Experimental investigation of the metamorphism of siliceous dolomites

For the reaction: 1 diopside+3 dolomite ?2 forsterite+4 calcite+2 CO₂ (14) the following P _total?T-brackets have been determined experimentally in the presence of a gasphase consisting of 90 mole%CO₂ and 10 mole%H₂O∶1 kb, 544°±20° C; 3kb, 638°±15° C; 5kb, 708°±10° C; 10kb, 861°±10° C. The determination was carried out with well defined synthetic minerals in the starting mixture. The MgCO₃-contents of the magnesian calcites formed by the reaction in equilibrium with dolomite agree very well with the calcite-dolomite miscibility gap, which can be recalculated from the activities and the activity coefficients of MgCO₃ as given by Gordon and Greenwood (1970). The equilibrium constant K _14b was calculated with respect to the reference pressure P ₀=1 bar using the experimentally determined \(P_{total} TX_{CO_2 }\) brackets, the activities of MgCO₃ and CaCO₃ (Gordon and Greenwood 1970; Skippen 1974) and the fugacities of CO₂ Holloway (1977) considering the correction of Flowers (1979). Results are plotted as function of the absolute reciprocal temperature in Fig. 1. For the temperature range of 530° to 750° C the following linear expression can be given for the natural logarithm of K_14b: (g) $$[ln K_{14b} ]_T^P = - \frac{{18064.43}}{{T\left( {^\circ K} \right)}} + 38.58 + \frac{{0.308(P - 1 bar)}}{{T\left( {^\circ K} \right)}}$$ where P is the total pressure in bars and T the temperature in degrees Kelvin. Combining Equation (g) with the activities of MgCO₃ and CaCO₃ gives the equilibrium fugacity \(f_{CO_2 }\) : (i) $$[ln f_{CO_2 } ]_T^P = - \frac{{11635.44}}{{T\left( {^\circ K} \right)}} + 21.09 + \frac{{0.154(P - 1 bar)}}{{T\left( {^\circ K} \right)}}$$ Equation (i) and the fugacities of CO₂ permit to calculate the equilibrium data in terms of \(P_{CO_2 }\) and T (see Fig. 3) or P _total, T and \(X_{CO_2 }\) (see Fig. 5). Combining the \(P_{total} TX_{CO_2 }\) equilibrium data of the above reaction with those of the previously investigated reaction (Metz 1976): 1 tremolite+11 dolomite ?8 forsterite+13 calcite+9 CO₂+1 H₂O yields the stability conditions of the four-mineral assemblage: diopside+calcian dolomite+forsterite +magnesian calcite and the stability conditions of the five-mineral assemblage: tremolite+calcian dolomite+forsterite +magnesian calcite+diopside both shown in Fig. 6. Since these assemblages are by no means rare in metamorphic siliceous dolomites (Trommsdorff 1972; Suzuki 1977; Puhan 1979) the data of Fig. 6 can be used to determine the pressure of metamorphism and to estimate the composition of the CO₂-H₂O fluid provided the temperature of the metamorphic event was determined using the calcite-dolomite geothermometer.     

Electron spin resonance of stabilized free radicals in sedimentary organic matter

Electron spin resonance (ESR) is evaluated as a method to study the thermal degradation of sedimentary organic matter which consists mainly of kerogen. Whole rock and separated kerogen samples were pyrolysed stepwise (ambient to 700°C at 50°C increments), extracted and analysed for elemental composition and ESR spectra at each step. Whole rock samples give rise to complex spectra which include those of paramagnetic metals and are therefore unsuitable in most cases for this purpose.The ESR parameters g value, ΔH and N_g differ for different types of immature organic matter. An increase in N_g,shift of g value to 2.0026–2.0028 and reduction in h are the main trends during pyrolysis and in natural heating of sedimentary organic matter.The peak generations of liquid and gaseous hydrocarbons coincide with maxima of free radical density. ESR spectroscopy in combination with complementary geochemical characterization of the sedimentary organic matter can serve to indicate maturity with respect to peak oil-gas generation.     

Geological significance of Coorong dolomites

Microcrystalline dolomite and related carbonate minerals have been forming throughout the Quaternary in shallow ephemeral alkaline lakes on the coastal plain of the Coorong area in southern Australia. These Coorong dolomites differ significantly from sabkha-type dolomites. They form in areas where evaporation rates during summer months exceed groundwater inflow rates to a series of alkaline lakes. This results in the lakes becoming desiccated during summer months. Brines resulting from this drying phase are then refluxed out of the system into seaward-flowing groundwaters of an unconfined coastal aquifer. Dolomites and other fine-grained carbonates remain behind, whilst saline and sulphate evaporite minerals are flushed out of the system. Progressive restriction by sedimentation in and around the Holocene coastal dolomite lakes results in an upward-shoaling sedimentary cycle. Basal sediments which formed in a restricted marine environment pass upwards to lacustrine dolomites or magnesites exhibiting desiccation and groundwater resurgence structures such as mudcracks and teepees. The upper Proterozoic Skillogallee Dolomite Formation, an early rift basin unit of the Adelaide Supergroup, contains dolomites which show many of the features characteristic of the peculiar groundwater hydrology which plays an important role in Coorong dolomite genesis. These features include aphanitic dolomites which lack relict saline or sulphate evaporite minerals. The Skillogallee Dolomite Formation in some areas overlies an earlier dolomitic unit, informally named the Callanna Beds, typified by abundant pseudomorphs after sulphate minerals. Sabkha style dolomites characterizing the Callanna Beds are replaced up-section by the Coorong-type dolomite of the Skillogallee Dolomite Formation. This implies the development of an increasingly more active groundwater regime. The ultimate source and mode of concentration of the necessary Mg required to form both the modern and ancient dolomites remain imperfectly understood.     

Electron microscopic investigation on a Pacific manganese concretion

In extension of earlier work by v. Heimendahl et al. (1976) a powder sample from Pacific manganese nodule DWHD 16 was investigated and analysed by TEM and SAD. In addition to phases reported in the earlier work psilomelane, goethite, micamanganese, glaucophane and three silicate phases were identified. Most of them were in agreement with earlier data gained from X-ray analyses.     

Metamorphism of siliceous dolomites at Naxos,Greece

Siliceous dolomitic marbles at Naxos, Greece, are crystallized in a range of metamorphic temperatures, estimated from 350 to 700 °C and a total pressure of about 6 kb. A number of low variant assemblages of this rock-system have been studied. The sequence of these metamorphic assemblages is a function of increasing metamorphism, and this is in agreement with other fielddata and with experimental data for the chemical system CaO-MgO-SiO₂-H₂O-CO₂ (-HF). The composition of the associated fluid inclusions may be considered reasonably correct in the light of experimentally obtained X _CO2 values for the mineral equilibria, extrapolated for a total pressure of about 6 kb at the interpolated temperatures at the sample locations.     

On phase equilibria in metamorphosed siliceous dolomites

Basing on calculations and experiments the equilibrium curves of 15 reactions occuring during metamorphism of siliceous dolomites are presented. In a T—X_{CO 2} diagram these curves intersect at four isobaric invariant points. This is consistent with the fact, that different reaction sequences are known from the nature.     

Electron microscope investigation of the structure of naturally and artificially metamorphosed kerogen

The alteration of organic materials during burial is similar to thermally induced carbonization. High resolution electron microscopy shows that samples of either natural or heat-treated kerogens are formed by stacks of two aromatic layers of 5–8 Å in diameter. During catagenesis and heat-treatment, these stacks orientate themselves parallel to each other and form clusters of increasing diameter.     

An investigation of the relationship between the geology of indonesian sedimentary basins and heat flow density

Geothermal data, collected from 929 wells drilled by oil companies in 20 Tertiary basins of Indonesia, have been related to the geology and tectonics of the area. It is found that the thermal conductivity increases with the depth of burial and degree of compaction in both transgressive and regressive sediments but decreases with increases in impurities and heterogeneous grain sizes. The temperature gradient is controlled mainly by the depth and temperature of a heat source beneath a basin. Very high heat-flow densities (> 125 mW m^?2) found in central Sumatra, South Sumatra, Salawati Basin and Bintuni Basin may be caused by relatively shallow magmatic diapirism.     

塔里木盆地寒武-奥陶系白云岩结构构造类型及其形成机理

塔里木盆地寒武-奥陶系白云岩度大、分布广,是重要的油气储集层.根据岩石学研究并结合地球化学特征将其分为4类,其特点如下:(1)泥晶-粉晶白云岩,白云石晶体小、晶形差,有序度在4类中最低(0.73);Na、K、Sr含量在4类中最高;δ13C值及Z值较高,分别为-0.94‰、122.3;Fe、Mn含量较低;阴极发光为亮桔红色;常呈纹层状,具暴露及成化标志.这些特征表明其结晶较快,形成环境蒸发强烈、盐度较高、氧化性较强,是在萨布哈环境中由浓缩海水发生白云石化所形成.(2)藻纹层白云岩,白云石晶体小,晶形较好,有序度较高(0.85);藻纹层基本保留了其原始微细结构;Na、K、Sr含量较低:δC值在4类中最高,平均为-0.50‰;含有较多黄铁矿.这些特征说明其可能形成于成岩作用的稍早期阶段且其成因与藻类活动密切相关,成岩环境盐度较低,可能是在藻类作用下,由富藻层浓集的镁与残留海水在浅埋藏环境中共同作用所形成.(3)雾心亮边白云岩,白云石普遍具雾心亮边结构,雾心含少量包裹体及灰质残余,亮边则少见或无;阴极发光下,雾心发亮桔黄色光,亮边发光暗或不发光;局部见此类白云石;呈星散状分布于亮晶颗粒灰岩或泥晶灰岩中;白云石晶体较大,晶形较好.此类白云岩的δ13C及Z值在4类中最低,K、Na、Sr、Fe含量相对较低,Mn含量最高;有序度较高,均值为0.83.这些特征表明此类白云岩中白云石的雾心可能是在早期浅埋藏环境中,由富镁孔隙水交代周围灰质所形成;亮边则形成于埋藏较深的环境,其所需镁可能来源于粘土矿物的转化.(4)重结晶白云岩:白云石晶体粗大且污浊,接触紧密;局部见白云石晶体具环带结构,局部见颗粒幻影结构;阴极发光较暗;Fe含量在4类中最高,Mn含量较高;有序度最高,平均为0.95;包裹体均一温度平均为110.2℃.这些特征表明其可能是在还原性较强的深埋藏环境中,由早期形成的白云岩经较强的重结晶作用所形成.     

Complex replacement of saddle dolomite by fluorite within zebra dolomites

A lateral transition of saddle dolomite into fluorite is observed within zebra dolomites of the Triassic Wetterstein Formation of the Drau Range (Carinthia/Austria). This lithological change is the result of a replacement of saddle dolomite by fluorite. Artificial staining of fluorite crystals by electron bombardment during cathodoluminescence indicates that fluorite crystals have a zonation typical of fluorite as well as of saddle dolomite. A combined dissolution/precipitation model is therefore proposed. Fluid inclusion studies indicate that these processes occurred at temperatures between 124 and 156 °C.     

Quantitative high resolution cathodoluminescence spectroscopy of diagenetic and hydrothermal dolomites

A combination of high resolution cathodoluminescence-spectroscopy (HRS-CL=high resolution spectroscopy of cathodoluminescence emission) with spatial resolving trace element analyses (PIXE=proton induced X-ray emission) is used to establish a method for the quantitative determination of the Mn-content of diagenetic and hydrothermal dolomites using the measurements of peak areas of Mn-activated CL emission bands. This method takes into account the overlap of the CL broad bands of Mn²⁺ in the Mg- and the Ca-lattice-position of dolomite. There is a linear correlation between the peak areas and Mn concentration up to approx. 1000–1500 ppm. Thus, CL spectroscopy allows a determination of Mn concentrations below the abilities of PIXE (10–15 ppm) to less than 1 ppm by extrapolation of this linear relation.

Up to an Fe-content of approx. 2000 ppm, no quenching effect of Fe on this linear relationship occurs. However, Fe-contents above 2000 ppm result in a decrease of Mn-induced luminescence. Even at Fe-concentration >25,000 ppm spectroscopy reveals that Mn-activated CL of dolomite is not entirely extinguished.     

Electron optical and X-ray powder diffraction study of synthetic and natural potassic cordierites

The microstructural and X-ray diffraction characteristics of natural K-bearing cordierites in buchites (Blaue Kuppe, Germany), and paralavas (Bokaro, India) are compared to those of three suites of synthetic, K-bearing Mg-cordierite, studied after annealing glasses of the requisite compositions for durations between 5 min and 255 days at 1,290° C and 1 bar. In analogy to pure Mg-cordierite, hexagonal high-cordierite initially crystallizes from the glass and subsequently transforms to orthorhombic low-cordierite. After annealing for 30–60 min, the crystals develop tweed-structure. With prolonged annealing, the pattern coarsens and develops into lamellar twinning. Higher K-contents favour earlier development of tweed-contrast. Distortion indices obtained by X-ray powder diffraction show a sharp initial increase of with annealing time, followed by a levelling off after approximately 10 h. Higher K-contents delay this initial increase, and decrease drastically the maximum distortion index that can be attained. The contrasting observations with respect to increasing K-content are due to the different levels of information yielded by TEM and X-ray diffraction. Analyses of electron diffraction patterns indicate that the metric state of individual crystals in any single sample annealed for more than one hour is highly heterogeneous, while no compositional differences could be detected. Hexagonal and variously distored crystals coexist. Thus intermediate structural states of cordierite in the classical sense are shown to exist, although intermediate distortion indices obtained by routine X-ray powder diffraction are largely due to a summation effect over such structurally heterogeneous populations. Although distinct differences in microstructure between the synthetic and the natural Fe²⁺-bearing cordierites exist, the Bokaro samples most closely resemble the early (1–10 h) tweed-structure of the synthetic products, whereas the Blaue Kuppe samples are comparable to a more mature (1–3 days) stage. It is thus concluded that the cordierite-bearing Bokaro paralavas cooled considerably faster than the Blaue Kuppe buchites.     

Metal release from dolomites at high partial-pressures of CO2

The potential for metal release associated with CO₂ leakage from underground storage formations into shallow aquifers is an important consideration in assessment of risk associated with CO₂ sequestration. Metal release can be driven by acidification of groundwaters caused by dissolution of CO₂ and subsequent dissociation of carbonic acid. Thus, acidity is considered one of the main drivers for water quality degradation when evaluating potential impacts of CO₂ leakage. Dissolution of carbonate minerals buffers the increased acidity. Thus, it is generally thought that carbonate aquifers will be less impacted by CO₂ leakage than non-carbonate aquifers due to their high buffering potential. However, dissolution of carbonate minerals can also release trace metals, often present as impurities in the carbonate crystal structure, into solution. The impact of the release of trace metals through this mechanism on water quality remains relatively unknown. In a previous study we demonstrated that calcite dissolution contributed more metal release into solution than sulfide dissolution or desorption when limestone samples were dissolved in elevated CO₂ conditions. The study presented in this paper expanded our work to dolomite formations and details a thorough investigation on the role of mineral composition and mechanisms on trace element release in the presence of CO₂. Detailed characterization of samples from dolomite formations demonstrated stronger associations of metal releases with dissolution of carbonate mineral phases relative to sulfide minerals or surface sorption sites. Aqueous concentrations of Sr²⁺, CO²⁺, Mn²⁺, Ni²⁺, Tl⁺, and Zn²⁺ increased when these dolomite rocks were exposed to elevated concentrations of CO₂. The aqueous concentrations of these metals correlate to aqueous concentrations of Ca²⁺ throughout the experiments. All of the experimental evidence points to carbonate minerals as the dominant source of metals from these dolomite rocks to solution under experimental CO₂ leakage conditions. Aqueous concentrations of Ca²⁺ and Mg²⁺ predicted from numerical simulation of kinetic dolomite dissolution match those observed in the experiments when the surface area is three to five orders of magnitude lower than the surface area of the samples measured by gas adsorption.     

The effect of Tschermak's substitution on assemblages in aluminous dolomites

A calculated petrogenetic grid for the system CaO-MgO-Al₂O₃-SiO₂-CO₂-H₂O (CaMASCH), incorporating Tschermak's substitutions in amphibole, chlorite, talc and clinopyroxene, is used to examine phase relationships in aluminous marbles. A series of diagrams illustrating the effect upon stable mineral assemblages of increasing the aluminium content of a bulk composition is used to show the way aluminous minerals enter mineral assemblages in progressively more aluminous rocks. The effects of changing pressure and the incorporation of Fe into the bulk composition on the stable mineral assemblages are also examined. The calculated equilibria are shown to be in reasonable agreement with natural assemblages, and the incorporation of new experimental data on amphiboles into the existing dataset is shown to improve the agreement between observed and natural amphibole compositions.     

Textural and geochemical alternations in Late Cenozoic Bahamian dolomites

Dolomitized intervals of a core from San Salvador Island, Bahamas, exhibit variations of two texturally and geochemically distinct end-members. In the Pliocene section of the dolomitized interval, the two end-members alternate in a pattern that may reflect originally and/or diagenetically modified depositional facies. Formerly mud-free intervals, locally capped by exposure surfaces are massive crystalline, mimetic dolomites (CM). Muddier sediments are replaced by friable microsucrosic dolomites (MS). CM and MS dolomites also differ in porosity (< 10% vs > 30%), permeability (< 10 md vs > 100 md), mol% MgCO₃ (44–9 vs 47–7) mol%), oxygen isotopic composition (1–7 vs 2–7‰) and strontium content (241 vs 106 ppm). These data indicate that depositional and diagenetic fabric are the principal controls governing the distribution of dolomite types. Differences in texture and geochemistry are suggested as arising through differential rates of crystallization produced as a result of variations in permeability and reactivity of the precursor sediments and rocks.     

Major and trace element associations in limestones and dolomites

Selective chemical separations of mineralogical constituents of limestones (Carboniferous limestones from the Isle of Man, and Lincolnshire limestone, Middle Jurassic, Lincolnshire) and dolomites (from Carboniferous limestone, Isle of Man) using dilute acetic acid and hydrogen peroxide have been used and the fractions obtained analysed to evaluate mineralogical associations of trace and major elements. Ca, Mg, Mn and Sr are mainly restricted to the carbonate fraction. Fe is found in carbonates, particularly dolomite, and also in sulphides with Zn, Cu, Ni and Pb, and with V and Cr and other traces in “residual” silicate minerals.It is concluded that mineralogical associations of trace elements are complex, and cannot be easily determined by statistical analysis. Selective chemical-separation methods of analysis offer direct indication of element associations with no loss of data. Calculated average concentrations in various fractions of analysed rocks (58 limestones and 19 dolomites) are tabulated.     

Origin of Dinantian zebra dolomites south of the Brabant-Wales Massif, Belgium

Zebra dolomites, characterized by a repetition of dark grey (a) and light (b) coloured dolomite sheets building up abbabba-sequences, occur in Dinantian strata from deep boreholes (> 2000 m) south of the Brabant-Wales Massif in Belgium. These zebra dolomite sequences are several tens of metres thick. The dark grey dolomite sheets (a) consist of non-planar crystals, 80–150 μm in diameter. These crystals display a mottled red–orange luminescence and are interpreted to be replacive in origin. The white dolomite sheets (b) consist of coarse crystalline nonplanar b₁ dolomite, which evolves outwards into transparent saddle shaped b₂ dolomite. The b₁ dolomites possess a mottled red–orange luminescence similar to the a dolomites, while the saddle shaped b₂ rims display red to dark brown luminescent-zones. The b₁ dolomites are possibly partly replacive and partly cavity filling. Their b₂ rims display criteria typical for a cement origin. Locally, cavities exist between two succeeding white dolomite sheets. These cavities make up ≈5% of the zebra rocks and are locally filled by saddle shaped ankerite and/or xenomorphic ferroan calcite. Geochemical and fluid inclusion data (T_h ≈ 120 °C) indicate a burial diagenetic origin for these zebra dolomites. The a and b₁ dolomites are characterized by similar geochemical compositions and fluid inclusion data pointing toward a related origin. To explain the development of the zebra textures, suprahydrostatic pressures in conjunction with late Variscan tectonic compression are invoked. A model involving dolomitizing fluids expelled during the Variscan orogeny is proposed. An overpressured system is also invoked to explain the important porosity development, the creation of centimetre-scale subvertical displacements of the zebra pattern and the microfractures affecting the b₁–b₂ dolomite crystals.     

Testing the preservation potential of early diagenetic dolomites as geochemical archives

Early marine diagenetic dolomite is a rather thermodynamically-stable carbonate phase and has potential to act as an archive of marine porewater properties. However, the variety of early to late diagenetic dolomite phases that can coexist within a single sample can result in extensive complexity. Here, the archive potential of early marine dolomites exposed to extreme post-depositional processes is tested using various types of analyses, including: petrography, fluid inclusion data, stable δ¹³C and δ¹⁸O isotopes, ⁸⁷Sr/⁸⁶Sr ratios, and U-Pb age dating of various dolomite phases. In this example, a Triassic carbonate platform was dissected and overprinted (diagenetic temperatures of 50 to 430°C) in a strike-slip zone in Southern Spain. Eight episodes of dolomitization, a dolostone cataclasite and late stage meteoric/vadose cementation were recognized. The following processes were found to be diagenetically relevant: (i) protolith deposition and fabric-preservation, and marine dolomitization of precursor aragonite and calcite during the Middle–Late Triassic; (ii) intermediate burial and formation of zebra saddle dolomite and precipitation of various dolomite cements in a Proto-Atlantic opening stress regime (T ca 250°C) during the Early–Middle Jurassic; (iii) dolomite cement precipitation during early Alpine tectonism, rapid burial to ca 15 km, and high-grade anchizone overprint during Alpine tectonic evolution in the Early Eocene to Early Miocene; (iv) brecciation of dolostones to cataclasite during the onset of the Carboneras Fault Zone activity during the Middle Miocene; and (v) late-stage regression and subsequent meteoric overprint. Data shown here document that, under favourable conditions, early diagenetic marine dolomites and their archive data may resist petrographic and geochemical resetting over time intervals of 10⁸ or more years. Evidence for this preservation includes preserved Late Triassic seawater δ¹³C_DIC values and primary fluid inclusion data. Data also indicate that oversimplified statements based on bulk data from other petrographically-complex dolomite archives must be considered with caution.     

滇东北矿集区茂租铅锌矿床热液白云石稀土元素特征

茂租铅锌矿床位于扬子地台西南缘,是滇东北矿集区内的一个大型矿床,矿体呈似层状产于震旦系灯影组白云岩中。矿石矿物以闪锌矿为主,次为方铅矿。脉石矿物主要为白云石、萤石和方解石。矿床的矿化蚀变分带明显,从围岩到矿体,矿化蚀变分带分别为:斑点状白云石化带、脉状白云石化带、星点状矿化带、细脉浸染状矿化带和矿体。白云石是该矿床的重要脉石矿物,除了震旦系灯影组的微晶-细晶白云石外,与成矿热液活动有关的白云石主要有斑点状白云石、脉状白云石和团块状白云石。文章对茂租铅锌矿床3种热液白云石及围岩灯影组白云岩的稀土元素地球化学特征进行了对比研究。结果表明:3种热液白云石与灯影组白云岩的稀土元素配分模式比较接近,总体上具有稀土元素总量低、轻稀土元素富集和Ce元素负异常的特征,这些相似的稀土元素特征表明3种蚀变白云石与围岩之间存在着成因联系。灯影组白云岩ΣREE含量较低,具有Eu元素负异常,而脉状和团块状热液白云石具有明显的Eu元素正异常,反映了存在较高温度的流体活动,热液蚀变白云岩是由高温热液流体形成。斑点状热液白云石Eu元素异常不太明显,可能是由于蚀变强度较弱,继承了原岩Eu元素负异常的特征。团块状白云石ΣREE和w(Y)、w(Sm)较高,表明有其他REE富集流体的加入。3种热液白云石是由高温流体形成,流体主要来源于地层,并有其他富含REE流体加入。