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.     

Supraglacial weathering crust dynamics inferred from cryoconite hole hydrology

Water levels in cryoconite holes were monitored at high resolution over a 3‐week period on Austre Brøggerbreen (Svalbard). These data were combined with melt and energy balance modelling, providing insights into the evolution of the glacier's near‐surface hydrology and confirming that the hydrology of the near‐surface, porous ice known as the ‘weathering crust’ is dynamic and analogous to a shallow‐perched aquifer. A positive correlation between radiative forcing of melt and drainage efficiency was found within the weathering crust. This likely resulted from diurnal contraction and dilation of interstitial pore spaces driven by variations in radiative and turbulent fluxes in the surface energy balance, occasionally causing ‘sudden drainage events’. A linear decrease in water levels in cryoconite holes was also observed and attributed to cumulative increases in near‐surface ice porosity over the measurement period. The transport of particulate matter and microbes between cryoconite holes through the porous weathering crust is shown to be dependent upon weathering crust hydraulics and particle size. Cryoconite holes therefore yield an indication of the hydrological dynamics of the weathering crust and provide long‐term storage loci for cryoconite at the glacier surface. This study highlights the importance of the weathering crust as a crucial component of the hydrology, ecology and biogeochemistry of the glacier ecosystem and glacierized regions and demonstrates the utility of cryoconite holes as natural piezometers on glacier surfaces. Copyright © 2015 John Wiley & Sons, Ltd.     

硫酸参与的长江流域岩石化学风化速率与大气CO2消耗

流域的岩石化学风化过程是全球碳循环中的重要环节。以往的流域水化学碳汇通量估算大多是基于碳酸的风化作用。而实际上,硫酸和碳酸一样,也参与了流域碳元素的地球化学循环,从而对全球碳循环过程产生影响。长江流域水体近几年出现酸化现象,大部分河段SO42-和Ca2+含量增高,其对应的岩石风化过程和大气CO2消耗速率也发生变化。文章对长江干流及主要支流2013年不同季节的离子组成进行监测,利用水化学平衡法和Galy估算模型,对长江流域岩石化学风化速率和CO2消耗通量进行了估算,对硫酸参与下的长江流域岩石风化和碳循环过程进行了分析。结果表明,长江流域水体离子主要来源于硅酸盐岩风化和碳酸盐岩风化。其中碳酸盐岩风化对河水离子贡献率为92%。在硅酸盐岩广泛分布的赣江流域,碳酸盐岩风化离子贡献也达85%。分析表明,硫酸参与了长江流域的岩石风化过程,对水体中离子产生一定影响。硫酸的参与加快了碳酸盐岩的化学风化速率,平均提高约30%,但是使流域大气CO2消耗速率降低。在不考虑蒸发岩溶蚀作用下,平均从516×103 mol/km2·a降至356×103 mol/km2·a,降低约31%。在各支流中,硫酸对乌江流域碳酸盐岩的风化和碳循环的影响最大,而对雅砻江的影响最小,这与乌江流域的含煤地层、矿床硫化物及大气酸沉降有关。     

Bacterially-mediated weathering of crystalline and amorphous Cu-slags

Two types of Cu-slags (CS: crystalline massive slag and GS: granulated amorphous slag) exhibiting a different chemical and mineral phase composition were compared with respect to their susceptibility to bacterial weathering using Pseudomonas aeruginosa (n° CIP 105094). Abiotic conditions e.g. sterile growth medium and ultrapure water were used for comparison. The experiments were extended up to 112 days with a systematic liquid phase renewal every 14 days. The results revealed significant release of elements in the bacterially mediated weathering experiments. Concentrations of elements (Si, Fe, Cu, Zn and Pb) in the biotic solutions were increased at least by 20% up to 99% compared to abiotic ones. From 3 to 77% of the leached elements were associated to the fraction >0.22 μm. Scanning electron microscope observations demonstrated greater weathering of mineral phases in biotic experiments than in abiotic ones which is in accordance with the solution chemistry exhibiting higher concentrations of elements leached in biotic set-ups. In the case of CS, glass and sulfides weathering was yet observed in abiotic experiment, whereas partial dissolution of fayalite (Fe₂SiO₄) was solely affected by the presence of bacteria. GS having a higher bulk content of metallic elements was found to be more stable than sulfide-bearing CS, while its (GS) glass matrix was found to weather easier under biotic conditions.     

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.     

滨里海盆地东缘北特鲁瓦地区白云岩特征及其储层发育机制

白云岩是滨里海盆地盐下石炭系碳酸盐岩的重要储层类型。在岩芯、薄片、物性与地球化学等资料分析的基础上,对研究区KT-Ⅰ油组的白云岩类型与储集性能进行了分析,并探讨了其储层发育的控制因素与模式。结果表明,白云岩类型与其储集物性具有较明显的相关性,以生屑铸模孔及溶蚀扩大孔为主的残余生屑白云岩物性与含油气性最好,以晶间（溶）孔为主的粉细晶白云岩和以生屑铸模孔及晶间孔为主的泥粉晶白云岩次之,而以晶间微孔为主的泥晶白云岩最差,难以成为有效储层。原生孔隙发育的相对高能生屑滩环境是该区优质白云岩储层发育的相带基础。晚石炭世准同生期大气淡水溶蚀作用与以渗透回流白云化（白云石有序度分布于0.32～0.67,δ13C介于-0.22‰～5.94‰,δ18O介于-1.09‰～2.45‰）为主的早期白云化作用为白云岩储层早期孔隙的发育与保存奠定了坚实的基础;早二叠世以来埋藏期各类裂缝的发育及酸性流体的溶蚀作用则对储层的晚期扩孔改造至关重要。     

基于五种油源的中重度风化溢油的常规鉴定指标的应用效果评估

本文利用采集于我国三大油田的五种原油样品开展了长达210天的溢油风化模拟实验,并依据相对偏差和重复性限数学分析法,进行溢油风化过程分析和诊断比值应用效果评估。研究结果表明:经过210天的风化,溢油鉴定诊断比值发生明显改变;其中来源于萜烷、甾烷和多环芳烃的诊断比值变化率要远低于正构烷烃,可用于中长期风化溢油鉴定。此外,研究发现,在这些有效诊断比值中有4个变化率较小,相对偏差低于5%,保持了较好的稳定性,更适合于重度风化溢油鉴定。     

丹霞山世界地质公园蜂窝状洞穴特征及成因分析

蜂窝状洞穴以其精致的形貌和众说纷纭的成因吸引着科研人员和普通大众的兴趣。丹霞山世界地质公园蜂窝状洞穴主要产于晚白垩世丹霞组二段(锦石岩段)风成砂岩的崖壁上。本文以园区长老峰锦石岩寺和睡美人禄意堂两处蜂窝状洞穴为研究对象,通过野外实地调查,了解洞穴生长环境,定量统计分析其形态特征,并采集砂岩样品进行显微镜下观察,探讨洞穴形成与盐风化作用的关系。研究表明:蜂窝状洞穴所在的岩性主要为中—细粒长石岩屑砂岩,发育大型高角度交错层理,渗透性较好;洞穴开口均向下朝向锦江,有利于来自锦江河流的湿润水汽较长时间地保持在小洞内部;洞穴开口基本服从泰森多边形分布。因此,碎屑颗粒相对比较均匀的风成砂岩为丹霞山蜂窝状洞穴的发育提供了重要的岩石基础,锦江河流为盐风化提供了必要的湿润水汽和盐分。在初始发育阶段,从岩壁上最适合盐风化作用的若干个点开始形成细小的坑洼,逐步向同层位扩张。单个小洞穴由于盐风化作用,洞穴内部风化速率大于洞穴开口边缘,导致蜂窝状洞穴内部空间扩大较快。然后,蜂窝状洞穴的发育突破纹层的限制,逐步加大、变深而呈泰森多边形规则分布。最终,随着洞穴加深,在重力、风力的影响下,蜂窝状洞穴隔壁减薄失稳,洞穴消亡。     

几内亚福雷卡里亚YML铁矿区的富铁矿床地质特征及找矿前景探讨

YML铁矿区位于几内亚福雷卡里亚省,富铁矿以条带状赤铁矿和铁角砾岩矿为主。矿区内共发育7条矿体,条带状赤铁矿体6条,铁角砾岩矿体1条。条带状赤铁矿体赋存部位多为向形地段,次级紧密褶皱发育,沿走向和倾向有逐渐变薄和尖灭的趋势;铁角砾岩矿体覆盖于地表,以风化壳的形式出现。矿床类型属复合类型,即海底热液喷气沉积叠加后期构造变质型+风化淋滤型。该区具备铁矿形成和保存的地质条件,且已发现具一定储量、品位较高的条带状赤铁矿和大面积的铁角砾岩分布区,区内铁矿找矿远景较好。