氯化物对方解石和白云石矿物溶解度的影响

借助PHREEQC软件,文章对方解石、白云石分别在无CO2和大气PCO2条件下NaCl、KCl、CaCl2和MgCl2溶液中的溶解度进行了模拟计算,结果显示:方解石在NaCl、KCl、和MgCl2溶液中以及白云石在NaCl、KCl溶液中的溶解度比纯水中大得多,其原因主要是盐效应。由于同离子效应,在CaCl2溶液中可降低方解石溶解度,而白云石在较高浓度CaCl2或MgCl2溶液中,虽发生同离子效应,其溶解度仍较纯水中有不同程度提高。模拟还显示,方解石在MgCl2溶液中以及白云石在CaCl2溶液中溶解时将分别发生白云石化和去白云石化反应,从而促使不全等溶解继续发生。在常规离子中,按方解石、白云石溶解度提高发挥作用的重要性排序为:阴离子中都是SO24->Cl-;对于方解石溶解,阳离子中Mg2+>Na+>K+>Ca2+;对于白云石溶解,当PCO2=0或PCO2=10-3.5bar且CaCl2浓度大约在1.5mol/L以下时,Na+>K+>Ca2+>Mg2+;当PCO2=10-3.5bar且CaCl2浓度大约在1.5mol/L以上时,Ca2+>Na+>K+>Mg2+。     

硫酸根离子对方解石和白云石溶解度的影响

在无CO2和有P_CO2条件下,利用目前成熟的水文地球化学模拟软件——PHREEQC,分别对方解石、白云石在Na2SO4、CaSO4和MgSO4溶液中的溶解度进行了模拟计算。结果显示：溶液中SO₄^2-的存在对方解石、白云石溶解度的提高作用很大。如在Pco2、浓度为1200mmol／L的Na2SO4溶液中,方解石和白云石溶解度分别为纯水中溶解度的9．544和9．897倍。其作用机理是：在无同离子效应时,SO₄^2-等所产生的盐效应和SO₄^2-与各种阳离子形成的离子对起重要作用;而有同离子效应时,将发生白云石化或去白云石化反应,从而促使不全等溶解继续发生。与此同时,即使存在同离子效应的条件下,特别是在较高浓度条件下,盐效应的作用也是不容忽视的。     

方解石,白云石,菱铁矿分别与含CO2水溶液反应平衡时的温度和压力

本文运用热力学原理确立了方解石、白云石、菱铁矿分别与含CO_2水溶液反应平衡时的温度和压力函数关系式。它们反应平衡所需要的最高临界温度分别为266K,264K和261K,最低临界压力分别为86.5MPa,106.8MPa和133.7MFa;在含CO_2水溶液中的溶解度均随压力增大、温度降低而增加;其生成则随压力减小和温度升高而变易。当温度、压力和水中含CO_2的量相同时,它们的溶解度大小顺序是方解石>白云石>菱铁矿。     

秦巴北部商县—卢氏地区变质方解石—白云石地质压力计的研究

秦巴北部的商县-卢氏县地区广泛分布有区域变质的方解石-白云石共生矿物对,它们对于估计变质作用和断裂构造作用的温压条件,有着重要的意义。本文着重就该地区Fe~(2+)在方解石-白云石中的X_(Fe)~(Co)>X_(Fe)~(Dol)分配情况,提出新的计压方法。     

黄土和沉积岩中分离方解石和白云石的方法实验

采用不同浓度的ＨＣｌ、ＨＡｃ、ＮＨ４Ａｃ及ＮＨ４Ａｃ－ＨＡｃ缓冲深液对典型黄土剖面的黄土样品进行了系统的浸取实验,结果表明,稀ＨＡｃ是分离方解石与白云石的最佳深剂,在浸取实验中对１４种不同元素含量进行测试,多数元素的含量有变化,用稀ＨＡｃ溶液浸取所得的浸取注中＾８７Ｓｒ／＾８６Ｓｒ的测定结果与使用稀ＨＣｌ浸取的浸取液中＾８７Ｓｒ／＾８６Ｓｒ测定值有一定的差别,方法可满足在古气候研究中对不同成因碳酸盐利用的要求。     

连续测定方解石和白云石中碳,氧同位素的比值的方法及其意义

本文提出了利用方解石和白云石二者的不同活性，在不同的温度条件下，在同一份 碳酸盐岩样品中，连续侧定碳、氧同位素比值的新方法。测定结果精度高，能用于判定白云石的 成因，具有实用价值。     

连续测定方解石和白云石中碳、氧同位素比值的方法及其意义

本文提出了利用方解石和白云石二者的不同活性,在不同的温度条件下,在同一份碳酸盐岩样品中,连续测定碳、氧同位素比值的新方法。测定结果精度高,能用于判定白云石的成因,具有实用价值。     

白云鄂博碳酸岩的方解石-白云石地质温度计

利用方解石-白云石地质温度计对白云鄂博地区碳酸岩的平衡温度进行了测定。出露于东矿下盘的白云岩质火山岩和出露于尖山的方解石-白云石型火山岩获得了较高的温度,分别为681℃和648℃。这些样品中的方解石呈二十微米左右晶形较完整的小片,被稍大粒度的白云石颗粒包裹,未受交代作用影响,推测这种碳酸岩在快速冷却的情况下保存下了其岩浆侵位时的成分特点,从而指示出接近碳酸岩浆侵位时的温度。但本区多数碳酸岩的平衡温度在400～500℃之间,有下列三种情况:(1)具有自形-半自形中粗粒粒状变晶结构的碳酸岩最后的平衡温度为415～496℃;(2)产自东矿的其余样品(火山岩),所测最后平衡温度为431～485℃,在测温的微区范围内可见极细粒白云石方解石与稀土等矿物共生的现象;(3)为交代重结晶结构的碳酸岩明显受到后期热液流体的交代,在流体的作用下共生方解石和白云石在成分上达到新的平衡,平衡温度为432～507℃。本文所分析的样品多数结果(371～507℃)与用白云石(方解石)和磁铁矿氧同位素温度计对白云鄂博碳酸岩的计算结果(360～546℃)十分一致。虽然有研究者对方解石-白云石温度计用于火成碳酸岩表示过质疑,但本文资料表明火成碳酸岩最后的平衡温度是可以运用方解石-白云石温度计法来计算的。     

方解石、白云石样品能谱无标样定量分析准确性探讨

利用Quanta 200环境扫描电镜、GENESIS能谱仪在不同的测试条件下,对方解石和白云石标样进行无标样定量分析实验,得到不同测试条件下对方解石和白云石类样品进行无标样定量分析时的碳的LEA因子和SEC因子。在高真空模式下,当加速电压分别为15 kV,20 kV和25 kV时,方解石和白云石样品的碳的LEA因子分别为61和51,55和37,48和20;碳的SEC因子分别为1.788 0和1.432,1.685 0和1.281,1.561 9和1.137。在低真空模式下,当加速电压分别为15 kV,20 kV和25 kV时;方解石和白云石样品的碳的LEA因子分别为56和41,38和29,32和20;碳的SEC因子分别为1.568 8和1.367,1.408 2和1.226,1.356 0和1.164。当使用这套碳的LEA因子或SEC因子定量分析方解石或白云石类样品时,得出的CO2质量分数与标准值的误差均在±1%左右。     

A model for the distribution of trace elements between calcite and dolomite

A crystal-growth model is proposed, which allows ions of a trace element to enter the Ca and Mg sites of dolomite in proportion to the size of the ions relative to that of Ca and Mg ions, and which assigns equal portions of the trace element to the Ca site of dolomite and the Ca site of associated calcite. The model produces calcite/dolomite distribution coefficients of 0.79 for Mn and 0.43 for Fe, which may be compared with 0.85 and 0.28 as observed in marble, and a distribution coefficient of 2.0 for Sr and Ba, which may be compared with observed values of 2.3 for Sr and 1.8 for Ba.     

Microcracking in calcite and dolomite marble: microstructural influences and effects on properties

Microstructure‐based finite-element analysis with a microcracking algorithm was used to simulate an actual degradation phenomenon of marble structures, i.e., microcracking. Both microcrack initiation and crack propagation were characterized, as were their dependence on lattice preferred orientation (LPO), grain shape preferred orientation (SPO), grain size, marble composition (calcite and dolomite) and grain‐boundary fracture toughness. Two LPOs were analyzed: a random orientation distribution function and an orientation distribution function with strong directional crystalline texture generated from a March–Dollase distribution. Three SPOs were considered: equiaxed grains; elongated grains and a mixture of equiaxed and elongated grains. Three different grain sizes were considered: fine grains of order 200 μm (only calcitic marble); medium size grains of order 1 mm (calcitic and dolomitic marbles); and large grains of order 2 mm (only dolomitic marble). The fracture surface energy for the grain boundaries, γ_ig, was chosen to be 20 and 40 % of the fracture surface energy of a grain, γ_xtal, so that both intergranular and transgranular fracture were possible. Studies were performed on these idealized marble microstructures to elucidate the range of microcracking responses. Simulations were performed for both heating and cooling by 50 °C in steps of 1 °C. Microcracking results were correlated with the thermoelastic responses, which are indicators related to degradation. The results indicate that certain combinations of LPO, SPO, grain size, grain‐boundary fracture toughness and marble composition have a significant influence on the thermal-elastic response of marble. Microstructure with the smallest grain size and the highest degree of SPO and LPO had less of a tendency to microcrack. Additionally, with increasing SPO and LPO microcracking becomes more spatially anisotropic. A significant observation for all microstructures was an asymmetry in microcracking upon heating and cooling: more microcracking was observed upon cooling than upon heating. Given an identical microstructure and crystallographic texture, calcite showed larger thermal stresses than dolomite, had an earlier onset of microcracking upon heating and cooling, and a greater microcracked area at a given temperature differential. Thermal expansion coefficients with and without microcracking were also determined.     

Qualitative analysis of three-dimensional strain using twins in calcite and dolomite

Turner's (1953) technique of locating the compression (C) and tension (T) axes from the known orientations of C-axis and twin pole ([022̄1] in dolomite and [011̄2] in calcite) for each grain yields the orientation of the unique stress system when a great majority of the grains in the rock shows only singlet twins. However, since it assumes the highest possible value for the coefficient of resolved shear stress s₀ (= 0.5), application of the technique to rocks in which a large number of grains show doublet and triplet twins results in great dispersion of the C- and T-axes. In such cases the unique stress system can be established by preparing separate C-axes fabric diagrams for the untwinned grains, grains with singlet twins, grains with doublet twins and grains with triplet twins; measurement of the orientations of the twin planes becomes unnecessary.     

方解石-白云石-菱镁矿的中远红外光谱学特征研究

利用拉曼光谱和红外光谱研究了方解石、白云石和菱镁矿的光谱学特征,探究了影响三种矿物红外辐射性能的因素。三种矿物的拉曼光谱(Raman)、中红外吸收光谱(MIR)、远红外吸收光谱(FIR)显示随着矿物中镁含量的增大将会影响CO₃^2-的面外弯曲振动(ν₂)、反对称伸缩振动(ν₃)和平面内弯曲振动(ν₄),使各光谱特征峰均向高频端迁移。基于黑体辐射定律以及在80 ℃、400~2 000 cm^-1矿物的辐射能量谱,结果显示方解石、白云石、菱镁矿的发射率依次减少(0.951,0.938,0.895)。三种矿物的红外吸收光谱和发射光谱中的振动位置均受CO₃^2-基频的显著影响,在1 300~1 650 cm^-1均产生宽的低吸收带,该吸收带与CO₃^2-的反对称伸缩振动相关,且吸收带范围(202,236,272 cm^-1)与发射率之间呈负相关关系。因此,当最强化学键的振动出现在发射光谱窄的吸收带范围内会产生相对较高的辐射能和发射率。此外,矿物的晶体结构也会影响发射率,大的离子半径、键长和晶胞体积将降低辐射过程中能量的吸收,增强辐射特性。综上研究结果,方解石、白云石和菱镁矿的拉曼光谱和红外光谱揭示了金属原子的相对质量对光谱学特征的显著影响,其发射率可能受到C—O键的反伸缩振动范围、最强吸收带控制的最低发射率以及矿物晶体结构的共同影响。这项研究呈现了必要的光谱信息和热发射率数据以识别特定的碳酸盐矿物,为类似矿物的光谱特征研究奠定了基础;同时为进一步认识地壳中大量的碳酸盐矿物提供了研究方法,也为地外勘探的深入研究给予相关的理论基础。     

Deformation twinning in calcite,dolomite, and other rhombohedral carbonates

Transmission electron microscope (tem) observations of single and multiple twins in calcite and dolomite are presented, and the results are analysed by means of selected area diffraction and trace analysis. Simple twinning in rhodochrosite and kutnahorite is also analysed. It is shown that the ordered carbonates, such as dolomite, have a common twinning plane {01 \(\bar 1\) 2} and this appears to be their only mode of deformation twinning. The carbonates with higher symmetry, such as calcite, have {01 \(\bar 1\) 8} as the primary twinning plane but calcite itself has other twinning mechanisms, of which the most important is illustrated. Crossing and stopping twins are also discussed. It is shown that twinning in calcite, which occurs predominantly at low temperatures, is characterized by the generation of large numbers of glide dislocations.     

Grain growth kinetics of dolomite,magnesite and calcite: a comparative study

The rates of grain growth of stoichiometric dolomite [CaMg(CO₃)₂] and magnesite (MgCO₃) have been measured at temperatures T of 700–800°C at a confining pressure P _c of 300 MPa, and compared with growth rates of calcite (CaCO₃). Dry, fine-grained aggregates of the three carbonates were synthesized from high purity powders by hot isostatic pressing (HIP); initial mean grain sizes of HIP-synthesized carbonates were 1.4, 1.1, and 17 μm, respectively, for CaMg(CO₃)₂, MgCO₃, and CaCO₃, with porosities of 2, 28, and 0.04% by volume. Grain sizes of all carbonates coarsened during subsequent isostatic annealing, with mean values reaching 3.9, 5.1, and 27 μm for CaMg(CO₃)₂, MgCO₃, and CaCO₃, respectively, in 1 week. Grain growth of dolomite is much slower than the growth rates of magnesite or calcite; assuming normal grain growth and n = 3 for all three carbonates, the rate constant K for dolomite (≃5 × 10⁻⁵ μm³/s) at T = 800°C is less than that for magnesite by a factor of ~30 and less than that for calcite by three orders of magnitude. Variations in carbonate grain growth may be affected by differences in cation composition and densities of pores at grain boundaries that decrease grain boundary mobility. However, rates of coarsening correlate best with the extent of solid solution; K is the largest for calcite with extensive Mg substitution for Ca, while K is the smallest for dolomite with negligible solid solution. Secondary phases may nucleate at advancing dolomite grain boundaries, with implications for deformation processes, rheology, and reaction kinetics of carbonates.     

Carbon and oxygen isotope analysis of calcite or dolomite associated with organic matter

A combined 5% sodium hypochlorite (<24 hr.) followed by silver phosphate (15–20 mn) pre-treatment process has been developed for the isotopic analysis of calcite- or dolomite-bearing samples associated with organic matter and sulphide minerals. This treatment purifies the CO₂ gas of contaminant sulphur-bearing organic species and H₂S which are generated during the reaction of the sample with phosphoric acid.