贵州省鸡场滑坡地下水化学特征反映的水-岩（土）作用

滑坡体水-岩(土)作用是一种复杂的物理化学综合作用,影响坡体的稳定性,但关于目前水-岩(土)相互作用对地质灾害发生方面的影响研究仍较为薄弱。以贵州省鸡场滑坡为研究对象,分析滑坡区岩土体矿物组成和化学成分特征,结合区域内基岩裂隙水、大气降水的成分变化,利用主成分分析方法,研究鸡场滑坡水-岩(土)作用过程,并分析水岩演化作用对滑坡稳定性的影响。结果表明：(1)滑体内玄武岩的风化过程是一种机械破碎-矿物蚀变耦合的水-岩相互作用,发生在“微观-细观-宏观”3种尺度上;(2)选取前3个因子Z₁、Z₂、Z₃(分别占总方差的49.365%、27.135%、15.092%)分析地下水的化学特征,主因子Z₁反映了玄武岩原生矿物的溶蚀作用对地下水化学成分的控制作用,主因子Z₂反映了地下水的蒸发作用与SiO₂溶解度随pH变化的矿物沉淀作用,主因子Z₃反映了地下水与岩(土)体间存在离子交换作用且主参与离子为Mg²⁺和K⁺     

Estimation of reactive mineral surface area during water-rock interaction using fluid chemical data

Mineral dissolution and precipitation reactions actively participate to control fluid chemistry during water-rock interaction. However, it is difficult to estimate and normalize bulk reaction rates if the mineral surface area effectively participating in the reactions is unknown. In this study, we evaluated the changing of the reactive mineral surface area during the interaction between CO₂-rich fluids and albitite rock reacting under flow-through conditions. Our methodology, adopting an inverse modelling approach, is based on the measured chemical fluid composition as raw data. We estimated the rates of dissolution and the reactive surface areas of the different minerals by reconstructing the chemical evolution of the interacting fluids. This was done by a reaction process schema that was defined by a fractional degree of advance of the irreversible mass-transfer process and by attaining the continuum limit during the water-rock interaction. Calculations were carried out for albite, microcline, biotite and calcite assuming that the ion activity of dissolved silica and aluminium ions was limited by the equilibrium with quartz and kaolinite.We found that the absolute dissolution rate of albite, microcline, biotite and calcite remains essentially constant as a function of time, and the calcite dissolution rate is orders of magnitude higher than silicate minerals. On the contrary, the reactive surface area of the parent minerals varied by more than two orders of magnitude during the observed reaction time, especially for albite. We propose that the reactive surface area depends mainly on the stability of the secondary mineral coating that may passivate the effective reactive surface area of the parent minerals.     

水-岩化学作用等效裂纹扩展细观力学模型

从化学腐蚀下岩石细观结构的变化出发,研究水化学溶液对岩石中裂纹的腐蚀作用。运用地球化学矿物-水反应的溶解动力学,考查水-岩反应化学溶液中不同时间段离子浓度的变化,从理论上探讨化学腐蚀下等效裂纹扩展的定量化分析方法。通过质量守恒定律计算出裂纹在迹长及隙宽方向的变化,将水化腐蚀等效成有效裂纹长度,建立了水-岩化学作用下等效裂纹扩展的计算公式并计算应力强度因子。通过对砂岩的研究结果表明,水-岩化学作用对岩石裂纹的扩展有显著影响,并且具有时间效应。同时,水化学溶液的离子浓度及pH值大小对裂纹的扩展存在影响,其中pH值的变化对岩石的断裂力学效应更加显著。当溶液的酸性越强或碱性越强,腐蚀越大,裂纹扩展越快;pH值为中性时,腐蚀作用得到较大缓解,裂纹发展缓慢。为定量研究裂隙岩体在水岩化学作用下的细观机理提供了一种新的思路。     

煤矿地下水库水岩作用时间规律模拟试验研究

矿井水在煤矿地下水库的停留时间会影响出水中离子浓度水平,而煤矿地下水库运行期间的水岩作用时间规律尚不明晰。为揭示煤矿地下水库不同运行阶段水岩作用的发生类型及强度,结合现场采样测试分析,设计细砂岩–矿井水(S-K)和泥岩–矿井水(N-K)2组水岩相互作用静态模拟试验,从试验前后岩石成分变化及水中主要离子变化2个方面解析水岩作用类型,并结合Q型聚类分析探讨水岩相互作用的时间规律。岩石矿物成分变化表明,水岩作用过程中发生了钠长石、正长石等矿物的溶解以及高岭石、石英等矿物的沉淀;离子比值分析与统计学分析表明,水岩作用过程中还发生了阳离子交换反应以及硅酸盐、蒸发岩等矿物的溶解和碳酸钙矿物的沉淀;Q型聚类分析表明,静态模拟试验水样样本按时间序列可划分为3类,分别代表水岩作用前期(0～0.5 d),中期(1～10 d或1～8 d)以及后期(12～47 d或10～47 d)。结合离子来源解析综合判定：在本试验中,水岩作用前期以阳离子交换反应为主,离子变化主要表现为Na+浓度激增,而Ca2+浓度锐减;中期以阳离子交换反应与矿物溶解-沉淀为主,离子变化主要表现为Na+、K+、Cl-浓度增高,Ca2+、HC...     

焦家金矿床水-岩反应过程及成矿流体组分变化规律

在野外和室内岩相学观察的基础上,详细剖析了蚀变-矿化时序,结合热力学数值模拟方法与定量结果,厘定了水- 岩反应过程中矿物的沉淀次序、流体组分的存在形式、迁移行为、浓度变化和矿物形成机制以及组分之间的化学反应,为 进一步研究水-岩反应与金矿化的关系奠定了基础。研究结果显示反应初期K+由流体带入围岩形成钾长石化,随着反应的 进行,H+浓度持续降低而Fe2+和Al3+含量升高,绢云母和石英大量沉淀,钾长石消失;反应后期各类硫化物开始沉淀,石英 持续沉淀贯穿整个反应过程。成矿流体中SO42-,HS-,Fe2+的含量对蚀变矿物组合影响很大;水-岩反应过程中硫酸盐 （SO42-） 减少生成等量的HS-并伴随着含三价铁矿物的沉淀,可能是焦家金矿床硫化物沉淀的一种重要机制。整个反应过程 中溶液pH值持续升高是原岩中Ca,K,Na,Mg等与溶液中H+发生交换反应的结果;同时pH值的升高也会降低金的溶解度 致使金沉淀。上述研究成果对于理解岩石中的矿物共生组合、生成顺序及蚀变分带的成因机制提供了新的依据。     

Alkali feldspar dissolution and secondary mineral precipitation in batch systems: 3. Saturation states of product minerals and reaction paths

In order to evaluate the complex interplay between dissolution and precipitation reaction kinetics, we examined the hypothesis of partial equilibria between secondary mineral products and aqueous solutions in feldspar-water systems. Speciation and solubility geochemical modeling was used to compute the saturation indices (SI) for product minerals in batch feldspar dissolution experiments at elevated temperatures and pressures and to trace the reaction paths on activity-activity diagrams. The modeling results demonstrated: (1) the experimental aqueous solutions were supersaturated with respect to product minerals for almost the entire duration of the experiments; (2) the aqueous solution chemistry did not evolve along the phase boundaries but crossed the phase boundaries at oblique angles; and (3) the earlier precipitated product minerals did not dissolve but continued to precipitate even after the solution chemistry had evolved into the stability fields of minerals lower in the paragenesis sequence. These three lines of evidence signify that product mineral precipitation is a slow kinetic process and partial equilibria between aqueous solution and product minerals were not held. In contrast, the experimental evidences are consistent with the hypothesis of strong coupling of mineral dissolution/precipitation kinetics [e.g., Zhu C., Blum A. E. and Veblen D. R. (2004a) Feldspar dissolution rates and clay precipitation in the Navajo aquifer at Black Mesa, Arizona, USA. In Water-Rock Interaction (eds. R. B. Wanty and R. R. I. Seal). A.A. Balkema, Saratoga Springs, New York. pp. 895-899]. In all batch experiments examined, the time of congruent feldspar dissolution was short and supersaturation with respect to the product minerals was reached within a short period of time. The experimental system progressed from a dissolution driven regime to a precipitation limited regime in a short order. The results of this study suggest a complex feedback between dissolution and precipitation reaction kinetics, which needs to be considered in the interpretation of field based dissolution rates.     

地质流体 岩石反应的地球化学动力学方法

摘 要　 提出了一个以矿物生成和溶解的速率确定体系矿物沉淀的量来模拟水 岩反应的新方 法。新固相在体系中沉淀的量只依赖于沉淀速率‚而不是依赖于水 岩之间的平衡。考察了一 个矿物溶解生成次生矿物最终趋于平衡的溶解沉淀反应演化‚结果表明在水 岩体系中对于次 生矿物的部分平衡假定在许多情况下都不能成立。在这样的反应演化过程中亚稳矿物与溶液 之间总保持过饱和态‚矿物的沉淀速率随反应的进展而变化。同时‚当主要溶解矿物达到平 衡而溶解作用停止时‚次生矿物沉淀尚未停止‚直到体系饱和指数全部趋于0时‚才达到总 体平衡。用动力学方法处理地球化学过程中的水 岩反应比准稳平衡的简单假设更合理‚因为 动力学方法更符合自然情况‚同时产生了关于时间过程的时间尺度信息。     

Sorption of silica by clay minerals

Clay minerals were reacted with silica-spiked solutions of unbuffered distilled water; water buffered at pH 5.5, 8 and 10; alkali chloride solutions; natural and artificial sea water to assess the influence of pH, silica and cation activities. The data are plotted as silica produced by dissolution or sorption of silica by clay surface as a function of initial silica concentration at a given pH and solution composition. This allows the determination of the dissolved silica value at which the clay mineral surface neither dissolves nor sorbs silica. The values of the various activities in different solutions are used to infer the phase equilibria between solution, clay mineral and the surface phase produced either by dissolution or sorption. Most intensively investigated were sorption reactions of kaolinite in sea water and other ionic solutions to form silica-rich, cation-rich surface phases in cationic solutions and silica-rich phases in cation-free solutions.Inferred equilibrium constants imply that silicate reconstitution is doubtful as a mechanism for partial control of silica and cation composition of sea water but is reasonable in silica-rich interstitial waters.     

考虑水化学损伤的砂岩流变损伤本构模型

通过对已有的水化学溶液腐蚀作用后红砂岩三轴蠕变试验结果的分析,可知水化学作用能够加快岩石损伤的发展,增强红砂岩的蠕变效应。根据水岩化学作用的动力学理论,将红砂岩中可溶解胶结物的流失作为水化学腐蚀作用下岩石力学性能劣化的根本原因。通过化学反应速率方程和测定浸泡过程中溶液pH值的变化,定义了考虑初始pH值和时间的化学损伤因子。考虑流变过程中的应力损伤,基于广义Kelvin模型,提出了考虑水化学作用的砂岩流变损伤本构模型。通过对水化学作用下红砂岩流变试验结果进行模拟,对该模型进行了参数辨识和验证。结果表明,所提出的模型能够较好地反映水化学作用下砂岩的流变特性,具有有效性和合理性。     

玄武岩—水相互作用的溶解机理研究

在常温常压排除大气干扰的封闭体系条件下,将一定粒度的玄武岩样品浸泡在不同酸度的水溶液里,研究玄武岩－水相互作用过程中元素释放和溶液酸度的变化情况。结果发现：（１）经过一段时间后,溶液中主要元素的浓度趋向平衡;（２）溶液酸度发生明显变化,即不论反应初始溶液是碱性的还是酸性的,最终都将趋于中性,我们把此现象称为溶液的中性化效应。根据溶液中溶解组分的浓度和样品表面组成的ＸＰＳ测定结果,提出玄武岩在碱性和酸性溶液中不同的溶解机理。     

新疆玛纳斯河流域平原地下水水-岩作用模拟

玛纳斯河流域平原区地下水化学演化较为复杂,从上游至下游的变化特点主要以Na+、Ca2+、 HCO3-、SO42-含量和TDS值的高低相间交替演化为主。本文对此演化机理进行了水-岩作用模拟研究,模拟结果表明:①矿物相的溶解、析出和蒸发作用、稀释作用共同控制着地下水水化学的演化;②从研究区上游往下,由于地层岩性颗粒逐渐变细,水中矿物相迁入、迁出的数量逐渐增大,水-岩作用逐渐增强;③研究区上游的水-岩作用主要是地表水或灌溉水入渗补给的影响,研究区中下游的水-岩作用主要受蒸发作用的影响;④由于地表水或灌溉水的大量混入,局部的水化学演化往往不符合一般演化规律,甚至于往相反的方向演化,TDS呈下降趋势,产生复杂的过渡水化学类型。     

Physico-chemical mechanisms of weathering processes and corresponding models of dynamics of mineral zonality evolution

The peculiarities of weathering processes involving duration, slow change of ambient conditions, isothermality as well as proceeding in open systems permit to study these processes in a steady-state approach (dC_i/dt = 0, where C_i is concentration of intermediates; and t is time). The most typical quasi-stationary processes for a water-rock system are: (1) non-equilibrium step - surface reaction of primary-mineral dissolution; and (2) non-equilibrium step - secondary-mineral precipitation. These respectively determine two extreme mechanisms of mineral formation: (1) pseudomorphous replacement; and (2) dissolution-transfer-crystallization. Besides non-stationary weathering processes are known. It is the case when a process is controlled by diffusion through a layer of secondary minerals which have been deposited on the surface of the primary mineral. A mathematical model of weathering dynamics of feldspar with its metasomatic replacement by clay minerals is presented. Numerical simulation led to the prediction of mineral zonality development along the weathering profile at any time.     

Geochemistry and chemical evolution of saline lakes of Western Mongolia

This paper presents data on the major and trace element composition of saline lakes of western Mongolia. The main geochemical types of lakes distinguished in the study are soda-, chloride-, and sulfaterich lakes. Lake water equilibria with major carbonate, sulfate, chloride, and other rock-forming minerals were calculated. The results show that the major factors controlling the formation of each lake type include evaporation and water-rock interaction processes, and the latter factor plays a critical role in freshwater and soda lakes and only a minor role in chloride lakes. Special attention was given to the soda lakes and the factors controlling lake water chemistry.     

紫红色松散土体在不同饱水环境中的化学反应特征试验研究

以特殊的紫红色土为研究对象,采取三峡地区黄腊石滑坡临江松散土进行室内饱水试验,根据能量最低原则建立热力学反应模型,通过线性规划求解,分析不同饱水环境下随时间积累过程中紫红色松散土矿物反应特征及规律。研究表明:松散土在不同溶液浸泡条件下化学反应类型不同,江水和弱碱性溶液中主要发生白云石矿物的溶解,自来水、纯水和弱酸性溶液中主要发生方解石矿物的溶解和Ca2+与K+的交换吸附。另外,不同浸泡环境中不同时间的水-土化学作用活跃程度明显差异,弱酸性溶液与松散土的化学反应在饱水1~7 d最为强烈,其他四种溶液与松散土的化学反应在饱水7~16 d最为强烈。饱水后期,不同溶液浸泡条件下的水-土化学作用都减弱并最终趋向于平衡。     

人工回灌条件下多组分溶质的反应迁移模拟

人工回灌技术在我国水资源管理中占据重要地位,但是其实施对地下水环境质量也造成了较大的影响。如何保障人工回灌条件下地下水环境质量的安全稳定性,已成为人工回灌技术发展的瓶颈。以上海市某人工回灌试验场为例,结合试验场的地质、水文地质勘探结果,以TOUGHREACT为数值模拟平台,模拟预测人工回灌条件下地下水中多组分溶质的迁移转化过程。模拟结果表明：地下水化学成分主要受混合作用、阳离子交换吸附作用及含水层矿物相溶解-沉淀作用等影响;含水介质中石英、白云石、钾长石、钠长石及蒙脱石发生溶解,方解石发生沉淀,伊利石与高岭石则先溶解后沉淀,但各矿物相反应量极其微弱;按不同压力方案回灌,水位恢复速率随压力增大而加快,但地下水中化学成分变化趋势几乎不受压力影响。     

煤矿采空区水-岩作用模拟试验研究

采空区积水在我国煤矿中广泛存在。明确在采空区封闭-半封闭环境条件下的水-岩相互作用机理,对实现煤矿区水污染减量以及地下水资源保护具有重要意义。以内蒙古某煤矿采空区积水为研究对象,设计高度还原采空区环境的箱式模拟试验,采用X射线衍射仪(XRD)和X射线荧光光谱仪(XRF)对模拟采空区填充物(煤、垮落岩体)中矿物成分及元素组成进行分析,借助离子色谱仪(IC)和电感耦合等离子体发射光谱分析仪(ICP-OES)等对水中水化学特征进行表征,探究采空区积水水质形成的水-岩相互作用机制。结果表明:水-岩相互作用主要为煤及垮落岩体中的矿物溶解-沉淀作用、阳离子交换作用、煤中黄铁矿氧化作用以及混合作用。矿物溶解作用占主导地位,采空区积水中的Na⁺、K⁺主要来源是钠长石、钾长石等硅酸盐矿物的溶解,而Ca²⁺和Mg²⁺主要来自于钙长石、方解石、绿泥石等矿物溶解;离子交换作用主要发生在采空区水-岩作用的初期(0～20 d),而后逐渐减弱;采空区底部残煤中黄铁矿氧化作用是积水SO₄^2-     

Chemical composition of natural waters and brines as a result of hydrogeochemical processes in water-rock-gas systems

Thermodynamic computer modeling was carried out to evaluate the formation of the chemical composition of main geochemical types of groundwaters. An explanation was proposed for the geochemical evolution of underground saline waters and brines along the calcic and sodic trends, the inversion of groundwater in the deep horizons of sedimentation structures, and the geochemical diversity of CO₂-rich waters in crystalline rocks. The occurrence of hydrogeochemical processes is controlled by the physicochemical conditions of the state of the water-rock-gas system. The following parameters (boundary conditions) are critical in natural hydrogeologic environments: the mass ratio of interacting rock and water (R/W), the openness (closeness) of hydrogeochemical systems with respect to CO₂ and O₂, the chemical and mineral composition of rocks, and temperature-pressure conditions. The estimation of boundary conditions showed the following.

1. The petrochemical type of rock affects the composition of the aqueous phase through the dissolution rates of minerals, especially volatile-bearing ones. A decrease in water exchange and an increase in R/W (10^?6??10²) are accompanied by an increase in the salinity of the aqueous phase and an increase in the fraction of Cl, Na, and Ca (in a closed system) or HCO₃, Cl, and Na (in a system open to CO₂).
2. The composition of the aqueous phase of water-rock systems is most strongly affected by the abundance in the rock of extractable Cl and reactive organic matter, which controls the geochemical type of the aqueous phase and its position in the Hardie-Eugster diagram.
3. The composition of the aqueous phase is shifted into the calcic field of the Hardie-Eugster diagram at the closure of the water-rock system and into the carbonate field at the opening of the water-rock system to CO₂. Waters showing pH ?? 8.5 are formed in feldspathic rocks with low contents of extractable volatiles. Alkaline waters with pH > 9 are formed in water-rock systems (a) under the influence of organic matter and (b) by the evaporative concentration waters under surface conditions.
4. The higher the degree of seawater concentration and the lower the R/W value, the more significant the effect of seawater composition on the aqueous phase chemistry of the water-rock system. With increasing degree of seawater concentration, the composition of the aqueous phase changes in the sequence Cl-SO₄-Na-Mg- ?? Cl-SO₄-Mg-Na?? Cl-Mg (at low R/W) and Cl-Na ?? Cl-Na-Mg (at high R/W). The influence of the petrochemical type of rock and CO₂ partial pressure, on the geochemical type of the aqueous phase in the seawater-rock system is more significant at high R/W.
5. A temperature increase shifts the acid-base state of the aqueous phase into the alkaline region and its redox state into the reducing region.

     

应力作用下岩石的化学动力学溶解机制研究

通过结合化学热力学及动力学、过渡态理论和岩石力学等方面的知识,建立了应力作用下岩石的溶解动力学模型,分析了应力作用对岩石固相物质活度及矿物溶解动力学速率的影响,探讨了应力作用下水岩相互作用机制。研究结果表明：岩石所承受应力与周围流体压力之间存在的应力差所产生的化学势差是应力作用下溶解反应的驱动力;应力的施加显著提高了岩石中固相物质的活度,由此加快了矿物溶解反应的动力学速率;应力作用下的岩石细观溶解机制可根据固液界面应力分配及优先溶解部位上的差别分别用水膜扩散模型或岛渠模型进行描述;应力作用下水岩相互作用存在着应力、化学与渗流的3场耦合问题：应力推动化学反应的发生,化学作用使得岩石表面的细观形貌发生改变,局部的应力分布及大小也随着形貌的变化而改变,进而影响化学反应发生的位置及进程,同时也改变渗流通道的演化规律     

高放废物处置库甘肃北山野马泉预选区地下水化学特征及水-岩作用模拟

在高放废物处置库场地选择和性能评价中,地下水化学特征是最重要的因素之一。文中以野外水文地球化学调查资料为基础,应用水文地球综合分析方法和地下水地球化学模拟技术,探讨中国高放废物处置库甘肃北山野马泉预选区地下水化学特征、时空分布规律及水岩作用机理。主要结论是:野马泉地区地下水以咸水为主, 具有高矿化的特征,水化学类型以Cl·SO4 Na和SO4·Cl Na型为主,pH值大多在7~8 之间;地下水化学成分显示出明显的分带特征;地下水对石盐和石膏欠饱和,对黄铁矿以及铝硅酸盐过饱和;方解石、钠长石在补给区地下水中呈不饱和状态,在排泄区地下水中呈饱和状态。由水岩作用模拟可知,沿水流路径地下水溶解岩石中的钠长石、黑云母、石盐等矿物,溶解二氧化碳,沉淀析出方解石、伊利石和萤石等矿物;发生明显地下水蒸发作用、二氧化碳溶解作用和Ca2+/ Na+离子交换作用, 说明溶滤、沉淀、离子交换和蒸发浓缩作用是区内地下水化学行为的控制因素。     

人工回灌过程中的水-岩相互作用模拟

人工回灌过程中所发生的水-岩相互作用是影响回灌层位地下水环境质量的重要因素。采用室内实验和水文地球化学模拟等技术对人工回灌过程中的水-岩相互作用机理进行了分析。研究结果表明：受混合作用影响,随着回灌水比例的增加,混合水中TDS质量浓度降低,水化学类型由Cl·HCO₃-Na型水逐渐转变为HCO₃·Cl-Na·Ca型水;受水-岩作用影响,在同一混合比例条件下,随着水-岩作用的进行,混合水中TDS质量浓度升高,各主要离子质量浓度呈现升高的趋势,但只有回灌水比例占10%时,混合水TDS质量浓度才大于原始地下水（涨幅约5%）。实验介质溶解于水的离子中,Ca²⁺、Mg²⁺和HCO^-₃主要来源于碳酸盐矿物的溶解, Na⁺主要来自岩盐的溶解。在人工回灌过程中,发生的水-岩相互作用主要包括方解石、白云石、钾长石、岩盐、CO₂的溶解和伊利石的沉淀。其中:钾长石溶解量与伊利石沉淀量、碳酸盐矿物溶解量与CO₂溶解量的相关性较强,其相关系数分别为1.00和0.78（显著性水平为0.05）;硅酸盐矿物反应量和回灌水比例之间的相关系数为0.97（显著性水平为0.01）,相关性极强;而碳酸盐矿物反应量和回灌水比例之间的相关系数为0.52（显著性水平为0.01）,相关性较弱。上述相关性分析为确定人工回灌过程中的水-岩相互作用机理、地下水中主要离子组分的来源途径以及定量分析人工回灌对含水层介质的影响提供了依据。