Refinement and comparison of the crystal structures of a dolomite and of an Fe-rich ankerite

Summary The crystal structures of a dolomite and of an iron rich ankerite were refined from three-dimensional X-ray data by least squares methods toR0.03. The angle of rotation of the CO₃ group is 6.35(5)^o in dolomite but only 5.28(5)^o in ankerite, a consequence of the different sizes of the (Mg, Fe)O₆ octahedra. The carbonate group deviates very slightly from planarity in both minerals. The Ca–O distances are somewhat larger in both minerals than in calcite; the Mg–O distance in dolomite, on the contrary, is somewhat smaller than in magnesite.

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Verfeinerung und Vergleich der Kristallstrukturen eines Dolomits und eines Fe-reichen Ankerits

Zusammenfassung Die Kristallstrukturen eines Dolomits und eines eisenreichen Ankerits wurden aus dreidimensionalen Röntgendaten mittels der Methode der kleinsten Quadrate aufR0,03 verfeinert. Der Verdrehungswinkel der CO₃-Gruppe ist im Dolomit 6,35(5)^o, im Ankerit nur 5,28(5)^o; das ist eine Folge der unterschiedlichen Größen der (Mg, Fe)O₆-Oktaeder. Die Gestalt der Karbonatgruppe weicht in beiden Mineralen ganz leicht von planar ab. Die Ca–O-Abstände sind in beiden Mineralen etwas größer als im Calcit, der Mg–O-Abstand ist hingegen im Dolomit etwas kleiner als im Magnesit.

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东地中海黎凡特盆地白垩纪阿尔布期白云岩成因研究

“白云岩问题”一直是碳酸盐岩研究的热点问题。镁作为白云石的主量元素之一,其同位素组成包含了白云岩化过 程和白云岩沉积环境的信息。本文以以色列黎凡特盆地早白垩世末阿尔布期（~100 Ma）Givat Ye’arim组和Soreq组白云岩 为研究对象,在岩石学、微量元素和C-O-Sr同位素地球化学研究基础之上,开展了高密度镁同位素分析。结果显示白云岩 主要由半自形-自形的泥微晶白云石组成,岩性致密,后期成岩改造作用较弱,因此元素及同位素组成基本可以反映原始 白云岩化流体的地球化学特征;C-Sr同位素组成与Albian期海水保持一致,表明同期咸化海水是白云岩化流体并为白云石 形成提供镁离子;白云岩δ26Mg值稳定在-2.0‰左右,没有明显的垂向差异,表明白云岩化过程中咸化海水供应充足,流体 以渗流方式而不是以扩散方式在松散沉积物中运移,孔隙水化学组成相对均一,白云岩镁同位素组成得以与同期海水相平 衡。白云岩中陆源风化指示元素Rb和ΣREE以及海水盐度指标Na元素含量表现出多期旋回性变化,反映半封闭体系对周期 性气候和环境变化的响应,然而垂向上稳定的白云岩δ26Mg值表明区域性的气候变化不会显著改变沉积盆地体系中的镁同位 素组成,因此对于地质历史时期在半局限海洋环境中沉积的巨厚白云岩而言,其镁同位素组成可以用来示踪全球海水镁同 位素波动。     

鄂尔多斯盆地膏质白云岩有利储层的成因及演化

膏质白云岩是鄂尔多斯盆地中东部下古生界马家沟组M5₁最有利储层,影响膏质白云岩储层性质的最大因素在于溶蚀作用。本文在已有的研究基础上,应用岩心资料及阴极发光、地球化学等方法,测定M5₁膏质白云岩及其特殊的示底构造的化学成分,并分析其成因模式。岩心、薄片以及物性资料显示:石膏溶蚀形成的大量膏模孔及伴生的次生孔是储层的主要储集空间,示底构造规模性出现于膏质云岩中。阴极发光、常微量元素分析结果显示:示底构造上部充填埋藏期方解石;下部充填碎屑白云石,与示底构造外围的准同生期泥-粉晶白云石具有相近的地球化学特征,与深部埋藏期形成的细-中晶白云石差异明显。示底构造的演化是膏质白云岩有利储层形成的重要依据,本文依据化学离子平衡原理,对不同成岩阶段发生的溶蚀作用、填充作用进行离子间相互置换的重演,分析得知不稳定的化学组成是石膏易被溶蚀的内在原因,石膏的规模性溶蚀是膏质云岩有利储层形成的关键。     

柴达木盆地西部SG-1钻孔中白云石成因探讨

由于无机环境下不能沉淀白云石,该矿物的成因一直是学术争论的焦点。柴达木盆地西部钻孔SG-1（长938 m）中出现了大量白云石和铁白云石,白云石主要分布在钻孔下部500 m,而铁白云石主要分布在下部418 m。结合湖泊从淡水湖、咸水湖、盐湖至干盐湖的演化过程,文章分析了白云石和铁白云石的成因。白云石是盐类矿物的一种、且无机环境下不能沉淀,蒸发作用和微生物介导是白云石矿物形成的两个重要影响因素。蒸发作用为白云石的形成提供了足够浓度的Mg2+,微生物的介导作用帮助Mg2+克服动力学障碍进入碳酸钙晶格形成白云石。白云石是湖泊演化早期析出的一种碳酸盐类矿物,主要在咸水湖环境中沉淀,盐湖环境中主要沉淀硫酸盐类和氯化物矿物,在盐湖这种高盐度环境下能够生存的微生物非常少,白云石含量明显降低。铁白云石是白云石矿物的一种,是Fe2+替代白云石中的Mg2+形成的次生矿物。Fe2+有两种来源：粘土矿物转换过程中的释放和深部热液来源。Fe2+进入白云石的过程主要是在无机、高温环境下完成的,但不排除微生物的介导作用。     

塔里木盆地中央隆起区上寒武统—下奥陶统白云岩储层中两类白云石充填物:特征与成因

在塔里木盆地中央隆起区,下古生界白云岩储层中的白云石充填物从形态上可分为菱形和鞍状两类,它们具有不同的岩石学特征,菱形白云石内部结构简单均一,而鞍状白云石内部结构比较复杂,由内核、环带和外缘三部分组成。地球化学组成分析表明,菱形白云石可能形成于成岩作用的早期,成岩物质可能来源于改造的海水,其沉淀是一个相对稳定的过程,后期仅少量受到富铁流体的改造。而鞍状白云石的形成则可能与断裂诱发的深部热流体活动密切相关,其物质可能来源于深部热液在运移过程中对围岩白云石的溶解,鞍状白云石内部复杂的结构可能反映了断裂的幕式活动。因此,两类白云石充填物反映了不同的成岩流体环境,特别是鞍状白云石很可能是热液溶蚀作用发生的重要标志。在白云岩储层研究中,今后需要进一步深入详细分析充填物的产状、充填作用发生的时间和机制,对于研究分析白云岩储层形成机制和储层预测都有重要意义。     

湖相原生白云石的微生物成因机理探讨*

近年来,随着对微生物白云石模式研究的不断深入,为解释“白云石问题”提供了新思路。前人对微生物白云石成因研究侧重于微生物对未固结沉积物的改造,即有机准同生白云石化作用,这与实验室中以微生物为媒介形成的“有机原生白云石”在成因机理上存在差异。笔者将微生物白云石机理引入湖相原生白云石成因解释中,认为在湖水—沉积物交界处也会发生微生物成因的原生白云石沉淀,即有机原生白云石。湖水与沉积物交界处的微环境存在明显区别,总体可分为有氧和缺氧2种亚环境,不同亚环境中生活有不同的微生物群落。根据湖泊亚环境特性和微生物种类及其在白云石形成过程中所发挥的作用,可以区分出细菌有氧氧化模式、硫酸盐还原模式和产甲烷模式3种微生物白云石模式。不同模式对应于不同的湖泊环境: 细菌有氧氧化模式主要发生于有氧、高Mg/Ca值的咸水/盐湖环境;硫酸盐还原模式主要发生于缺氧、高Mg/Ca值的咸水/盐湖环境;产甲烷模式主要发生于缺氧、低Mg/Ca值的淡水/咸水湖环境。另外,还探讨了pH值变化、SO42-的存在和硫化物对镁水合物脱水的影响以及微生物白云石沉淀的环境因子。对微生物成因的原生白云石模式的深入认识,将为湖相白云石成因研究提供新的理论基础和研究思路。     

塔里木盆地和田河气田下奥陶统白云岩成因

塔里木盆地和田河气田是最近探明的大型碳酸盐岩气田,下奥陶统主要发育两类白云岩。下部为层状白云岩,以细晶为主,阴极发光呈紫红色和蓝紫色,有序度为0.57～0.68,Sr、Na含量低,碳氧同位素偏负,成岩深度约1500m;上部斑状灰质白云岩与层状白云岩相比,晶形较粗、以中晶为主,有序度较高、为0.85～0.90,Sr偏高、Na偏低,碳氧同位素更偏负,成岩深度约2000m。通过对上述特征综合研究,认为层状白云岩形成于早期浅埋藏海水-淡水混合环境,提出斑状灰质白云岩形成于晚期深埋藏压实流-淡水混合环境,总结了两种成因机理,建立了相关的白云石化模式。     

The partitioning of Fe and Mg between olivine and carbonate and the stability of carbonate under mantle conditions

We have investigated the effect of Fe on the stabilities of carbonate (carb) in lherzolite assemblages by determining the partitioning of Fe and Mg between silicate (olivine; ol) and carbonates (magnesite, dolomite, magnesian calcite) at high pressures and temperatures. Fe enters olivine preferentially relative to magnesite and ordered dolomite, but Fe and Mg partition almost equally between disordered calcic carbonate and olivine. Measurement of K _d (X _Fe ^carb X _Mg ^ol /X _Fe ^ol X _Mg ^carb ) as a function of Fe/ Mg ratio indicates that Fe–Mg carbonates deviate only slightly from ideality. Using the regular solution parameter for olivine W _FeMg ^ol of 3.7±0.8 kJ/mol (Wiser and Wood 1991) we obtain for (FeMg)CO₃ a W _FeMg ^carb of 3.05±1.50 kJ/mol. The effect of Ca–Mg–Fe disordering is to raise K _d substantially enabling us to calculate W _CaMg ^carb -W _CaFe ^carb of 5.3±2.2 kJ/mol. The activity-composition relationships and partitioning data have been used to calculate the effect of Fe/Mg ratio on mantle decarbonation and exchange reactions. We find that carbonate (dolomite and magnesian calcite) is stable to slightly lower pressures (by 1 kbar) in mantle lherzolitic assemblages than in the CaO–MgO–SiO₂(CMS)–CO₂ system. The high pressure breakdown of dolomite + orthopyroxene to magnesite + clinopyroxene is displaced to higher pressures (by 2 kbar) in natural compositions relative to CMS. CO₂. We also find a stability field of magnesian calcite in lherzolite at 15–25 kbar and 750–1000°C.     

Integrated hydrochemical assessment of the Quaternary alluvial aquifer of the Guadalquivir River, southern Spain

The alluvial aquifer of the Guadalquivir River comprises shallow Quaternary deposits located in the central-eastern part of the Province of Jaén in southern Spain, where groundwater resources are used mainly for crop irrigation in an important agricultural area. In order to establish the baseline hydrochemical conditions and processes determining the groundwater quality, groundwater and river water samples were collected as part of an integrated investigation that coupled multivariate statistical analysis with hydrochemical methods to identify and interpret the groundwater chemistry of the aquifer system. Three main hydrochemical types (Mg–Ca–HCO₃, Ca–Mg–SO₄–HCO₃–Cl and Na–Ca–Mg–Cl–SO₄) were identified. Further interpretation, using R-mode principal components analysis (PCA) conducted with 13 hydrochemical variables, identified two principal components which explain ⅔ of the variance in the original data. In combination with the hydrochemical interpretation, mineralogical analyses of the aquifer sediment together with inverse geochemical modelling using NETPATH showed that dedolomitization (calcite precipitation and dolomite dissolution driven by gypsum dissolution) is the principal hydrochemical process controlling the regional groundwater chemistry. Other processes such as silicate weathering, ion exchange, mixing between river water and groundwater, and agricultural practices also affect the groundwater chemistry.     

鄂尔多斯盆地下奥陶统马家沟组马五段白云岩的地球化学特征

鄂尔多斯盆地奥陶系马家沟组马五段属于浅海碳酸盐层系,间夹蒸发岩层。盆地中东部通常含有白云岩,它们是主要油气储集层。一些研究者把它们看成近地表回流白云岩。然而白云岩的岩石学和地球化学表明这些白云岩具有埋藏成因的证据。〓〓马家沟组白云岩（马五段）具有暗红色阴极发光,微量元素Fe为5 500×10-6～6 200×10-6,Mn为170×10-6~210×10-6,稳定同位素氧组分为-7.093‰～-9.932‰PDB,（平均值为-8.671‰PDB）,稳定同位素锶（87Sr/86Sr）为0.709 766～0.708 65（有硅质碎屑物的放射性87Sr的影响）。薄片下可以看到白云石沿着裂缝交代,上述特征表明白云岩可能在埋藏条件下形成。〓〓白云岩稀土元素的分布模式与海水的稀土元素分布有明显的差别,缺少Ce和Eu的负异常,表明交代流体不会是海水或蒸发海水。包裹体的均一化温度为160~220℃,盐度为5wt%～25wt%,暗示白云石化作用温度高,压力大,交代流体为卤水。〓〓密西西比谷型（MVT）矿化作用（方铅矿和闪锌矿）以及共生的低温热液矿物——钾长石、萤石、石英、黄铁矿等表明白云岩具有区域热液特征。     

Tentative kinetic model for dolomite precipitation rate and its application to dolomite distribution

The dolomite problem has a long history and remains one of the most intensely studied and debated topics in geology. Major amounts of dolomite are not directly forming today from seawater. This observation has led many investigators to develop geochemical/hydrologic models for dolomite formation in diagenetic environments. A fundamental limitation of the current models for the growth of sedimentary dolomite is the dearth of kinetic information for this phase, in contrast to that available for calcite and aragonite.We present a simple kinetic model describing dolomite growth as a function of supersaturation using data from published high temperature synthesis experiments and our own experimental results. This model is similar in form to empirical models used to describe precipitation and dissolution rates of other carbonate minerals. Despite the considerable uncertainties and assumptions implicit in this approach, the model satisfies a basic expectation of classical precipitation theory, i.e., that the distance from equilibrium is a basic driving force for reaction rate. The calculated reaction order is high (~ 3), and the combined effect of high order and large activation energy produces a very strong dependence of the rate on temperature and the degree of supersaturation of aqueous solutions with respect to this phase.Using the calculated parameters, we applied the model to well-documented case studies of sabkha dolomite at Abu Dhabi (Persian Gulf), and organogenic dolomite from the Gulf of California. Growth rates calculated from the model agree with independent estimates of the age of these dolomites to well within an order of magnitude. A comparison of precipitation rates in seawater also shows the rate of dolomite precipitation to converge strongly with that of calcite with increasing temperature. If correct, this result implies that dolomite may respond to relatively modest warming of surface environments by substantial increases in accumulation rate, and suggests that the distribution of sedimentary dolomite in the rock record may be to some extent a temperature signal.     

近地表温压条件下白云岩溶解过程的实验研究

与溶解作用有关的次生孔隙是碳酸盐岩最主要的油气储集空间,从实验模拟角度研究碳酸盐溶解机制具有重要的理论与应用价值。本文在近地表的温度和压力条件下,进行了具相同成分和结构的白云岩在CO2和乙酸介质中的对照溶解实验,两种类型的具相同成分和不同结构的白云岩在CO2介质中添加和不添加硬石膏的对照溶解实验,以及方解石含量50%的岩石在CO2介质中添加和不添加硬石膏的对照溶解实验。实验结果表明:(1)近地表温压条件的酸性环境中,乙酸对碳酸盐矿物的溶解能力显著大于CO2流体,乙酸对白云石的溶解是接近化学计量的,而CO2流体则是非化学计量的,白云石中Ca优先溶出而Mg滞留;(2)溶解CaSO4的加入会显著改善近地表温压条件下CO2流体对白云石的溶解效果,使得白云石溶解接近化学计量组成,该过程是通过抑制Ca的溶出和加速Mg的溶出来实现的;(3)对于白云石含量大于90%的较纯的白云岩来说,溶解CaSO4的加入会使得白云岩溶出离子的Ca、Mg合量增加,因而总体上有利于白云岩溶解,与之相反,溶液中CaSO4的沉淀可能导致白云石的沉淀。实验结果可以帮助我们更深刻理解近地表环境白云岩的溶解过程,尤其是与膏盐伴生的白云岩的溶解及相应岩溶过程和次生孔隙的形成机制。      

四川盆地震旦系灯影组白云岩成因

基于岩芯观察、薄片鉴定、地球化学分析,结合区域地质背景,系统研究了四川盆地震旦系灯影组白云岩成因。岩石学特征分析发现,灯影组白云岩可分为泥粉晶云岩、粒屑云岩、微生物云岩、岩溶角砾云岩4类,其结构类型一般为泥晶—粉晶,说明白云岩化时间较早,为准同生期。地球化学分析表明,灯影组白云岩δ^13C平均值与震旦纪原始海水较为接近,δ^18O值呈现中—高负偏的特征,有序度和Fe、Mn含量相对偏低,Na含量相对较高,稀土元素配分模式则与海水配分曲线类似,表明白云岩化主要受到海源流体的影响。盆地周缘的古陆和水下隆起使盆内海水极易封隔浓缩,盆内发育的富Ca^2+菌藻类可间接提高海水的Mg^2+/Ca^2+比值,加之灯影期干旱炎热的古气候让盆内蒸发作用强烈,可伴生石膏等蒸发性矿物,促进白云石化。综合上述特征,四川盆地灯影组白云岩成因为微生物参与的蒸发海水回流渗透白云石化。     

四川盆地西南部中二叠统白云岩成因分析——来自锶同位素、稀土元素证据

白云岩作为优质的油气储层,其成因一直是沉积学研究热点,通过地球化学分析揭示其流体性质是探究白云岩成因的重要途径。本文通过对川西南中二叠统典型剖面和钻井的碳酸盐岩样品进行岩石学、稀土元素和锶同位素特征研究,分析结果显示:（1）其岩石类型主要有石灰岩、泥微晶白云岩、细-中晶白云岩和鞍形白云石4种。（2）研究区白云岩锶同位素比值（平均值0.709 77）明显高于石灰岩和同期海水,接近全球壳源锶同位素平均比值,显示白云岩化流体是热液来源,同时部分泥微晶白云岩显示海水锶同位素特征。（3）研究区碳酸盐岩相较于同期海相沉积物有较高的δCe值（平均值0.86）,显示其开放的成岩环境。（4）3种类型的白云岩相较于石灰岩有较高的δEu值（平均值0.99）和显著不同的稀土总量特征,显示研究区白云岩与石灰岩成岩流体性质不同且白云岩受到高温影响。综合分析表明,川西南地区白云岩主要是受构造控制的热液白云岩,部分为被岩浆和热液加热的海水改造的热对流白云岩。      

Dolomite dissolution: An alternative diagenetic pathway for the formation of palygorskite clay

Palygorskite is a fibrous, magnesium‐bearing clay mineral commonly associated with Late Mesozoic and Early Cenozoic dolomites. The presence of palygorskite is thought to be indicative of warm, alkaline fluids rich in Si, Al and Mg. Palygorskite has been interpreted to form in peritidal diagenetic environments, either as a replacement of detrital smectite clay during a dissolution–precipitation reaction or solid‐state transformation, or as a direct precipitate from solution. Despite a lack of evidence, most diagenetic studies involving these two minerals posit that dolomite and palygorskite form concurrently. Here, petrological evidence is presented from the Umm er Radhuma Formation (Palaeocene–Eocene) in the subsurface of central Qatar for an alternative pathway for palygorskite formation. The Umm er Radhuma is comprised of dolomitized subtidal to peritidal carbonate cycles that are commonly capped by centimetre‐scale beds rich in palygorskite. Thin section, scanning electron microscopy and elemental analyses demonstrate that palygorskite fibres formed on both the outermost surfaces of dissolved euhedral dolomite crystals and within partially to completely dissolved dolomite crystal cores. These observations suggest that dolomite and palygorskite formed sequentially, and support a model by which the release of Mg²⁺ ions and the buffering of solution pH during dolomite dissolution promote the formation of palygorskite. This new diagenetic model explains the co‐occurrence of palygorskite and dolomite in the rock record, and provides valuable insight into the specific diagenetic conditions under which these minerals may form.     

白云石化作用及白云岩储层研究进展

白云石化作用和白云岩储层一直都是碳酸盐岩研究中的重要领域。近年来,随着实验分析技术的进步以及油气勘探的深入,对白云岩的研究也取得了诸多进展:1数值模拟技术逐步应用到白云岩研究中,实现了白云石化模式研究由定性到定量的转变;2对微生物白云石化的研究不断加强,识别出了微生物相关白云石的特殊显微形貌特征并对其生物矿化机制进行了分析;3对已有白云石化模式的重新审视:包括对混合水白云石化的修正、对回流白云石化的扩展以及对构造—热液白云石化模式的丰富;4在白云石化与孔隙相关关系的研究中,突破了白云石化增孔的传统认识,逐步强调白云石化在孔隙保存方面的作用;5注重研究白云岩结构、成岩环境、原始相带以及白云岩形成之后的溶蚀改造等因素对白云岩储层发育的控制作用。在未来的研究中,应加强3个方面内容,一是对白云岩结构演化规律的定量研究,二是在成岩流体示踪方面要加强对新技术手段(如二元同位素、Mg同位素)的使用,同时注意借鉴成矿流体研究中的成熟技术和方法,三是要加强对深部白云岩储层形成和保存机制的探索。     

Dolomite formation within microbial mats in the coastal sabkha of Abu Dhabi (United Arab Emirates)

Microbial mediation is the only demonstrated mechanism to precipitate dolomite under Earth surface conditions. A link between microbial activity and dolomite formation in the sabkha of Abu Dhabi has, until now, not been evaluated, even though this environment is cited frequently as the type analogue for many ancient evaporitic sequences. Such an evaluation is the purpose of this study, which is based on a geochemical and petrographic investigation of three sites located on the coastal sabkha of Abu Dhabi, along a transect from the intertidal to the supratidal zone. This investigation revealed a close association between microbial mats and dolomite, suggesting that microbes are involved in the mineralization process. Observations using scanning electron microscopy equipped with a cryotransfer system indicate that authigenic dolomite precipitates within the exopolymeric substances constituting the microbial mats. In current models, microbial dolomite precipitation is linked to an active microbial activity that sustains high pH and alkalinity and decreased sulphate concentrations in pore waters. Such models can be applied to the sabkha environment to explain dolomite formation within microbial mats present at the surface of the intertidal zone. By contrast, these models cannot be applied to the supratidal zone, where abundant dolomite is present within buried mats that no longer show signs of intensive microbial activity. As no abiotic mechanism is known to form dolomite at Earth surface conditions, two different hypotheses can reconcile this result. In a first scenario, all of the dolomite present in the supratidal zone formed in the past, when the mats were active at the surface. In a second scenario, dolomite formation continues within the buried and inactive mats. In order to explain dolomite formation in the absence of active microbial metabolisms, a revised microbial model is proposed in which the mineral‐template properties of exopolymeric substances play a crucial role.     

微生物成因白云石研究进展

"白云岩问题"一直是沉积地质学研究的热点和难点之一,白云岩在我国和世界范围内都是重要的油气储层。因此,深入认识白云岩成因对于碳酸岩油气勘探具有重要参考意义。白云岩成因有多种解释模式,如萨布哈蒸发模式、渗透回流模式、埋藏调节模式、混合水模式、潮汐泵模式等。近几十年来,随着低温白云石研究的不断深入,微生物白云石模式作为一种新的成因模式被提出并不断被完善。本文回顾了微生物成因白云石的研究进展,总结了低温白云石形成的3个动力学障碍(镁离子的高水合能、硫酸根的存在、碳酸根离子的低浓度和低活度),简要介绍了微生物成因白云石模式的建立、微生物成因白云石的生长过程及发育特征,系统分析了微生物在白云石形成过程中的调节作用,指出微生物(如硫酸盐还原菌、古甲烷菌)的存在可以改变溶液中的离子平衡,进而有利地克服白云石形成过程中的动力学障碍,并列举了低温微生物成因白云石的氧同位素指标在古温度恢复和过去气候变化研究中的应用,最后对微生物成因白云石相关研究方向(如多学科交叉、新技术应用等)加以展望。对微生物成因白云石模式的深入认识,将为正确解释"白云岩问题"提供新的途径,也将为石油学家关心的白云岩储层问题提供新的理论基础和研究思路。     

Geochemistry and stable isotopic composition of tufa waters and precipitates from the Interlake Region, Manitoba, Canada: Constraints on groundwater origin, calcitization, and tufa formation

New major, trace and isotopic geochemical results from a regional study of springs discharging from the major carbonate rock aquifer in the Interlake Region of Manitoba, Canada, are used to understand water–rock reactions, timing of recharge/discharge, tufa formation processes, and as baseline data. Spring waters are fresh with total dissolved solids (TDS) concentrations ranging from 150 to 880 mg/L. Waters discharging in the northern part of the study area have lower TDS, are dominantly Ca–Mg–HCO₃ waters with low SO₄ concentrations (<< 50 mg/L), and appear to have interacted primarily with Silurian carbonate lithologies. In contrast, waters in the southeastern part of the study area have higher TDS and have elevated SO₄ concentrations (up to 210 mg/L). Spring waters have elevated Mg/Ca_molar (1.23 ± 0.23), typically greater than congruent dissolution of dolomite. Ca and Mg concentrations and Mg/Ca_molar indicate that groundwater residence times were sufficient to allow equilibration with bedrock dolomite lithologies; elevated tritium in northern waters indicates a significant recharge component in the 1960's and 1970's. Tufa precipitates that have formed from many of the spring waters are low-Mg calcite (MgO = 1.70 to 5.80 wt.%). Sr concentrations are variable (57 to 657 ppm) and tufa Sr/Ca_molar ratios appear to be entirely controlled by spring water Sr/Ca_molar. Empirically determined Sr distribution coefficients (D_Sr = 0.389 ± 0.083) indicate rapid crystallization following CO₂ degassing, consistent with heavier δ¹³C_VPDB compared to spring waters. Sulfate concentrations are generally too low for calcitization (dedolomitization) reactions driven by anhydrite dissolution to be the dominant control on the elevated groundwater Mg/Ca_molar, implying either extensive sulfate reduction along the flow paths (however, δ¹³C_DIC suggests the elevated SO₄ is more consistent with Fe-sulfide oxidation), or that other processes are involved. Major ion ratios suggest that the waters in the southern part of the study area are more consistent with interaction with siliciclastic rocks than with anhydrite dissolution. We suggest that calcitization (dedolomitization) reactions driven by anhydrite dissolution may not dominate all carbonate aquifers and that mixing of waters in karst conduits combined with ion exchange reactions are important controls on water chemistry in these systems.     

Microcrystalline dolomite in a middle Permian volcanic lake: Insights on primary dolomite formation in a non-evaporitic environment

Lacustrine dolomite nucleation commonly occurs in modern and Neogene evaporitic alkaline lakes. As a result, ancient lacustrine microcrystalline dolomite has been conventionally interpreted to be formed in evaporitic environments. This study, however, suggests a non-evaporitic origin of dolomite precipitated in a volcanic–hydrothermal lake, where hydrothermal and volcanic processes interacted. The dolomite occurs in lacustrine fine-grained sedimentary rocks in the middle Permian Lucaogou Formation in the Santanghu intracontinental rift basin, north-west China. Dolostones are composed mainly of nano-sized to micron-sized dolomite with a euhedral to subhedral shape and a low degree of cation ordering, and are interlaminated and intercalated with tuffaceous shale. Non-dolomite minerals, including quartz, alkaline feldspars, smectite and magnesite mix with the dolomite in various proportions. The ⁸⁷Sr/⁸⁶Sr ratios (0.704528 to 0.705372, average = 0.705004) and δ²⁶Mg values (−0.89 to −0.24‰, average = −0.55‰) of dolostones are similar to those of mantle rocks, indicating that the precipitates mainly originated from fluids that migrated upward from the mantle and were subject to water–rock reactions at a great depth. The δ¹⁸O values (−3.1 to −22.7‰, average = −14.0‰) of the dolostones indicate hydrothermal influence. The trace and rare earth element concentrations suggest a saline, anoxic and volcanic–hydrothermally-influenced subaqueous environment. In this subaqueous environment of Lucaogou lake, locally high temperatures and a supply of abundant Mg²⁺ from a deep source induced by volcanic–hydrothermal activity formed favourable chemical conditions for direct precipitation of primary dolomite. This study's findings deepen the understanding of the origin and processes of lacustrine primary dolomite formation and provide an alternative possibility for environmental interpretations of ancient dolostones.