The Geochemistry of Carbonate Rocks in Igwe Igarra, Southwestern Nigeria

Nigeria has an abundance of valuable solid minerals and rocks which can generate revenue for the government if they are fully exploited. Carbonate rock is one of such rocks that occur prominently in Igwe Igarra area of Edo State. Five (5) carbonate rock samples (Four marble and One Calcsilicate) were subjected to geochemical analyses. A petrographic study reveals that marble and calcsilicate contain calcite, quartz, microcline, plagioclase, biotite and opaque minerals. Geochemical data shows that carbonate rocks have variable geochemical characteristics: Igwe marble is highly Calcitic (96% - 98%) and very low in dolomite Mg(CO3). Calcsilicate rock is low in CaO (27.5%) and higher in marble. The Igwe marble is pure and contains fewer impurities compared to calcsilicate rock which makes it unideal for usage. Based on these characteristics the marble from Igwe is suitable as raw materials for the productions of glass, papers, beet sugar, aggregates, lubricants and fillers.

The constructing of pore structure factor in carbonate rocks and the inversion of reservoir parameters

With a more complex pore structure system compared with clastic rocks, carbonate rocks have not yet been well described by existing conventional rock physical models concerning the pore structure vagary as well as the influence on elastic rock properties. We start with a discussion and an analysis about carbonate rock pore structure utilizing rock slices. Then, given appropriate assumptions, we introduce a new approach to modeling carbonate rocks and construct a pore structure algorithm to identify pore structure mutation with a basis on the Gassmann equation and the Eshelby-Walsh ellipsoid inclusion crack theory. Finally, we compute a single well＇s porosity using this new approach with full wave log data and make a comparison with the predicted result of traditional method and simultaneously invert for reservoir parameters. The study results reveal that the rock pore structure can significantly influence the rocks＇ elastic properties and the predicted porosity error of the new modeling approach is merely 0.74%. Therefore, the approach we introduce can effectively decrease the predicted error of reservoir parameters.

Weathering-pedogenesis of Carbonate Rocks and Its Environmental Effects in Subtropical Region

We investigated the weathering-pedogenesis of carbonate rocks and its environmental effects in subtropical regions of China. The investigation demonstrated that the weathering- pedogenesis of carbonate rocks is the process of a joint action of corrosion and illuviation and metasomatism in subtropical region. It is characterized by multi-stage, multi-path and multi-style. With the persisting development of weathering-pedogenesis of carbonate rocks, metasomatic pedogenesis progressively became the main process of the weathering-pedogenesis and the dominant style of formation of minerals. And it proceeds through the whole process of evolution of the weathering-pedogenesis of carbonate rocks. The stage evolution of weathering-pedogenesis of carbonate rocks and the fractionation evolution of newly produced minerals are characterized by obvious vertically zoning structures and the rules of gradation of elements geochemical characteristics in the carbonate rocks weathering profiles. The geochemical process of weathering-pedogenesis of carbonate rocks can be divided into three geochemical evolution stages, i.e., the Ca, Mg-depletion and Si, Al-enrichment stage; the Fe, Mn enrichment stage and the Si-depletion and Al-enrichment stage in the subtropical regions. Consistent with the three geochemical evolution stages, the sequence of formation and evolution of minerals can be divided into the clay mineral stage; the Fe, Mn oxide and the gibbsite stage. The influence of weathering-pedogenesis of carbonate rocks on the chemical forms of heavy elements is mainly affected via newly produced components and minerals in the process of weathering-pedogenesis, e.g., iron oxide minerals and organic matters. The important mechanism for the mobilization, transport and pollution of F and As is affected the selective adsorption and desorption of F and As on the surface of iron oxide minerals in the subtropical karst zones, i.e., the selective adsorption and desorption on mineral surfaces of newly produced minerals in the process of weathering-pedogenesis control the geochemical behavior of elements on the Earth＇s surface and environmental quality in subtropical regions.

A New Example of Retrograde Solubility Model for Carbonate Rocks

Objective The dissolution and precipitation of carbonate during burial diagenetic process controls the reservoir property in deep buried strata. The geological process related with it has become a research focus during recent years. The most important dissolution fluids to carbonates are probably H2S and CO2 as byproducts of sulfate reduction in deep-buried setting with sulfate minerals, but carbonates are more soluble in relatively low temperature, which is the so-called retrograde solubility. Several geological processes can result in the decrease of temperature, including the upward migration of thermal fluids and tectonic uplift.

Effect of overburden pressure on determination of reservoir rock types using RQI/FZI,FZI^* and Winland methods in carbonate rocks

Rock typing is an important tool in evaluation and performance prediction of reservoirs.Different techniques such as flow zone indicator(FZI),FZI~*and Winland methods are used to categorize reservoir rocks into distinct rock types.Generally,these methods are applied to petrophysical data that are measured at a pressure other than reservoir pressure.Since the pressure changes the pore structure of rock,the effect of overburden pressure on rock typing should be considered.In this study,porosity and permeability of 113 core samples were measured at five different pressures.To investigate the effect of pressure on determination of rock types,FZI,FZI~*and Winland methods were applied.Results indicated that although most of the samples remain in the same rock type when pressure changes,some of them show different trends.These are related to the mineralogy and changes in pore system of the samples due to pressure change.Additionally,the number of rock types increases with increasing pressure.Furthermore,the effect of overburden pressure on determination of rock types is more clearly observed in the Winland and FZI~*methods.Also,results revealed that a more precise reservoir dynamic simulation can be obtained by considering the reservoir rock typing process at reservoir conditions.

Carbon Isotope Excursions and Paleo-Oceanography of the Ordovician–Silurian Boundary Carbonate Rocks from the Xainza Area, Tibet

Objective The Ordovician–Silurian transitional period is a special time when the global paleo-environment changed greatly.It witnessed the first mass extinction as of Phanerozoic period and glaciations that occurred frequently at a large scale in a very short time,which has thus attracted much attention among geoscientists at home and abroad.

The First Report of Thermochemical Sulfate Reduction Reaction in the Upper Paleozoic Carbonate Rocks of Southeastern Ordos Basin

Thermochemical sulfate reduction （TSR） is the reaction between anhydrite and petroleum fluids at elevated temperatures to produce H2S and CO2. TSR has been studied in many sedimentary basins such as China＇s Sichuan and Tarim basins because it has a profound impact on the commercial viability of petroleum resources, with HzS typically being undesirable.

Estimating Hydrogeological Parameters in Covered Carbonate Rocks Using a Discrete-State Compartment Model and Environmental Tritium

Nowadays, isotope environmental technique tends to be used as a reconnaissance tool , both qualitative and quantitative, to calculate the aquifer parameters particularly in carbonate rock aquifers. But, the heterogeneous flow is still problematic when Lumped parameter Models are usually used to calculate the residence times and hydraulic parameters. However, Discrete State Compartment Model can provide a powerful model to heterogeneous medium. One such study was carried on in Dazha valley, where the environmental tritium was used as a tracer for determining hydrogeological parameters based on a discrete state compartment model

A study of some Egyptian carbonate rocks for the building construction industry

A number of geotechnical analyses were carried out on selected carbonate rock samples from eight sites located in Egypt. This analysis was to assess the suitability of these rocks for building construction aggregate. The analyses included properties of uniaxial compressive strength, tensile strength, porosity, water absorption, and dynamic fragmentation. The success of building construction depends to a large extent on the availability of raw materials at affordable prices. Raw materials commonly used in the building industry include sands, gravels, clays and clay-derived products. Despite the widespread occurrence of carbonate rocks throughout Egypt, the low premium placed on their direct application in the building sector may be explained in two ways: firstly, the lack of awareness of the potential uses of carbonate rocks in the building construction industry(beyond the production of asbestos, ceiling boards, roof sheets and Portland cement); and secondly, the aesthetic application of carbonate rocks in the building construction depends mainly on their physical attributes, a knowledge of which is generally restricted to within the confines of research laboratories and industries. Thus this paper addresses the physical and mechanical characteristics of some Egyptian carbonate rocks, evaluating them for their suitability as building construction aggregates.

Fission Track Dating of Authigenic Quartz in Red Weathering Crusts of Carbonate Rocks in Guizhou Province

The Cenozoic evolution history of Guizhou Province, which is located on the southeastern flank of the Qinghai-Tibet Plateau, is unclear because of the lack of sedimentation records. The red weathering crusts widespread on the Yunnan-Guizhou Plateau may bear critical information about their evolution history. This work firstly determined the ages of four red weathering crusts in eastern, central and northern Guizhou. The material used in fission track dating is well-crystallized quartz occurring in many in-situ weathering crusts of carbonate rocks. The results showed that the fission track ages of quartz vary over a wide range from 1 to 25 Ma in the four profiles, significantly younger than the ages of the Triassic and Cambrian parent rocks. In combination with the evolution history of the regional geology during the period from 25 to 1 Ma, the ages of quartz can exclude the possibility that the origin of quartz has nothing to do with primary clastic minerals in parent rocks, authigenesis during diagenesis and hydrothermal precipitation or roplacement by volcanic activities. It is deduced that the well-crystallized quartz was precipitated from Si-rich weathering fluids during the weathering process of carbonate rocks. The recorded ages of quartz from the four profiles are consistent with the episodes of the planation surfaces on the Qinghai-Tibet Plateau, the forming stages of red soil in the tropics of South China, the tectonically stable periods in Guizhou, and the ages of weathering in other parts of the world during the Cenozoic era. That is to say, the ages of authigenic quartz dated by the fission track method are well feasible and credible.

Heterogeneity of Parent Rocks and Its Constraints on Geochemical Criteria in Weathering Crusts of Carbonate Rocks

Owing to the low contents of their acid-insoluble components, carbonate rocks tend to decrease sharply in volume in association with the formation of weathering crust. The formation of a 1 m-thick weathering crust would usually consume more than ten meters to several tens of meters of thickness of parent rocks. The knowledge of how to identify the homogeneity of parent rocks is essential to understand the formation mechanism of weathering crust in karst regions, especially that of thick-layered red weathering crust. In this work the grain-size analyses have demonstrated that the three profiles studied are the residual weathering crust of carbonate rocks and further showed that there objectively exists the heterogeneity of parent rocks in the three studied weathering crusts. The heterogeneity of parent rocks can also be reflected m geochemical parameters of major elements, just as the characteristics of frequency plot of grain-size distribution. Conservative trace element ratios Zr/Hf and Nb/Ta are proven to be unsuitable for tracing the heterogeneity of parent rocks of weathering crust, but its geochemical mechanism is unclear. The authors strongly suggest in this paper that the identification of the homogeneity of parent rocks of weathering crust in karst regions is of prime necessity.

Mixed carbonate rocks lithofacies features and reservoirs controlling mechanisms in a saline lacustrine basin in Yingxi area,Qaidam Basin,NW China

Taking the mixed pre-salt carbonate rocks in the upper member of Eocene Xiaganchaigou Formation(E_(3)^(2))of Yingxi area in the Qaidam Basin as an example,the lithofacies and controlling mechanisms of reservoir formation are analyzed based on a large dataset of cores,thin sections and geochemical analysis.The reservoirs in E_(3)^(2)pre-salt layers have five types of lithofacies,of them,mixed granular calcareous dolostone,massive calcareous dolostone,plaque calcareous dolostone,and laminated dolomtic limestone are of sedimentary origin,and breccia calcareous dolostone is of tectonic origin.The four types of sedimentary lithofacies are divided into two types of saline sedimentary sequence lithofacies combinations,low-energy type in the sag area and low to high-energy type in the slope and paleo-uplift zone in the depression.Affected by high-frequency supply of continental clastic material,the two types of salty sedimentary sequences are mostly incomplete subtypes of lithofacies.Lithofacies have strong impacts on pre-salt reservoirs in E_(3)^(2):(1)Lithofacies type and sedimentary sequence controlled the formation and distribution of dolomite intercrystalline pores and dissolved pores during the pene-sedimentary period.(2)The structure of laminated dolomitic limestone controlled the formation of large-scale laminated fractures and high permeability channels during the diagenetic period.(3)Granular,massive,plaque calcareous dolostones have low mud content and strong brittleness,in the late tectonic reactivation period,the distribution of the three types of lithofacies,together with their distance from the top large slip faults and secondary faults,controlled the formation and distribution of high-efficiency fracture-cave brecciaed calcareous dolostone reservoirs.The above research led to the composite lithofacies-tectonic formation model of pre-salt reservoir in E_(3)^(2)of Yingxi area.The tempo-spatial distribution of tectonic breccia calcareous dolostone reservoirs,laminated dolomitic limestone shale oil reservoirs and granular,massive calcareous dolostone dissolved-intercrystalline pore tight reservoirs in various structural belts of the studied area have been figured out.These findings gave new insights into tight-shale oil accumulation theory in mixed carbonate successions from saline lacustrine basins,aiding in high efficient exploration and development of petroleum in the studied area.

An Experimental Study of Mixture Corrosion Effects of Carbonate Rocks in the Transitional Zone of Littoral Karst Areas

The mechanism for development of littoral karst differs from that of inland karst, and the mixture corrosion effects are one of the most important factors that control the development of littoral karst. Through seven groups of static experiments carried out in a closed CO2-H2O system, basic conclusions can be drawn as follows: (1) the basic law of corrosion process in a transitional zone of seawater-freshwater in littoral karst areas is identical with that in the fresh water, i.e., the lithologic characteristics and rock structure are the main factors which control the development of littoral karst; (2) the mixture corrosion rate of the carbonate rock in the above transitional zone is faster than that in fresh water or seawater; (3) the mechanism for development of carbonate rocks differs at various pressures of CO2 in a transitional zone in littoral karst areas.

Combination and distribution of reservoir space in complex carbonate rocks

This paper discusses the reservoir space in carbonate rocks in terms of types,combination features,distribution regularity,and controlling factors,based on core observations and tests of the North Truva Oilfield,Caspian Basin.According to the reservoir space combinations,carbonate reservoirs can be divided into four types,i.e.,pore,fracture-pore,pore-cavity-fracture,and pore-cavity.Formation and distribution of these reservoirs is strongly controlled by deposition,diagenesis,and tectonism.In evaporated platform and restricted platform facies,the reservoirs are predominately affected by meteoric fresh water leaching in the supergene-para-syngenetic period and by uplifting and erosion in the late stage,making both platform facies contain all the above-mentioned four types of reservoirs,with various pores,such as dissolved cavities and dissolved fractures,or structural fractures occasionally in favorable structural locations.In open platform facies,the reservoirs deposited continuously in deeper water,in an environment of alternative high-energy shoals（where pore-fracture-type reservoirs are dominant） and low-energy shoals（where pore reservoirs are dominant）.

Autochthonous Dolomitization and Dissolution in the Microbial Carbonate Rocks of the Fengjiawan Formation in the Ordos Basin

Many euhedral dolomite crystals and related pores are found in the microbial siliceous stromatolite dolomite and siliceous oolitic dolomite in the Fengjiawan Formation of the Mesoproterozoic Jixian System in the southern Ordos Basin.With the application of the microscope,scanning electron microscope,cathodoluminescence and in-situ trace element imaging,it can be seen that different from the phase I dolomite that was damaged by silicification,the intact euhedral phase II dolomite occurred through dolomitization after silicification,concentrated mainly in the organic-rich dark laminae of the stromatolite and the dark spheres and cores of the ooids.A considerable number of phase II dolomite crystals were dissolved,giving rise to mold pores and vugs which constituted the matrix pores and also the major pore space of the Fengjiawan Formation.The formation and dissolution of the dolomite were controlled by the microenvironment favorable,respectively,for carbonate precipitation and dissolution under the influence of microbial biological activities and related biochemical reactions.The driving force and material supply of dolomitization and dissolution were confined to the fabrics enriched with microorganisms,which are highly autochthonous.This mechanism may be a key factor for the development of Precambrian dolomite and related reservoirs,in the context of the domination of microbial rocks.

Formation of fractures in carbonate rocks by pad acid fracturing with different states of carbon dioxide

Carbonate outcrops were taken from Ma 51 sub-member in the Lower Paleozoic in the Yan’an gas field to conduct true tri-axial hydraulic fracturing experiments with water, liquid CO_(2) and supercritical CO_(2). CT scan was applied to analyze initiation and propagation laws of hydraulic fractures in carbonate rocks. The experiments show that supercritical CO_(2) has low viscosity, strong diffusivity and large filtration during fracturing, which is more liable to increase pore pressure of rocks around wellbore and decrease breakdown pressure of carbonate rocks. However, it would cost much more volume of supercritical CO_(2) than water to fracture rocks since the former increases the wellbore pressure more slowly during fracturing. For carbonate rocks with few natural fractures, tensional fractures are generated by fracturing with water and liquid CO_(2), and these fractures propagate along the maximum horizontal principal stress direction;while fracturing with supercritical CO_(2) can form shear fractures, whose morphology is rarely influenced by horizontal stress difference. Besides, the angle between propagation direction of these shear fractures near the wellbore and the maximum horizontal principal stress is 45°, and the fractures would gradually turn to propagate along the maximum horizontal principal stress when they extend to a certain distance from the wellbore, leading to an increase of fracture tortuosity compared with the former. For carbonate rocks with well-developed natural fractures, fracturing with fresh water is conducive to connect natural fractures with low approaching angle and form stepped fractures with simple morphology. The key to forming complex fractures after fracturing carbonate rocks is to connect the natural fractures with high approaching angle. It is easier for liquid CO_(2) with low viscosity to realize such connection. Multi-directional fractures with relatively complex morphology would be formed after fracturing with liquid CO_(2).

Geochemical characteristics and sedimentary environment significance of carbonate rocks in Nanfen Formation of Qingbaikou System in Tonghua,Jilin Province

In order to reveal the sedimentary environment of carbonate rocks in Nanfen Formation of Qingbaikou System in Tonghua,Jilin Province,the mineral composition and petrochemistry of carbonate rocks in Nanfen Formation were analyzed.The mineral compositions of five carbonate rock samples in Nanfen Formation mainly consist of calcite,with minor clay minerals and quartz,and the rock type is siliceous marlite.The Mn/Sr va-lues range from 1.52 to 4.08,with an average of 2.64,indicating that the carbonate rocks experienced weak diagenesis;the Sr/Ba values range from 1.26 to 2.51,with an average of 1.93,indicating marine environment;the ratio of Mg/Al ranges from 35.33 to 86.34,with an average of 62.95,indicating the seawater environment,which is consistent with the result from Sr/Ba;the MgO/CaO values range from 0.01 to 0.04,with an average of 0.02,indicating humid environment;the values of V/(V+Ni)range from 0.63 to 0.73,with an average of 0.70,indicating anoxic environment.In summary,geochemical analyses show that the Nanfen Formation carbonate rocks are marine deposits,in a warm,humid,anoxic environment with poor flow of seawater,and subsequently underwent weak diagenetic alteration.

Method for evaluation of geological strength index of carbonate cliff rocks:Coupled hyperspectral-digital borehole image technique

The deterioration of unstable rock mass raised interest in evaluating rock mass quality.However,the traditional evaluation method for the geological strength index(GSI)primarily emphasizes the rock structure and characteristics of discontinuities.It ignores the influence of mineral composition and shows a deficiency in assessing the integrity coefficient.In this context,hyperspectral imaging and digital panoramic borehole camera technologies are applied to analyze the mineral content and integrity of rock mass.Based on the carbonate mineral content and fissure area ratio,the strength reduction factor and integrity coefficient are calculated to improve the GSI evaluation method.According to the results of mineral classification and fissure identification,the strength reduction factor and integrity coefficient increase with the depth of rock mass.The rock mass GSI calculated by the improved method is mainly concentrated between 40 and 60,which is close to the calculation results of the traditional method.The GSI error rates obtained by the two methods are mostly less than 10%,indicating the rationality of the hyperspectral-digital borehole image coupled evaluation method.Moreover,the sensitivity of the fissure area ratio(Sr)to GSI is greater than that of the strength reduction factor(a),which means the proposed GSI is suitable for rocks with significant fissure development.The improved method reduces the influence of subjective factors and provides a reliable index for the deterioration evaluation of rock mass.

Impact of effective stress on permeability for carbonate fractured-vuggy rocks

To gain insight into the flow mechanisms and stress sensitivity for fractured-vuggy reservoirs,several core models with different structural characteristics were designed and fabricated to investigate the impact of effective stress on permeability for carbonate fractured-vuggy rocks(CFVR).It shows that the permeability performance curves under different pore and confining pressures(i.e.altered stress conditions)for the fractured core models and the vuggy core models have similar change patterns.The ranges of permeability variation are significantly wider at high pore pressures,indicating that permeability reduction is the most significant during the early stage of development for fractured-vuggy reservoirs.Since each obtained effective stress coefficient for permeability(ESCP)varies with the changes in confining pressure and pore pressure,the effective stresses for permeability of four representative CFVR show obvious nonlinear characteristics,and the variation ranges of ESCP are all between 0 and 1.Meanwhile,a comprehensive ESCP mathematical model considering triple media,including matrix pores,fractures,and dissolved vugs,was proposed.It is proved theoretically that the ESCP of CFVR generally varies between 0 and 1.Additionally,the regression results showed that the power model ranked highest among the four empirical models mainly applied in stress sensitivity characterization,followed by the logarithmic model,exponential model,and binomial model.The concept of“permeability decline rate”was introduced to better evaluate the stress sensitivity performance for CFVR,in which the one-fracture rock is the strongest,followed by the fracture-vug rock and two-horizontalfracture rock;the through-hole rock is the weakest.In general,this study provides a theoretical basis to guide the design of development and adjustment programs for carbonate fractured-vuggy reservoirs.

Effects of Different Concentrations of Sulfate Ions on Carbonate Crude Oil Desorption:Experimental Analysis and Molecular Simulation

Low salinity water containing sulfate ions can significantly alter the surface wettability of carbonate rocks.Nevertheless,the impact of sulfate concentration on the desorption of oil film on the surface of carbonate rock is still unknown.This study examines the variations in the wettability of the surface of carbonate rocks in solutions containing varying amounts of sodium sulfate and pure water.The problem is addressed in the framework of molecular dynamics simulation(Material Studio software)and experiments.The experiment’s findings demonstrate that sodium sulfate can increase the rate at which oil moisture is turned into water moisture.The final contact angle is smaller than that of pure water.The results of the simulations show that many water molecules travel down the water channel under the influence of several powerful forces,including the electrostatic force,the van der Waals force and hydrogen bond,crowding out the oil molecules on the calcite’s surface and causing the oil film to separate.The relative concentration curve of water and oil molecules indicates that the separation rate of the oil film on the surface of calcite increases with the number of sulfate ions.