碳酸盐矿物的包裹有机质及其生油意义

Fluorescent slice observations have revealed a considerable amount of organic matter enclosed in carbonate minerals, most of it giving off yellow-brown fluorescence and being zonally distributed in calcite and dolomite. The amount of enclosed organic matter released from the enclosure when treated with HCl is two times higher than that of extractable organic mattes in the same rock sample. In comparison to the extractable organic matter, the enclosed organic matter is possessed of some compositional characters of its own. In terms of the distribution of biological markess, it is suggested that the enclosed organic matter may be low in maturity relative to the extractable organic matter in the same source rock.Results of the simulating experiments under high temperatures and pressures show that this kind of organic matter enclosed in carbonate minerals can be converted into oil-generating substances. Therefore, detailed studies of the enclosed organic matter are of much help to the evaluation of oil-generating potentiality of carbonate source rocks.     

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 weath     

碳酸岩分散有机质的基本存在形式、演化特征与碳酸岩地层油气评价

Two major characters are recognized with respect to the evolution of organic matter during diagenesis of carbonate rocks; (1) expellation of organic matter from carbonate minerals through crystallization, which could reduce the amount of organic matter significantly in the early stage of diagenesis; (2) protection of organic matter by the minerals, especially in the late stage of diagenesis. According to their nature and relations to the protection during diagenesis, three majer forms of disseminated organic matter in carbonate rocks can be distinguished: adsorbed, ctystallization-trapped organic matter and organic inclusions. Owing to the protection by minerals the maturation process of disseminated organic matter proceeds very slowly, and the matority of crystallization-trapped organic matter may play an important role in carbonate source rocks. Most of the organic inclusions are migrated organic matter, such as hydrocarb ons; so organic inclusions may be a good indicator which can be used to study the primary,secondary migration and the concentration of oil and gas in carbonate source rocks and carbonate reservoir strata,     

http://www.sciencedirect.com/science/article/pii/S1674987115000250

Oil and gas exploration in carbonate rocks was extremely successful in recent years in the Ordovician in Tarim Basin.NW China.Here,we investigate the carbonate reservoirs in the Bachu area of the Tarim Basin through petrological and geochemical studies combined with oil and gas exploration data.Geochemical analysis included the major,trace,and rare earth elements;fluid inclusion thermometry;clay mineral characterization;and carbon and oxygen isotopes of the carbonate rocks.Homogenization temperatures of the fluid inclusions of Well He-3 in the Bachu area indicate three groups,60-80 ℃,90-130 ℃,and 140-170 ℃,and suggest that the carbonate rocks experienced modification due to heating events.The porosity in the reservoir is defined by fractures and secondary pores,and there is a notable increase in the porosity of the carbonate reservoirs in proximity to magmatic intrusion,particularly approximately 8-10 m from the intrusive rocks.The development of secondary pores was controlled by lithofacies and corrosion by various fluids.We identify supercritical fluids with high density(138.12-143.97 mg/cm~3) in the Bachu area.The negative correlations of δ~(13)C(-2.76‰ to-0.97‰) and δ~(18)O(-7.91‰ to-5.07‰) suggest that the carbonate rocks in the study area were modified by high-salinity hydrothermal fluid.The formation of clay minerals,such as illite and montmorillonite,caused a decrease in porosity.Our study demonstrates the effect of magmatic intrusions in modifying the reservoir characteristics of carbonate rocks and has important implications for oil and gas exploration.     

A Novel Type of Oil—generating Organic Matter —Crystal—enclosed Organic Matter

The comparative study of organic matter in carbonate rocks and argillaceous rocks from the same horizon indicates that the organic thermal maturities of carbonate rocks are much lower than those of argillaceous rocks .Ana extensive analysis of extracted and inclused organic matter from the same sample shows that inclused organic matter is different from extracted organic matter,and the thermal maturity of the former is usually lower than that of the latter in terms of biomarker structural parameters.It seems that carbonate mineras could preserve organic matter and retard organic maturation.The inclused organic matter,abundant in most carbonate rocks,will be released from minerals and transformed into oil and gas during the high-thermal maturity stage.     

热分析法在确定碳酸盐矿物类质同象方面的应用

Being rather common in carbonate minerals, isomorphism has practical importance in the identification of these minerals. The percentage of CO2, which can be measured by using thermogravimaetry, is a function of the components involved in isomorphism. Therefore, thermal analysis can be used to determine the isomorphism contribution to the compositional characteristics of earbonate minerals.     

Metallogenic Mechanism of the Tianbaoshan Pb—Zn Deposit,Sichuan

The Tianbaoshan Pb-Zn deposit in Sichuan Province,exhibiting open-space-filling and /or replacement textures,occurs as being of vine style in the Sinian(Late Proterozoic) carbonate rocks,and is simple in ore composition.A systematic study of lead isotope and rareearth elements reveals that the ore-forming materials were derived from multiple sources.The ultimate source of the sulfur in all stages in seawater sulfate but the reducing mechanisms are different,The carbon was derved from marine carbonate and organic matter,The ore-forming fluid,meteoric in origin,belongs to a Ca^2 -Mg^2 -Cl^--Hco3^- type of weak acidic to alkalic solutions with a salinity of about 5wt% NaCl.The ore was formed at the depth of about 1 km from 150 to 250℃ during the main stage of ore deposition.The heated meteoric water,after extracting ore materials from wall rocks,evolved into ore-forming solution with a low salinity, in which metals were trasported as chloride complexes such as PbCl,ZnCl and ZnCl.The metal-bearing solution moved upward along deep faults to low-pressure zones,where the metal ions reacted with reduced sulfur and were precipitated as sulfied minerals.The textures of the minerals were controlled by the rate at which the reduced sulfur was supplied.     

Separation of Clay Minerals from Host Sediments Using Cation Exchange Resins

Classic physical and chemical treatments applied to separating clay minerals from the host sediments are often difficult or aggressive for clay minerals. A technique using cation exchange resins (amberlite IRC-50H and amberlite IR-120) is used to separate clay minerals from the host sediments. The technique is based on the exchange of cations in the minerals that may be associated clay minerals in sediments, such as Ca and Mg from dolomite; Ca from calcite, gypsum and francolite with cations carried by resin radicals. The associated minerals such as gypsum, calcite, dolomite and francolite are removed in descending order. Separation of clay minerals using cation exchange resins is less aggressive than that by other classic treatments. The efficiency of amberlite IRC-50H in the removal of associated minerals is greater than that of amberlite IR-120.     

REE Geochemical Characteristics of Apatite,Sphene and Zircon from Alkaline Rocks

The accessory minerals apatite and sphene are the main carriers of REE in alkaline rocks.Their chondrite-normalized REE patterns decline sharply to the right as those of the host rocks,In the patterns an obvious negative Eu anomaly and a positive Ce anomaly can be seen in apatite and sphene,respectively.Zircon from alkaline rocks is different in REE pattern,I,e,. a nearly symmetric“V“-shaped pattern with a maximum negative Eu anomaly.Compared with the equivalents from granites,apatite,sphene and zircon from alkaline rocks are all characterized by higher (La/Yb)N ratio and less Eu depletion,As to the relative contents of REE in minerals,apatite,sphene and zircon are enriched in LREE,MREE and HREE respectively,depending on their crystallochemical properties.     

Reform of Carbonate Rock Subsurface by Crustose Lichens and Its Environmental Significance

Crustose lichens are distributed extensively in karst areas in Southern China. They can be found on the surface of carbonate rocks. Through biophysical and biochemical processes, crustose lichens reform the subsurface of carbonate rocks and in the meanwhile change their physical and chemical properties: (1) the mechanical strength decreases by 17.04° on average (up to 33.2° ); (2) the chemical solution surface area increases from 28.26% to 75.36% (lichen microholes considered only); and (3) the water-holding capacity is greatly improved. Comparative field experiments between biokarst samples underneath crustose lichens and fresh rock samples with the same composition and texture show that the corrosional rate of carbonate rocks of the former is 1.264-1.643 times higher than that of the latter. Crustose lichens are considered as an activator of the surface corrosion of carbonate rocks.     

地质体中氨基酸的研究

A clearer idea about the distribution of total amino acid content has been obtained through its quantitative determination in various geological bodies. Because amino acid content is strongly correlated with organic carbon content in the same sedimentary rock, therefore, an attempt has been made to use their ratio to distinguish the primary types of biological debris in sediment. In addition, the quantitative determination of individual amino acids has been also carried out on several specimens from ancient sedimentary rocks, and the results show that their amino acid pattern is almost similar to that of the recent sedimentary muds.     

Dissipative Structures of Rock—and Ore—forming Systems in Faults

The dissipative structure is an ordered structure.When a ssyterm is far from reaching equilibrium in the condition of non-equilibrium and exchanges some energy and material with the surroundings,this structure will be formed and preserved.Starting with the analysis of practical data,we attempt to use this theory to discuss the tectono-geochemical problems of some rock and ore-forming systems in faults.1.Ordered structure:Under the geological condition,due to the opening of a system in which energy and material are involved in geochemical action,the entropy tends to reduce gradually and substances evolve from non-ordered to ordered in structure.In the processes of formation of rocks and ores in faults,various layer-bands will be formed in rocks.2.Functional action:The physico-chemical activities which include pressure-creeping and thermal-diffusion as well as liquid diffusion have been shown.3.Fluctuating cycle:In the process of metamorphism,various changes in pressure,temperature and liquid are of fluctuation and periodicity.These may play an important role in the formation of rocks and minerals and the occurrence of ordered structures in fault zones.A few examples of mineral deposits in the middle and lower Yangtze River Valley are presented here,and the dissipative activities of rock-forming minerals and mineral-forming elements have been preliminarily established.     

Interaction of copper with fatty acids in Soxhlet extraction and its influence

Treatment with metallic copper for the removal of elemental sulfur from bitumen extracted from sedimentary rocks or petroleum is the most widely used method. Little attention has been paid, however, to its disadvantages. It was observed that copper can interact with some polar organic substances during conventional sulfur removal, which can strongly influence the quantitative and qualitative determination of bitumen, as has been confirmed by interaction of long-chain fatty acids with copper. The copper soap generated was analyzed by element analysis, inductively coupled plasma optical emission spectrometry （ICP-OES）, thermal analysis （TG-DSC） and Fourier Transform Infrared spectroscopy （FFIR）. Mechanism of the interaction was investigated and elucidated. Our experimental results would necessitate improvement of the present method for sulfur removal and/or a search for a new one.     

REE Geochemical Study of the Permian—Triassic Marine Sedimentary Environment in Guizhou Province

This paper deals with the REE geochemical characteristics of Permian-Triassic marine carbonate rocks in Guizhou Province.It is found that there are two broad categories of strati-graphic units in the region studied in accordance with their ΣREE contents and REE distribu-tion patterns: one is characterized by LREE enrichment and slight Ce depletion,with the REE distribution patterns similar to those of North American shales,and the other featrures relative HREE enrichment and relatively remarkable Ce depletion,with the REE distribution patterns close to those of pelagic sediments.In terms of their different ΣREE contents,five types of stratigraphic units can be distinguished.Incorporation of detrital minerals,REE complexing ca-pability,oxidation-reduction conditions of the media are the main factors affecting the REE com-position and REE distribution patterns of marine carbonate rocks in the region studied.In the light of REE geochemical characteristics of carbonate rocks,coupled with sedimentary facies analysis,this paper discusses the characteristics of the Permian-Triassic marine sedimentary environment in Guizhou Province and its evolutional rules.     

Thermogravimetry-differential thermal analysis coupled with chromatography as a thermal simulation experimental method and its application to gaseous hydrocarbons from different source rocks

In this paper a thermogravimetry-differential thermal analysis method coupled with chromatography （TG-DTA-GC） has been adopted to simulate the generation of gaseous hydrocarbons from different hydrocarbon source rocks such as coals, mudstones, and carbonate rocks with different maturities. The temperature programming for thermal simulation experiment is 20℃/min from ambient temperature to 700℃. As viewed from the quantities and composition of generated gaseous hydrocarbons at different temperatures, it is shown that low-mature coal has experienced the strongest exothermic reaction and the highest loss of weight in which the first exothermic peak is relatively low. Low-mature coal samples have stronger capability of generating gaseous hydrocarbons than high-mature samples. The amounts and composition of gaseous hydrocarbons generated are closely related not only to the abundance of organic carbon in source rocks, but also to the type of kerogen in the source rocks, and their thermal maturity. In the present highly mature and over-mature rock samples organic carbon, probably, has already been exhausted, so the production of gaseous hydrocarbons in large amounts is impossible. The contents of heavy components in gaseous hydrocarbons from the source rocks containing type- Ⅰ and - Ⅱ kerogens are generally high ; those of light components such as methane and ethane in gaseous hydrocarbons from the source rocks with Ⅲ-type kerogens are high as well. In the course of thermal simulation of carbonate rock samples, large amounts of gaseous hydrocarbons were produced in a high temperature range.     

Metamorphic Rock-hosted Disseminated Gold Deposits—A Case Study of the Xiaotongjiapuzi Gold Deposit of Eastern Liaoning

The Xiaotongjiapuzi gold deposit occurs in a Palaeoproterozoic rift accretionary terrane in eastern Liaoning and is hosted by a carbonate formation of the Dashiqiao Formation, Liaohe Group. The metamorphic grade of the host rock is low amphibolite-high greenschist facies. Gold, which is mainly invisible, is distributed in pyrite and arsenopyrite. The grains of Au-bearing sulphide minerals are fine, ranging from 0.0 n to 1 mm. The wall-rock alterations are characterized by low-temperature silification, hydro-sericitization, sericitization and carbonatization. The homogenization temperatures of the fluid inclusions in quartz closely associated with gold mineralization range from 140 to 240° C. The metallogenic age represented by the Ar-Ar isotopic age of sericite is 167 Ma. Comparisons and studies show that the Xiaotongjiapuzi gold deposit can be classified as the submicron-sized disseminated deposit (analogous to the Carlin-type) hosted in metamorphic rocks.     

鲁中“淄河式”层控铁矿床岩相特征及形成机理

The Lower Palaeozoic system is a series of iron-bearing rocks consisting mainly of shallow sea-facies carbonates. On the basis of micrafacies analysis of the carbonate rocks,the Lower Palaeozoic sedimentary sea basin is divided into two broad sedimentary-structural regions,four sedimentary facies and nine subfacies. Original iron-rich carbonates were deposited in the restricted basins, such as salt-lake, lagoon, etc. Over the long period of geological history, the original iron formations were reconstructed by late tectonic processes to various extents. Geological observations and studies of the equilibrium mechanism of oxygen and sulfur isotope fraetionation and the composition and temperatures of fluid inclusions in the minerals indicate that thermal brines played an important role in the reworking process of the original iron-rich carbonate rocks, which thus led to the formation of sedimentary-reworked strata-bound ore deposits.     

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 diagenesi     

Interactions between basalts and oil source rocks in rift basins： CO2 generation

Basalts interbedded with oil source rocks are discovered frequently in rift basins of eastern China, where CO2 is found in reservoirs around or within basalts, for example in the Binnan reservoir of the Dongying Depression. In the reservoirs, CO2 with heavy carbon isotopic composition (δ13C>-10‰ PDB) is in most cases accounts for 40% of the total gas reserve, and is believed to have resulted from degassing of basaltic magma from the mantle. In their investigations of the Binnan reservoir, the authors suggested that the CO2 would result from interactions between the source rocks and basalts. As the source rocks around basalts are rich in carbonate minerals, volcanic minerals, transition metals and organic matter, during their burial history some of the transition metals were catalyzed on the thermal degradation of organic matter into hydrocarbons and on the decomposition of carbonate minerals into CO2, which was reproduced in thermal simulations of the source rocks with the transition metals (Ni and Co). This kind of CO2 accounts for 55%-85% of the total gas reserve generated in the process of thermal simulation, and its δ13C values range from -11‰- -7.2‰ PDB, which are very similar to those of CO2 found in the Binnan reservoir. The co-generation of CO2 and hydrocarbon gases makes it possible their accumulation together in one trap. In other words, if the CO2 resulted directly from degassing of basaltic magma or was derived from the mantle, it could not be accumulated with hydrocarbon gases because it came into the basin much earlier than hydrocarbon generation and much earlier than trap formation. Therefore, the source rocks around basalts generated hydrocarbons and CO2 simultaneously through catalysis of Co and Ni transition metals, which is useful for the explanation of co-accumulation of hydrocarbon gases and CO2 in rift basins in eastern China.