoid vein and in the damaged host rock indicates the derivation of the fluids from the hydrous melt phase. The aqueous inclusions bear abundant daughter crystals, mainly silicates, and may represent a hydrous melt. The volatile composition is variable in the system H₂O–CO₂, with mostly subordinate amounts of N₂. Phase separation with partitioning of CO₂ into the fluid phase coexisting with the hydrous melt, and possibly immiscibility in the subsolidus range, govern fluid evolution during cooling. The variable CO₂/N₂ ratio suggests mixing with fluids from an external source in the host rock and vigorous circulation at an early stage of high transient permeability. Experiments have shown that healing of microcracks at high temperatures is a matter of hours to weeks, hence similar in time scale to the cooling of the cm‐ to dm‐thick granitoid veins. In this case, rapid cooling and concomitant crack healing in a system undergoing phase separation causes a broad compositional variability of the inclusions due to necking down, and the underpressure developing in closed compartments precludes a meaningful thermobarometric interpretation.     

Hybrid finite element–finite volume discretization of complex geologic structures and a new simulation workflow demonstrated on fractured rocks

The generation of computational meshes of complex geological objects is a challenge: their shape needs to be retained, resolution has to adapt to local detail, and variations of material properties in the objects have to be represented. Also mesh refinement and adaptation must be sufficient to resolve variations in the computed variable(s). Here, we present an unstructured hybrid finite element, node‐centred finite‐volume discretization suitable for solving fluid flow, reactive transport, and mechanical partial differential equations on a complex geometry with inhomogeneous material domains. We show that resulting meshes accurately capture free‐form material interfaces as defined by non‐uniform rational B‐spline curves and surfaces. The mesh discretization error is analysed for the elliptic pressure equation and an error metric is introduced to guide mesh refinement. Finite elements and finite volumes are represented in parametric space and integrations are conducted numerically. Subsequently, integral properties are mapped to physical space using Jacobian transformations. This method even retains its validity when the mesh is deformed. The resulting generic formulation is demonstrated for a transport calculation performed on a complex discrete fracture model.     

Roman pottery production in Civitas Tungrorum,central Belgium,during the first–third centuries ce

Aspects of Roman pottery production at the workshops of Kontich, Tienen, Rumst, Grobbendonk and Clavier-Vervoz in the Civitas Tungrorum of central Belgium are explored. A total of 150 wasters from five sites were studied macroscopically, as well as via a combination of thin-section petrography, geochemistry and scanning electron microscopy, in order to gain insights into ceramic technology and aspects of the organization of production. Particular emphasis was given to the individual technological sequences and shared strategies of raw material selection, paste preparation and firing employed at the five adjacent sites. The integration of petrographic and geochemical data permitted the establishment of compositional reference groups for the Roman kiln sites of Civitas Tungrorum, which can be used to track their products within the surrounding landscape.     

Geoarchaeology and spatial distributions of the ‘Coche Quemado' obsidian source in north-western Patagonia

In north-western Patagonia, obsidian was used during the entire Holocene, and its importance increased with time. Recent fieldwork discovered a new obsidian source located in the Río Grande, which was called ‘Coche Quemado' (CQ). The results indicate that the CQ source has a different geochemical signal than all other sources in the region. Its use is spatially restricted to piedmont and, to a lesser extent, the plains. Chronologically, CQ was exploited in the middle and late Holocene, and its use accounts for a range of spatial distribution between 150 and 200 km.     

Role of compressive tectonics on gas charging into the Ordovician sandstone reservoirs in the Sbaa Basin,Algeria: constrained by fluid inclusions and mineralogical data

Structure‐ and tectonic‐related gas migration into Ordovician sandstone reservoirs and its impact on diagenesis history were reconstructed in two gas fields in the Sbaa Basin, in SW Algeria. This was accomplished by petrographical observations, fluid inclusion microthermometry and stable isotope geochemistry on quartz, dickite and carbonate cements and veins. Two successive phases of quartz cementation (CQ1 and CQ2) occurred in the reservoirs. Two phase aqueous inclusions show an increase in temperatures and salinities from the first CQ1 diagenetic phase toward CQ2 in both fields. Microthermometric data on gas inclusions in quartz veins reveal the presence of an average of 92 ± 5 mole% of CH₄ considering a CH₄‐CO₂ system, which is similar to the present‐day gas composition in the reservoirs. The presence of primary methane inclusions in early quartz overgrowths and in quartz and calcite veins suggests that hydrocarbon migration into the reservoir occurred synchronically with early quartz cementation in the sandstones located near the contact with the Silurian gas source rock at 100–140°C during the Late Carboniferous period and the late Hercynian episode fracturing at temperatures between 117 and 185°C, which increased in the NW‐direction of the basin. During the fracture filling, three main types of fluids were identified with different salinities and formation temperatures. A supplementary phase of higher fluid temperature (up to 226°C) recorded in late quartz, and calcite veins is related to a Jurassic thermal event. The occurrence of dickite cements close to the Silurian base near the main fault areas in both fields is mainly correlated with the sandstones where the early gas was charged. It implies that dickite precipitation is related to acidic influx. Late carbonate cements and veins (calcite – siderite – ankerite and strontianite) occurred at the same depths resulting from the same groundwater precipitation. The absence of methane inclusions in calcite cements result from methane flushing by saline waters.     

Carbon dioxide controlled earthquake distribution pattern in the NW Bohemian swarm earthquake region,western Eger Rift,Czech Republic – gas migration in the crystalline basement

The ascent of magmatic carbon dioxide in the western Eger (Oh?e) Rift is interlinked with the fault systems of the Variscian basement. In the Cheb Basin, the minimum CO₂ flux is about 160 m³ h^?1, with a diminishing trend towards the north and ceasing in the main epicentral area of the Northwest Bohemian swarm earthquakes. The ascending CO₂ forms Ca‐Mg‐HCO₃ type waters by leaching of cations from the fault planes and creates clay minerals, such as kaolinite, as alteration products on affected fault planes. These mineral reactions result in fault weakness and in hydraulically interconnected fault network. This leads to a decrease in the friction coefficient of the Coulomb failure stress (CFS) and to fault creep as stress build‐up cannot occur in the weak segments. At the transition zone in the north of the Cheb Basin, between areas of weak, fluid conductive faults and areas of locked faults with frictional strength, fluid pressure can increase resulting in stress build‐up. This can trigger strike‐slip swarm earthquakes. Fault creep or movements in weak segments may support a stress build‐up in the transition area by transmitting fluid pressure pulses. Additionally to fluid‐driven triggering models, it is important to consider that fluids ascending along faults are CO₂‐supersaturated thus intensifying the effect of fluid flow. The enforced flow of CO₂‐supersaturated fluids in the transitional zone from high to low permeability segments through narrowings triggers gas exsolution and may generate pressure fluctuations. Phase separation starts according to the phase behaviour of CO₂‐H₂O systems in the seismically active depths of NW Bohemia and may explain the vertical distribution of the seismicity. Changes in the size of the fluid transport channels in the fault systems caused, or superimposed, by fault movements, can produce fluid pressure increases or pulses, which are the precondition for triggering fluid‐induced swarm earthquakes.     

Fluid effect on hydraulic fracture propagation behavior: a comparison between water and supercritical CO2‐like fluid

The initiation of hydraulic fractures during fluid injection in deep formations can be either engineered or induced unintentionally. Upon injection of CO₂, the pore fluids in deep formations can be changed from oil/saline water to CO₂ or CO₂ dominated. The type of fluid is important not only because the fluid must fracture the rock, but also because rocks saturated with different pore fluids behave differently. We investigated the influence of fluid properties on fracture propagation behavior by using the cohesive zone model in conjunction with a poroelasticity model. Simulation results indicate that the pore pressure fields are very different for different pore fluids even when the initial field conditions and injection schemes (rate and time) are kept the same. Low viscosity fluids with properties of supercritical CO₂ will create relatively thin and much shorter fractures in comparison with fluids exhibiting properties of water under similar injection schemes. Two significant times are recognized during fracture propagation: the time at which a crack ceases opening and the later time point at which a crack ceases propagating. These times are very different for different fluids. Both fluid compressibility and viscosity influence fracture propagation, with viscosity being the more important property. Viscosity can greatly affect hydraulic conductivity and the leak‐off coefficient. This analysis assumes the in‐situ pore fluid and injected fluid are the same and the pore space is 100% saturated by that fluid at the beginning of the simulation.     

Precipitation of lead–zinc ores in the Mississippi Valley‐type deposit at Trèves,Cévennes region of southern France

The Trèves zinc–lead deposit is one of several Mississippi Valley‐type (MVT) deposits in the Cévennes region of southern France. Fluid inclusion studies show that the ore was deposited at temperatures between approximately 80 and 150°C from a brine that derived its salinity mainly from the evaporation of seawater past halite saturation. Lead isotope studies suggest that the metals were extracted from local basement rocks. Sulfur isotope data and studies of organic matter indicate that the reduced sulfur in the ores was derived from the reduction of Mesozoic marine sulfate by thermochemical sulfate reduction or bacterially mediated processes at a different time or place from ore deposition. The large range of δ³⁴S values determined for the minerals in the deposit (12.2–19.2‰ for barite, 3.8–13.8‰ for sphalerite and galena, and 8.7 to ?21.2‰ for pyrite), are best explained by the mixing of fluids containing different sources of sulfur. Geochemical reaction path calculations, based on quantitative fluid inclusion data and constrained by field observations, were used to evaluate possible precipitation mechanisms. The most important precipitation mechanism was probably the mixing of fluids containing different metal and reduced sulfur contents. Cooling, dilution, and changes in pH of the ore fluid probably played a minor role in the precipitation of ores. The optimum results that produced the most metal sulfide deposition with the least amount of fluid was the mixing of a fluid containing low amounts of reduced sulfur with a sulfur‐rich, metal poor fluid. In this scenario, large amounts of sphalerite and galena are precipitated, together with smaller quantities of pyrite precipitated and dolomite dissolved. The relative amounts of metal precipitated and dolomite dissolved in this scenario agree with field observations that show only minor dolomite dissolution during ore deposition. The modeling results demonstrate the important control of the reduced sulfur concentration on the Zn and Pb transport capacity of the ore fluid and the volumes of fluid required to form the deposit. The studies of the Trèves ores provide insights into the ore‐forming processes of a typical MVT deposit in the Cévennes region. However, the extent to which these processes can be extrapolated to other MVT deposits in the Cévennes region is problematic. Nevertheless, the evidence for the extensive migration of fluids in the basement and sedimentary cover rocks in the Cévennes region suggests that the ore forming processes for the Trèves deposit must be considered equally viable possibilities for the numerous fault‐controlled and mineralogically similar MVT deposits in the Cévennes region.