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.     

A study of the serpentinisation in the Vempalle dolomitic limestones near Pulivendala,Cuddapah District

The calcite-dolomite ratio of the Vempalle dolomitic limestones, serpentinised dolomitic limestones, and serpentines from the mineralised zone of the asbestos is determined by infrared spectroscopy. The ratio varies between 2 and 5·4 in the dolomitic limestones, between 1 and 1·5 in the serpentinised dolomitic limestones and it is taken as zero in the serpentines as both calcite and dolomite bands are absent in their infrared absorption spectra. The release of calcite during the serpentinisation is identified, which confirms the formation of serpentine.     

室温条件下青海湖水中镁离子浓度对沉淀碳酸钙同质多像类型的调控

青海湖是我国唯一报道过的现代湖底沉积物中白云石、方解石和文石等多种碳酸盐矿物共存的高原内陆咸水湖泊.以青海湖水和除菌青海湖水作为载体,以CaCl2和MgCl2·6 H2O作为反应原料,在实验室常温条件下采取控制变量法制备出不同浓度Mg2+参与下的钙质沉淀物,探讨Mg2+浓度对沉淀物类型的影响.仅添加CaCl2时,青海湖...     

Alkali carbonate reaction expansion of dolomitic limestone aggregates with porphyrotopic texture

Effects of porphyrotopic textures on expansion of dolomitic limestone aggregates due to alkali–carbonate reaction (ACR) are presented. The dispersed distribution of dolomites in the texture of aggregates can be divided into pophyrotopic-M, psedoporphyrotopic-M and porphyrotopic-S types. It is proved that porphyrotopic textures are more important to ACR expansion than lithologic species of dolomitic limestones. The dolomitic limestones with both porphyrotopic-M or psedoporphyrotopic-M texture and the small size of dolomite crystals are expected to be highly alkali–carbonate reactive. These aggregates can be found not only in dolomitic micritic limestones but also in dolomitic micritic allochemical limestones as well as dolomitic sparry allochemical limestones.     

Crack damage stress as a composite function of porosity and elastic matrix stiffness in dolomites and limestones

Twenty-five uniaxial compression tests were performed to determine stress at onset of dilation, referred to herein as “the crack damage stress,” in heterogeneous dolomites and limestones. A simplified model for crack damage stress (σ_cd) is developed here using porosity, elastic modulus, Poisson's ratio and three empirical coefficients. The model shows that when porosity decreases and elastic modulus increases, σ_cd rapidly increases and approaches its maximum value. On the other hand, when porosity increases and elastic modulus decreases, σ_cd rapidly decreases and approaches its minimum value. The proposed model is validated for six heterogeneous limestone and dolomite formations which are widely distributed in Israel.     

Biohermal and concretionary limestones and their significance in classification of carbonate rocks

A rational classification of organogenic limestones is suggested, based on biological, physical, and mechanical aspects and specificities of their origins and transformations.--IGR Staff     

The determination of calcium and magnesium in carbonate rocks by atomic-absorption spectrophotometry after acetic-acid decomposition

An atomic-absorption spectrophotometric method is described for the determination of Ca and Mg in carbonate rocks after an acetic-acid decomposition. KCl is used as a releasing agent instead of the more commonly used LaCl₃. Results obtained using both releasing agents compare favourably in accuracy and precision, KCl having the advantage that it is much less expensive.     

The stability of transition metal dolomites in carbonate systems: a discussion

The instability of transition metal dolomites [CaR²⁺(CO₃)₂ where R²⁺ is Fe, Co, Ni, Cu, or Zn] and the limited substitution of transition metal cations for Mg in the dolomite structure can be accounted for by the effect of octahedral distortion. For example, trigonal elongation of the Fe octahedron, due to the Jahn-Teller effect, observed in siderite and ankerite, results in elongation of the Ca octahedron which is sensitive to distortion because the radius of Ca²⁺ is close to the upper limit for octahedral coordination. Co, Ni, Cu, Zn octahedra are also thought to be deformed, relative to Mg octahedra, in carbonates.The free energy of formation (ΔG^o_f) of R²⁺CO₃ becomes more positive with increasing octahedral distortion. Estimated ΔG^o_f(dolomite) as well as stabilities and solubility limits of R²⁺ in natural and synthetic dolomites suggest a series in order of decreasing stability: Mg >Mn >Zn >Fe >Co >Ni >Cu.ΔG^o_f(est.) for the terminal Fe-dolomite solid solution [72 mol% CaFe(CO₃)₂] in the system CaCO₃-MgCO₃-FeCO₃ may represent an empirical threshold value for dolomite stability which lies between ΔG^o_f for Mn- and Zn-dolomites. While Zn-dolomite is probably not a stable phase, very extensive solid solution toward CaZn(CO₃)₂ is to be expected in the system CaCO₃-MgCO₃-ZnCO₃. The tendency for transition metal dolomites to contain excess CaCO₃ can also be accounted for in terms of octahedral distortion and AG^o_f.     

鲁西地区含白云石碳酸盐岩的矿物学特征及其形成环境分析

白云石的成因受到地质学界的广泛关注,现今在实验室中能够利用微生物合成高有序度的白云石,但天然白云石的成因与原始沉积环境特征的相关性并未完全揭示。本研究选取鲁西地区馒头组含白云石碳酸盐岩沉积地层为研究对象,通过矿物学、元素地球化学等分析,初步判断该地层白云石成因并重建白云石地层的古沉积环境,探讨了两者之间的关系。结果表明：白云石含量在本套地层中的均值为52.45%。Sr/Cu值(均值为23.59)与Ga/Rb值(均值为0.17)指示其整体表现为炎热干旱的古气候特征。δ¹³C值(均值为-1.56‰)与δ¹⁸O值(均值为-6.68‰)指示本套地层为海相沉积,推测古水温平均为23.5℃,古氧化还原特征表现为弱还原至常氧化的平稳过渡。灰岩地层δ¹³C值平均为-0.80‰,而白云岩地层δ¹³C值平均为-6.52‰,存在轻碳的明显富集,结合宏观叠层构造,判断白云石为生物成因。本研究中白云石沉积环境中的古气候、古氧化还原条件、古水温和古生产力特征与白云石发育情况存在明显耦合,为白云石生物成因提供了相关依据与指示意义...     

含白云石天然碳酸盐岩在中红外波段的辐射特性研究

利用红外发射光谱研究了含白云石天然碳酸盐岩及主要组成矿物的红外发射光谱特征,探究了影响其红外辐射性能的因素。X射线衍射(XRD)和微区拉曼光谱(Raman)结果显示白云石(70%)、方解石(25%)和石英(5%)是该天然碳酸盐的主要组成物相。基于黑体辐射定律以及在80℃时、400～2 000 cm-1各矿物的辐射能量谱,显示碳酸盐岩、白云石、方解石和石英的发射率依次减少(1. 010、1. 000、0. 997、0. 958),白云石是碳酸盐岩红外辐射性能的主要贡献者。在本文研究的温度和波长范围内,含白云石碳酸盐岩中主要组成矿物的热容是温度的函数,白云石高的热容有利于提高整体的热辐射性能;矿物颗粒直径对热辐射的传播有一定的影响,颗粒直径接近于辐射波长时热辐射出现衰减导致发射率降低;当化学键(C—O键、Si—O键)的振动出现在发射光谱窄的发射带范围内(1 350～1 500 cm-1和950～1 275 cm-1)则会导致相对较高的辐射能和发射率。     

石棉尾矿硫酸铵焙烧法提取氧化镁制备碱式碳酸镁的实验研究

基于石棉尾矿中富含氧化镁组分的特点,在矿物学特征研究基础上,采用硫酸铵焙烧法提取氧化镁,利用浸出液硫酸镁制备碱式碳酸镁。采用XRD、SEM、FT-IR和TG-DTA对不同温度条件下所获得的产物的物相、形貌、分子振动光谱和热效应变化等特征进行了分析和表征。结果表明:利用硫酸铵焙烧产物的浸取液,在低于65℃的水溶液中所制备的产物为针状水合碳酸镁;在高于85℃时制备的产物为片状碱式碳酸镁;在75℃温度时形成短柱状或颗粒状水合碳酸镁和片状碱式碳酸镁的混合物。对水合碳酸镁加热,在100℃脱去部分水合水和二氧化碳后转变为片状碱式碳酸镁。研究结果对石棉尾矿的资源化利用和环境保护具有一定的理论和实际意义。     

A comparative study of the Rare Earth Element (REE) distributions within the Lower Cretaceous dolomites and limestones of Central Tunisia

REE distribution, strontium content and oxygen isotopic composition have been studied in the Lower Cretaceous dolomites and their interbedded and/or parental limestones of Central Tunisia. Dolomites, as indicated by previous sedimentologic, geochemical and isotopic study, are different in origin. Environments of dolomite formation include: evaporitic sabkha, deep phreatic, karst and lacustrine. With the exception of the sabkha environment, dolomitizing fluids presumably have been essentially meteoric. The comparison between REE distributions in dolomites and limestones clearly suggests that the general shapes of the REE patterns are preserved during dolomitization. Nevertheless, the total REE amounts are somewhat lowered in dolomites comparatively to parental limestones. Moreover, within the dolomites, the total REE contents are positively correlated to the Sr and δ¹⁸O contents; thus indicating that the decrease in REE, Sr, and δ¹⁸O contents is related to a decrease in the salinity of dolomitizing fluids. In addition, dolomites associated with emergence surfaces (karst) are the most impoverished in REE. Furthermore, they are relatively enriched in light REE, indicating a more or less important fractionation with the REE distributions. This enrichment has been related to the influence of the inorganic complexes which favours the greatest solubility of the heavy REE in basic solution with respect to the lightest members of the REE group.     

Soil pH governs production rate of calcium carbonate secreted by the earthworm Lumbricus terrestris

Lumbricus terrestris earthworms exposed to 11 soils of contrasting properties produced, on average, 0.8 ± 0.1 mg_CaCO3 earthworm^?1 day^?1 in the form of granules up to 2 mm in diameter. Production rate increased with soil pH (r² = 0.68, p < 0.01). Earthworms could be a significant source of calcite in soils.     

Precipitation of calcium carbonate and calcium phosphate under diffusion controlled mixing

Multi-component mineral precipitation in porous, subsurface environments is challenging to simulate or engineer when in situ reactant mixing is controlled by diffusion. In contrast to well-mixed systems, the conditions that favor mineral precipitation in porous media are distributed along chemical gradients, which evolve spatially due to concurrent mineral precipitation and modification of solute transport in the media. The resulting physical and chemical characteristics of a mixing/precipitation zone are a consequence of coupling between transport and chemical processes, and the distinctive properties of individual chemical systems. We examined the spatial distribution of precipitates formed in “double diffusion” columns for two chemical systems, calcium carbonate and calcium phosphate. Polyacrylamide hydrogel was used as a low permeability, high porosity medium to maximize diffusive mixing and minimize pressure- and density-driven flow between reactant solutions. In the calcium phosphate system, multiple, visually dense and narrow bands of precipitates were observed that were reminiscent of previously reported Liesegang patterns. In the calcium carbonate system, wider precipitation zones characterized by more sparse distributions of precipitates and a more open channel structure were observed. In both cases, formation of precipitates inhibited, but did not necessarily eliminate, continued transport and mixing of the reactants. A reactive transport model with fully implicit coupling between diffusion, chemical speciation and precipitation kinetics, but where explicit details of nucleation processes were neglected, was able to qualitatively simulate properties of the precipitation zones. The results help to illustrate how changes in the physical properties of a precipitation zone depend on coupling between diffusion-controlled reactant mixing and chemistry-specific details of precipitation kinetics.     

Dissolution rates of earthworm-secreted calcium carbonate

The dissolution of CaCO₃ granules secreted by earthworms in soil leaching columns was governed by soil pH and exchange sites available for Ca. Results indicate that granules could last for significant periods of time in soils and that, therefore, granules could be an important source of soil calcite.     

Undications of current action in late Jurassic limestones,radiolarian limestones,saccocoma limestones and associated rocks from the subbetic of SE Spain

In the Vélez Blanco region (province of Almeia), filament limestones occur associated with pellet limestones, crinoidal limestones, radiolarian limestones, Saccocoma limestones and tintinnid limestones. These predominantly Late Jurassic rocks are underlain by Middle Jurassic oolitic limestones and overlain by Cretaceous pelagic limestones and marls.A distinction can be made between long and short filaments. The former are interpreted as undamaged valves, the latter as shell fragments of the pelagic pelecypod Bositra buchi. Bositra valves and fragments have been sorted by weak current (and/or wave) action.In the Saccocoma limestones, evidence for similar sorting of Saccocoma debris has been found.The radiolarian limestones represent a low-energy basin environment, but are not comparable with recent deep-sea radiolarian oozes.Nodular limestone intercalations and hiatuses represent a current- (and/or wave-) swept environment.The occurrence of filament-rich and Radiolaria-bearing, but benthos-poor, intervals within the oolitic limestone indicates that the deposition of such rocks can take place at moderate sea depths.     

Chalk deformation and large-scale migration of calcium carbonate

Sixty Upper Cretaceous chalk exposures were examined and sampled in Dorset, the Isle of Wight and Guildford, South England, in order to investigate the effects of tectonic deformation on the chalk fabric. Light and scanning-electron microscopes were used extensively, and chemical, mineralogical and isotopic analyses ware carried out. Two types of fabric modification were distinguished. The first type involves more than 90% volume loss by mechanical compaction at the early stages of deformation followed by dissolution and removal of calcium carbonate in the advanced stages of deformation. Chalks which have undergone this type of fabric modification are dense and consist of well rounded 0.5–3 μ calcite crystals with well developed pressure-solution contacts. These chalks contain a high proportion of calcispheres (many of which are plastically deformed) but very few well preserved planktonic foraminifera and coccoliths. They are relatively enriched in insoluble constituents and depleted in strontium. The second type of fabric modification involves introduction of calcium carbonate into the pore spaces. Chalks which have undergone this type of modification are dense and contain a high proportion of 3–5 μ polygonal interlocking calcite crystals. Fossils are virtually never deformed, and delicate foraminifera and coccoliths are well preserved. Insoluble constituents similar to those found in the unmodified chalks occur in low concentrations. Removal of calcium carbonate at crystal contacts has taken place in chalks which have been subjected to high effective tectonic stresses and at crystal peripheries in chalks which have been subjected to high pore fluid pressure. Dissolution at crystal peripheries is responsible for the extensive calcium carbonate losses, and it is termed herein ‘confining pressure solution’. Introduction of calcium carbonate occurs in rocks which were under low tectonic stresses. During deformation calcium carbonate migrates from chalks under high stresses towards those under tow stresses, while some goes into solution in sea water. Well developed joints and high pore fluid pressure might increase the rate of calcium carbonate removal by three orders of magnitude. Petrographic and isotopic data suggest-that all fabric modifications studied took place in meteoric water.     

Large fractionation of calcium isotopes during cave-analogue calcium carbonate growth

We have measured δ^44/42Ca of laboratory-precipitated calcite grown in an experimental setup that closely replicates stalagmite formation. Calcium solutions were dripped onto two different substrates in tightly-controlled conditions and calcite precipitated due to rapid CO₂ degassing. With seeded glass slides as the substrate, we observe a Ca isotope ratio in the calcite which is ∼0.5‰ per amu lower than that in the growth solution. This fractionation is generally almost twice that observed in previously published calcite growth experiments and indicates a large kinetic effect on Ca isotopes in the stalagmite growth environment. The precipitate forming near the spot where the drip lands shows slightly greater solution-to-precipitate fractionation than calcite further from the drip reflecting a decrease in this kinetic fractionation as precipitation continues. We interpret these results in the context of the model of Fantle and DePaolo (2007) which involves surface entrapment of light Ca isotopes to decrease calcite δ^44/42Ca, and depletion of Ca from the solution in the direct vicinity of the growing calcite to increase calcite δ^44/42Ca. In the stalagmite setting, the second of these effects is minimized so that calcite Ca isotope ratios are unusually light. This interpretation suggests that stalagmite Ca isotope ratios should decrease with the saturation state of the drip water (i.e. with the growth rate of calcite). Ca isotopes might therefore allow reconstruction of surface entrapment of trace metals and isotopes more generally and might, for instance, allow an assessment of the appropriate relationship between oxygen isotope fractionation and temperature for periods of past growth in stalagmites.     

碳酸钙矿物表面润湿性的控制机理

系统论述了碳酸钙矿物浮选中常用的捕收剂和抑制剂及其相关作用机理。这些药剂通过包括静电作用、氢键、半胶束吸附和化学吸附等多种机理,吸附在碳酸钙矿物表面,从而控制矿物表面的润湿性。捕收剂的功能在于增强矿物表面的疏水性,抑制剂的功能在于增强矿物表面的亲水性。选择合适的捕收剂和抑制剂复配方案对高效浮选分离至关重要。     

Variation in production,input and preservation of metastable calcium carbonate off Somalia during the last 90,000 years

To improve our understanding of the Late Pleistocene and Holocene carbonate system of the western Arabian Sea a high-resolution sedimentary record off Somalia has been analysed. The 15.26-m-long piston core 905 comprises a complete record of the last 90,000 years. We have measured concentrations of carbonate minerals, i.e., aragonite, calcite, Mg-calcite, and element ratios (Sr/Ca) together with pteropod counts and an estimation of the preservation state of pteropod shells to trace temporal changes in carbonate production and preservation.The Sr/Ca ratio shows strong similarities to the aragonite percentage and the δ¹⁸O record of the planktic foraminifer Neogloboquadrina dutertrei. High Sr/Ca ratios together with fragments of corals found in the coarse fraction indicate that most of the aragonite is of shallow water origin (high-Sr aragonite) and pteropods contribute much less than expected. High resuspensional input of shallow-marine aragonite occurs during sea-level highstands (interglacials) and low input during lowstands (glacials).The Mg-calcite concentration record resembles the whole pteropod abundance and pteropod shell preservation records confirming the use of Mg-calcite in combination with pteropod preservation proxies to reconstruct past fluctuations in carbonate dissolution. Preservation of aragonite and Mg-calcite increases during stadials, H-equivalents, YD and late Marine Isotope Stage (MIS) 3. During late MIS 5/early MIS 4 and in the Late Holocene absence of few pteropods as well as low Mg-calcite weight percentages point to strong dissolution of aragonite and Mg-calcite.