Fluid generation and evolution during exhumation of deeply subducted UHP continental crust: Petrogenesis of composite granite–quartz veins in the Sulu belt,China

Composite granite–quartz veins occur in retrogressed ultrahigh pressure (UHP) eclogite enclosed in gneiss at General's Hill in the central Sulu belt, eastern China. The granite in the veins has a high‐pressure (HP) mineral assemblage of dominantly quartz+phengite+allanite/epidote+garnet that yields pressures of 2.5–2.1 GPa (Si‐in‐phengite barometry) and temperatures of 850–780°C (Ti‐in‐zircon thermometry) at 2.5 GPa (~20°C lower at 2.1 GPa). Zircon overgrowths on inherited cores and new grains of zircon from both components of the composite veins crystallized at c. 221 Ma. This age overlaps the timing of HP retrograde recrystallization dated at 225–215 Ma from multiple localities in the Sulu belt, consistent with the HP conditions retrieved from the granite. The ε_Hf(t) values of new zircon from both components of the composite veins and the Sr–Nd isotope compositions of the granite consistently lie between values for gneiss and eclogite, whereas δ¹⁸O values of new zircon are similar in the veins and the crustal rocks. These data are consistent with zircon growth from a blended fluid generated internally within the gneiss and the eclogite, without any ingress of fluid from an external source. However, at the peak metamorphic pressure, which could have reached 7 GPa, the rocks were likely fluid absent. During initial exhumation under UHP conditions, exsolution of H₂O from nominally anhydrous minerals generated a grain boundary supercritical fluid in both gneiss and eclogite. As exhumation progressed, the volume of fluid increased allowing it to migrate by diffusing porous flow from grain boundaries into channels and drain from the dominant gneiss through the subordinate eclogite. This produced a blended fluid intermediate in its isotope composition between the two end‐members, as recorded by the composite veins. During exhumation from UHP (coesite) eclogite to HP (quartz) eclogite facies conditions, the supercritical fluid evolved by dissolution of the silicate mineral matrix, becoming increasingly solute‐rich, more ‘granitic’ and more viscous until it became trapped. As crystallization began by diffusive loss of H₂O to the host eclogite concomitant with ongoing exhumation of the crust, the trapped supercritical fluid intersected the solvus for the granite–H₂O system, allowing phase separation and formation of the composite granite–quartz veins. Subsequently, during the transition from HP eclogite to amphibolite facies conditions, minor phengite breakdown melting is recorded in both the granite and the gneiss by K‐feldspar+plagioclase+biotite aggregates located around phengite and by K‐feldspar veinlets along grain boundaries. Phase equilibria modelling of the granite indicates that this late‐stage melting records P–T conditions towards the end of the exhumation, with the subsolidus assemblage yielding 0.7–1.1 GPa at <670°C. Thus, the composite granite–quartz veins represent a rare example of a natural system recording how the fluid phase evolved during exhumation of continental crust. The successive availability of different fluid phases attending retrograde metamorphism from UHP eclogite to amphibolite facies conditions will affect the transport of trace elements through the continental crust and the role of these fluids as metasomatic agents interacting with the mantle wedge in the subduction channel.     

Numerical modeling of toxic nonaqueous phase liquid removal from contaminated groundwater systems: mesh effect and discretization error estimation

Numerical modeling has now become an indispensable tool for investigating the fundamental mechanisms of toxic nonaqueous phase liquid (NAPL) removal from contaminated groundwater systems. Because the domain of a contaminated groundwater system may involve irregular shapes in geometry, it is necessary to use general quadrilateral elements, in which two neighbor sides are no longer perpendicular to each other. This can cause numerical errors on the computational simulation results due to mesh discretization effect. After the dimensionless governing equations of NAPL dissolution problems are briefly described, the propagation theory of the mesh discretization error associated with a NAPL dissolution system is first presented for a rectangular domain and then extended to a trapezoidal domain. This leads to the establishment of the finger‐amplitude growing theory that is associated with both the corner effect that takes place just at the entrance of the flow in a trapezoidal domain and the mesh discretization effect that occurs in the whole NAPL dissolution system of the trapezoidal domain. This theory can be used to make the approximate error estimation of the corresponding computational simulation results. The related theoretical analysis and numerical results have demonstrated the following: (1) both the corner effect and the mesh discretization effect can be quantitatively viewed as a kind of small perturbation, which can grow in unstable NAPL dissolution systems, so that they can have some considerable effects on the computational results of such systems; (2) the proposed finger‐amplitude growing theory associated with the corner effect at the entrance of a trapezoidal domain is useful for correctly explaining why the finger at either the top or bottom boundary grows much faster than that within the interior of the trapezoidal domain; (3) the proposed finger‐amplitude growing theory associated with the mesh discretization error in the NAPL dissolution system of a trapezoidal domain can be used for quantitatively assessing the correctness of computational simulations of NAPL dissolution front instability problems in trapezoidal domains, so that we can ensure that the computational simulation results are controlled by the physics of the NAPL dissolution system, rather than by the numerical artifacts. Copyright © 2014 John Wiley & Sons, Ltd.     

The influence of coupled physical swelling and chemical reactions on deformable geomaterials

Coupled thermo‐hydro‐mechanical‐chemical modelling has attracted attention in past decades due to many contemporary geotechnical engineering applications (e.g., waste disposal, carbon capture and storage). However, molecular‐scale interactions within geomaterials (e.g., swelling and dissolution/precipitation) have a significant influence on the mechanical behaviour, yet are rarely incorporated into existing Thermal‐Hydro‐Mechanical‐Chemical (THMC) frameworks. This paper presents a new coupled hydro‐mechanical‐chemical constitutive model to bridge molecular‐scale interactions with macro‐physical deformation by combining the swelling and dissolution/precipitation through an extension of the new mixture‐coupling theory. Entropy analysis of the geomaterial system provides dissipation energy, and Helmholtz free energy gives the relationship between solids and fluids. Numerical simulation is used to compare with the selected recognized models, which demonstrates that the swelling and dissolution/precipitation processes may have a significant influence on the mechanical deformation of the geomaterials.     

Chemo‐mechanics of cemented granular solids subjected to precipitation and dissolution of mineral species

This paper studies the chemo‐mechanics of cemented granular solids in the context of continuum thermodynamics for fluid‐saturated porous media. For this purpose, an existing constitutive model formulated in the frame of the Breakage Mechanics theory is augmented to cope with reactive processes. Chemical state variables accounting for the reactions between the solid constituents and the solutes in the pore fluid are introduced to enrich the interactions among the microstructural units simulated by the model (i.e., grains and cement bonds). Two different reactive processes are studied (i.e., grain dissolution and cement precipitation), using the chemical variables to describe the progression of the reactions and track changes in the size of grains and bonds. Finally, a homogenization strategy is used to derive the energy potentials of the solid mixture, adopting probability density functions that depend on both mechanical and chemical indices. It is shown that the connection between the statistics of the micro‐scale attributes and the continuum properties of the solid enables the mathematical capture of numerous mechanical effects of lithification and chemical deterioration, such as changes in stiffness, expansion/contraction of the elastic domain, and development of inelastic strains during reaction. In particular, the model offers an interpretation of the plastic strains generated by aggressive environments, which are here interpreted as an outcome of chemically driven debonding and comminution. As a result, the model explains widely observed macroscopic signatures of geomaterial degradation by reconciling the energetics of the deformation/reaction processes with the evolving geometry of the microstructural attributes. Copyright © 2015 John Wiley & Sons, Ltd.     

Why asymptotic limit of the acid dissolution capacity can lead to a sharp dissolution front in chemical dissolution of porous rocks?

The use of the asymptotic limit can greatly simplify the theoretical analysis of chemical dissolution front instabilities in fluid‐saturated rocks and therefore make it possible to obtain mathematical solutions, which often play a crucial role in understanding the propagation behavior of chemical dissolution fronts in chemical dissolution systems. However, there has been a debate in recent years that the asymptotic limit of the acid dissolution capacity (i.e., the acid dissolution capacity number approaching zero) alone cannot lead to a sharp dissolution front of the Stefan type in the acidization dissolution system, in which the dissolvable minerals of carbonate rocks are chemically dissolved by the injected acid flow. The acid dissolution capacity number is commonly defined as the ratio of the volume of the carbonate rock dissolved by an acid to that of the acid. In this paper, we use four different proof methods, including (i) direct use of the fundamental concepts; (ii) use of the mathematical governing equations of an acidization dissolution system; (iii) use of the different time scaling approach; and (iv) use of a moving coordinate system approach, to demonstrate that the asymptotic limit of the acid dissolution capacity can indeed lead to sharp dissolution fronts of the Stefan type in acidization dissolution systems on a much larger time scale (than the dissolution time scale). Our new finding is that on the reaction time scale, the condition of the conventional time derivative of porosity approaching zero alone can ensure that the acidization dissolution front has a sharp shape of the Stefan type. Copyright © 2017 John Wiley & Sons, Ltd.     

Sedimentary evidence and luminescence and ESR dating of Early Pleistocene high lake levels of Megalake Tengger,northwestern China

The timing of high lake-level stands during the Late Pleistocene in western China remains controversial. Here we report new results from Megalake Tengger based on a study of palaeo-shorelines and a drill core from Baijian Lake in the northwestern Tengger Desert. Multiple dating methods, based on luminescence signals (quartz optically stimulated luminescence, K-feldspar post infrared-infrared stimulated luminescence) and electron spin resonance signals of quartz, were used to date beach sands from palaeo-shoreline profiles at altitudes of ~1310 m (+20 m above lake level), ~1320 m (+30 m) and ~1350 m (+60 m), and from the top 20 m of sandy sediments from the drill core obtained from the modern beach of Baijian Lake. The dating results show that high lake-level stands associated with the previously reported Megalake Tengger (~1310–1320 m) occurred during the late Early to Middle Pleistocene, which is much earlier than previously reported. In addition, no geomorphological evidence of shorelines and sedimentary evidence from the drill core profile were found to support the previously reported Late Pleistocene lake levels. Our results indicate that the exact age of the previously reported ‘high lake level event’ in a large part of northwestern China during the Late Pleistocene needs to be re-evaluated.     

新疆三塘湖盆地马朗凹陷中二叠统芦草沟组泥页岩层系SiO2赋存状态与成因

为了弄清新疆三塘湖盆地马朗凹陷芦草沟组泥页岩层系中SiO_2对储集层物性、脆性等特性的影响,通过全岩和黏土矿物X衍射、岩石力学性质、阴极发光、扫描电镜及电子能谱等实验手段对其中SiO_2的赋存状态进行了研究,初步探讨了SiO_2不同形态赋存的机理,并在此基础上探究了石英含量对储层的影响。研究表明:凝灰岩、泥页岩和粉砂质泥岩中二氧化硅多以非晶态形式存在。二氧化硅在凝灰岩中多呈不规则球粒状,而在泥页岩和粉砂质页岩中无固定形态。凝灰质泥岩、凝灰质白云岩和白云岩中二氧化硅呈现一定的晶体形态。在凝灰质泥岩中,二氧化硅以自生石英形态聚集呈条带状,在凝灰质白云岩中则以自生石英形态发育于孤立的孔、洞之中,而白云岩中二氧化硅只能生长成Opal-A/Opal-CT阶段。凝灰质成分及其脱玻化作用为自生石英的生长提供了二氧化硅和生长空间,是控制SiO_2赋存状态的根本因素。此外,储集层孔隙度、渗透率和抗压强度都与石英含量呈一定正相关性,泊松比则与其呈负相关性。     

Evidence of technetium and iodine release from a sodalite-bearing ceramic waste form

Sodalites have been proposed as a possible host of certain radioactive species, specifically ⁹⁹Tc and ¹²⁹I, which may be encapsulated into the cage structure of the mineral. To demonstrate the ability of this framework silicate mineral to encapsulate and immobilize ⁹⁹Tc and ¹²⁹I, single-pass flow-through (SPFT) tests were conducted on a sodalite-bearing multi-phase ceramic waste form produced through a steam reforming process. Two samples made using a steam reformer samples were produced using non-radioactive I and Re (as a surrogate for Tc), while a third sample was produced using actual radioactive tank waste containing Tc and added Re. One of the non-radioactive samples was produced with an engineering-scale steam reformer while the other non-radioactive sample and the radioactive sample were produced using a bench-scale steam reformer. For all three steam reformer products, the similar steady-state dilute-solution release rates for Re, I, and Tc at pH (25 °C) = 9 and 40 °C were measured. However, it was found that the Re, I, and Tc releases were equal or up to 4.5x higher compared to the release rates of the network-forming elements, Na, Al, and Si. The similar releases of Re and Tc in the SPFT test, and the similar time-dependent shapes of the release curves for samples containing I, suggest that Re, Tc, and I partition to the sodalite minerals during the steam reforming process.