Fluid environment for preservation of pore spaces in a deep dolomite reservoir

Well TS1 reveals many uncemented pores and vugs at depths of more than 8000 m in a deep Cambrian dolomite reservoir in the Tarim Basin, northwestern China. The fluid environment and mechanism required for the preservation of reservoir spaces have yet not been well constrained. Carbon, oxygen, and strontium isotope compositions and fluid inclusion data suggest two types of fluids, meteoric water and hydrothermal fluid, affecting the Lower Paleozoic carbonate reservoirs in the Tarim Basin. Based on simulation using a thermodynamic model for H₂O‐CO₂‐NaCl‐CaCO₃ system, meteoric water has the ability to continuously dissolve carbonate minerals during downward migration from the surface to deep strata until it reaches a transition depth, below which it will begin to precipitate carbonate minerals to fill preexisting pore spaces. In contrast, hydrothermal fluid has the ability to dissolve carbonate in deep strata and precipitate carbonate in shallow strata during upward migration. Based on the dissolution–precipitation characteristics of the two types of fluids, the ideal fluid environment for the preservation of preexisting reservoir spaces occurs when carbonate reservoir is neither in the CaCO₃ precipitation domain of meteoric water nor in the CaCO₃ precipitation domain of hydrothermal fluid. Taking the Lower Paleozoic carbonate reservoirs in the north uplift area as an example, the spaces in the deep Cambrian dolomite reservoir near well TS1 were seldom filled because thick Ordovician deposits blocked meteoric water from migrating downward into the Cambrian dolomite reservoir and because the Cambrian dolomite reservoir has been in the domain of hydrothermal dissolution since the Permian. The deep carbonate layers in basins elsewhere with a similar fluid environment may have high uncemented porosity and consequently have good hydrocarbon exploration potential.     

Chemical Weathering of Detrital Sediments in the Taklamakan Desert,Northwestern China

Based on the analysis of major‐element compositions of detrital sediments from the Taklamakan Desert of northwestern China, this paper aims to study chemical weathering in a hyper‐arid desert environment. The major‐element compositions are basically similar to the Upper Continental Crust but show a clear enrichment of CaO and depletion of Na₂O and K₂O, indicating the enrichment of carbonates and the decomposition of sodium and potassium silicates. The indexes of chemical alteration are relatively low and correlate negatively with the content of Na₂O, implying that the degree of chemical weathering is weak and mainly controlled by the weathering of sodium feldspars. An A‐CN‐K model demonstrates that the detrital sediments from the Taklamakan Desert have a high homogeneity in the trend of chemical weathering. They are weathered less than sands and soil in many other Chinese deserts, and also less than similar detrital sediments in many other countries. This evidence suggests a low degree of mineralogical maturity in the Taklamakan Desert. The aeolian sediments of different ages have similar indexes of chemical weathering, suggesting that the degree of chemical weathering was consistent in the Taklamakan Desert throughout the period of aeolian deposition. The low degree of chemical weathering is caused principally by extreme aridity, rapid rejuvenation of detrital sediments associated with strong aeolian processes, and an intensive input of fluvial deposits, as well as a lack of vegetation. Due to the high concentration of erodible minerals, the desert is quite vulnerable to soil erosion and land degradation.     

Fluid mapping in deeply buried Ordovician paleokarst reservoirs in the Tarim Basin,western China

The storage spaces within deeply buried Ordovician paleokarst reservoirs in the Tarim Basin are mostly secondary and characterized by strong heterogeneity and some degree of anisotropy. The types of fluids that fill the spaces within these reservoirs are of great importance for hydrocarbon exploration and exploitation. However, fluid identification from seismic data is often controversial in this area because the seismic velocity for this particular reservoir could be significantly influenced by many factors, including pore shapes, porosity, fluid types, and mineral contents. In this study, we employ the differential effective medium‐Gassmann rock physics model to interpret and discuss the characteristics of conventional karstic carbonate reservoirs in the Tarim Basin that are filled with different fluids (oil, gas, and water) using logging data and thus objectively build corresponding fluid identification criteria. These criteria are subsequently evaluated by amplitude versus offset (AVO) forward analysis based on typical logging data and further applied to ascertain the reservoir fluid types in two different areas in the Tarim Basin based on prestack inversion results. For conventional carbonate reservoirs, gas can be distinguished from heavy oil and water, but heavy oil and water are broadly similar on seismic data. For condensate carbonate reservoirs, water can be differentiated from light oil (i.e., condensates) and gas, but light oil and gas demonstrate substantial similarities in terms of their seismic responses. The predicted fluid results are in good agreement with the results of drilling and oil testing. In particular, modeling the seismically resolvable reservoirs in the carbonate strata in the Tarim Basin, which have needle‐ and sphere‐shaped storage spaces (pore aspect ratio > 0.3) and clay content that is lower than 5%, indicates that fluid properties could be properly evaluated if the porosity is larger than 5% for conventional carbonate reservoirs and >7% for condensate carbonate reservoirs.     

劣化石刻表层生物矿化加固材料的探索性研究

许多濒危石质文物表层劣化现象严重。但是,以往使用的表层加固材料很难令人满意,探索新的疏松岩石表层加固材料已是当务之急。由于天然生物矿化物耐候性优越,与基底岩石相容性良好,具有较好的加固作用,本工作依据生物矿化的原理,以不同生物大分子溶液作为有机模板,分别控制草酸钙、磷灰石和碳酸钙过饱和溶液于室温下在疏松岩石仿制样品的表层及孔隙内结晶生长。通过抗压强度、表面硬度和耐水浸泡等试验进行了加固效果评价,以考察仿生物矿化材料对含钙疏松岩石的加固能力。实验结果表明,仿生合成的生物矿化材料均具有一定的加固效果,其中以磷灰石仿生矿化材料的加固强度最大,以硫酸软骨素为模板的加固效果为佳。并且,在考察的3种加固方式中,以"直接混合"的加固强度更好,以"表面渗透"的耐水浸泡能力更强。本工作为开发濒危石质文物表层加固材料提供了新的思路。     

花山岩画岩体开裂机理统计分析

岩体开裂是危害花山岩画最严重的病害,会对岩画造成毁灭性的破坏。为制定有效的灌浆加固措施,在对岩体开裂成因及影响因素分析和现场调查的基础上,做了统计分析。结果表明:1)岩画区共有418处开裂病害,开裂岩体以风化开裂体为主,占69%,且构造开裂体的厚度大于风化开裂体;2)构造开裂体的钙质、钙质与泥质共同充填比例为78%,高于风化开裂体的52%;3)构造裂隙和风化裂隙的张开度均以小于6mm为主,可知当张开度大于6mm时,开裂体将发生剥离掉块;4)风化开裂体的危险性I级、Ⅱ级所占的比例为57%和22%,小于构造开裂体的64%和27%,但风化开裂体多发育于岩画存在部位,易出现开裂和掉块,破坏更大;5)构造开裂体的厚度较大、裂隙连通性好、危险等级高,而风化开裂体厚度较薄、裂隙贯通性差、危险等级较高。本研究结果可为开裂岩画岩体灌浆加固及后期修复提供理论依据。     

土遗址病害的评估体系研究

土遗址病害评估是对土遗址进行科学保护、管理、利用的一项基础性工作,但土遗址病害评估的体系还没有建立。为此,通过对土遗址病害的分析,借鉴地质工程、岩土工程的相关理论和方法,采用逐次分析的方法评估土遗址的载体和本体病害,探讨了土遗址病害评估体系。通过研究认为,可以从地质灾害、稳定性、表面风化三方面对土遗址病害程度进行评估。地质灾害和稳定性有其它学科相对成熟的理论和方法可以借鉴和采用。表面风化评估应考虑到风化剥蚀速率、遗址保存程度和文物价值三个方面,引进风化度和文物价值权重系数的概念,利用模糊数学原理对表面风化的危险程度进行综合评估是一种新思路。     

Origin of dolomites in the Cambrian (upper 3rd‐Furongian) formation,south‐eastern Sichuan Basin,China

The origin of large‐scale ancient dolomite is one of the most hotly debated topics in sedimentology. The Loushanguan group of the upper 3rd‐Furongian Cambrian series on the south‐eastern margin of the Sichuan Basin consists of numerous dolomites, and the origins of these dolomites have never been reported previously although they are probably good hydrocarbon reservoirs. Based on a systematic analysis of petrology, fluid inclusions, carbon and oxygen isotopes, trace elements and rare earth elements (REEs), this study provides some unique insights into the origins of the dolomites. Four dolomite types have been identified in the study area: dolomicrite, fabric‐retentive oolitic dolomite, fabric‐obliterative dolomite and saddle dolomite cement. In the dolomicrite and fabric‐retentive oolitic dolomite, high Sr contents (with respect to the fabric‐obliterative dolomite) and the lack of two‐phase aqueous inclusions suggest that they formed at shallow‐to‐intermediate burial depths at low temperatures (<50–60°C). Carbon and oxygen isotopes and seawater‐like REE+Y characteristics of the dolomicrite and fabric‐retentive oolitic dolomite indicate that the dolomitizing fluids were evaporated seawater or slightly modified seawater. The obliteration of the original sedimentary fabric and relatively low δ¹⁸O and Sr values compared to the fabric‐retentive dolomite indicate that fabric‐obliterative dolomite formed at intermediate‐to‐deep burial diagenesis. The chemical composition approaches pure dolomite and the REE+Y characteristics are similar to those of the fabric‐retentive dolomite, indicating that the fabric‐obliterative dolomite was formed due to the recrystallization of the previously formed fabric‐retentive dolomite at elevated burial depths and temperatures. High fluid inclusion homogenization temperatures (115–150°C), low δ¹⁸O values, nonplanar‐a crystals and seawater‐like REE+Y characteristics suggest that saddle dolomite cement formed by reprecipitation of dolomite that related to seawater‐driven and deep burial fluid. In the study area, dolomicrite and fabric‐retentive oolitic dolomite may have been formed by penecontemporaneous or seepage‐reflux dolomitization during early‐stage diagenesis. Subsequently, during progressive burial, most of the fabric‐retentive dolomite was converted into fabric‐obliterative dolomite by recrystallization. This study confirms that fabric‐obliterative dolomite was the main dolomite type, and although deeply buried, these Cambrian dolomites most likely have preserved coeval seawater geochemical signals.     

A SCULPTURAL MARBLE OF PRIME QUALITY IN ANTIQUITY—THE DOLOMITIC MARBLE OF THE SIVEC MOUNTAINS IN MACEDONIA

This paper presents analytical data on a major occurrence of fine‐grained dolomitic marble in the Sivec Mountains, close to the city of Prilep in today's former Yugoslavian Republic of Macedonia. This is the first presentation of an analytical database of a large‐scale source of fine‐grained dolomitic marble, whose ancient use can be demonstrated by tool marks and archaeological evidence. Many traces of ancient mining have fallen victim to a big modern quarrying operation in this area, which for decades has produced high‐quality blocks of marble (‘Macedonian Carrara’) and exported them all over the world. A combination of different analytical methods is used to characterize the marbles and to present a database for investigating ancient artefacts made of fine‐grained dolomites. Petrographic investigations revealed the very homogeneous micro‐fabric of this marble, which is of high purity with very low silicate contamination and has a maximum grain‐size of 1 mm. In addition to analysis of the stable isotopes, trace element analyses of carbonate lattice elements (Mg, Fe, Mn and Sr) were performed. An alternative method, the analysis of the chemical composition of the inclusion fluids, was also employed. On the basis of these techniques, a multivariate discrimination analysis was performed, and a clear separation of the different dolomitic marbles (Thasos, Ephesos, Proconnesos and Karacasu) was obtained. Finds of artefacts of high artistic quality made from this dolomite prove the existence of a significant workshop in the neighbourhood of the Sivec quarries. Because of its vulnerability to weathering, this fine‐grained dolomitic marble was used preferentially for indoor applications. Sculptures of prime artistic quality made of Sivec marble have so far been found in several locations of the Republic of Macedonia.     

Diagenesis in bone and enamel apatite carbonate; the potential of density separation to assess the original composition

This paper presents a new approach to the isotopic measurement of diagenetically altered archaeological bone apatite carbonate. We describe how the existing differential dissolution method may be combined with a new approach to remove diagenetically reformed material on the basis of its greater specific gravity. We show that heavier, more diagenetically altered fraction has a higher (altered) δ¹³C and also increased crystallinity within one individual. In addition, we proposed one potential tool to check the validity of bone carbonate by comparing bone collagen, enamel carbonate and bone carbonate values of δ¹³C and radiocarbon content from the same individual. In the case of Danebury cattle, we estimated the biogenic δ¹³C_apa value for DC83 and DC89, although it is still difficult to overcome diagenesis in order to meet the expected value, which is shown to be 1.9‰ (DC83) and 3.5‰ (DC89).     

Iron mineralization and dolomitization in the Paran Fault zone,Israel: implications for low‐temperature basinal fluid processes near the Dead Sea Transform

Petrography, Eh‐pH calculations and the stable isotope composition of oxygen are used to interpret geochemical processes that occurred during iron oxide mineralization and dolomitization along the Menuha Ridge segment of the Paran Fault, southern Israel, adjacent to the Dead Sea Transform (DST). Iron mineralization is strongly localized in the fault zone as ferruginous lenses, whereas Fe dolomitization spreads laterally into the Cenomanian‐Turonian carbonate host rock as stratabound beds. The average oxygen isotope fractionation between syngenetic quartz and iron oxides in the ferruginous lenses gives a temperature of 50 ± 10°C and δ¹⁸O SMOW water = ?3.5‰; consistent with an origin from metalliferous groundwater flow in the sedimentary basin. Ferroan dolomite initially formed under strongly reducing conditions, but this was followed by oxidation and pseudomorphic replacement of the dolomite by a mesh of fine‐grained iron oxides (simple zoned dolomites). This cycle of ferroan dolomite formation and replacement by iron oxides was repeated in complex zoned dolomites. Dolomite oxygen isotope compositions fall into two groups: a high δ¹⁸O group corresponding to the simple zoned dolomites and non‐ferroan dolomites and a low δ¹⁸O group corresponding to the complex zoned dolomites. Water‐rock calculations suggest that the epignetic dolomites formed under fluid‐buffered conditions: the high δ¹⁸O group are indicated to have formed at temperatures of ca. 25°C for waters with δ¹⁸O = ?4 to 0‰; the low δ¹⁸O complex zoned dolomites at 50–75°C for waters with the same isotopic composition. A kinetic calculation for a complex zoned dolomite‐bearing bed indicates that dolomitization must have occurred at high values of the dolomite saturation index. This requirement for high Mg supersaturation and the indication that epigenetic dolomitization is more protracted in stratigraphically deeper formations located closer to the DST is consistent with models proposing that Mg‐rich solutions originated in the Dead Sea Rift.     

山东青州香山汉墓出土西汉彩绘陶器腐蚀病害及其机理分析

为保护山东青州香山汉墓出土大量精美的西汉彩绘陶器,针对出土器物的腐蚀病害现状,运用X-射线衍射分析和偏光显微分析等技术手段,对出土彩绘陶器表面的白色盐分产物和陶片本体进行了检测。检测结果表明,表面盐分产物成分为碳酸钙和硫酸钙;该批陶器烧制材料主要由砂屑及粘土构成,所用粘土为岩土矿长期风化的积聚产物;制作工艺以模为主,模、塑结合;并结合以上的几种分析结果对其腐蚀病害及产生机理进行了论述,发现陶器表面风化是云母类矿物内部化学键断裂以及保存环境中的可溶盐的破坏应力所致。本研究结果为彩绘陶器保护修复提供了科学依据。     

Hydrothermal dolomitization,mixing corrosion and deep burial porosity formation: numerical results from 1‐D reactive transport models

Major corrosion has been found at depth in carbonate hydrocarbon reservoirs from different geologic provinces. Fluid inclusion microthermometry and stable isotopic compositions of carbonate cements, predating major corrosion, constrain the interpretation of the evolution of parental fluids during progressive burial and prior to the major corrosion event. Post‐major corrosion mineral paragenesis includes pyrite (‐marcasite), anhydrite, kaolinite (dickite) and fluorite. Although the post‐corrosion mineral paragenesis represents minor volumes of rock, it may provide valuable insights into the post‐corrosion brine chemistry. Using reactive transport numerical models, the roles of cooling and/or mixing of brines on corrosion have been evaluated as controls for dolomitization, deep burial corrosion and precipitation of the post‐corrosion mineral paragenesis. Modelling results show that cooling of deep‐seated fluids moving upward along a fracture may cause minor calcite dissolution and porosity generation. Significant dolomitization along a fracture zone and nearby host‐rock only occurs when deep‐seated fluids have high salinities (4 mol Cl kg^?1 of solution) and Darcian flow rates are relatively high (1 m³ m^?2 year^?1). Only minor volumes of quartz and fluorite precipitate in the newly formed porosity. Moreover, modelling results cannot reproduce the authigenic precipitation of kaolinite (dickite at high temperatures) by cooling. As an alternative to cooling as a cause of corrosion, mixing between two brines of different compositions and salinities is represented by two main cases. One case consists of the flow up along a fracture of deep‐seated fluids with higher salinities than the fluid in the wall rock. Dolomite does not precipitate at a fracture zone. Nevertheless, minor volumes of dolomite are formed away from the fracture. The post‐corrosion mineral paragenesis can be partly reproduced, and the results are comparable to those obtained from cooling calculations. Minor volumes of quartz and fluorite are formed, and kaolinite‐dickite does not precipitate. The major outputs of this scenario are calcite dissolution and slight net increase in porosity. A second case corresponds to the mixing of low salinity deep‐seated fluids, flowing up along fractures, with high salinity brines within the wall rock. Calculations predict major dissolution of calcite and precipitation of dolomite. The post‐corrosion mineral paragenesis can be reproduced. High volumes of quartz, fluorite and kaolinite‐dickite precipitate and may even completely occlude newly formed porosity.     

Luminescence Properties of Chert and some Archaeological Applications

We have examined the cathodoluminescence (CL) and induced thermoluminescence (TL) properties of chert collected from the Ozark Mountains area of the central United States. The cherts showed predominately orange CL with occasional blue CL. X-ray diffraction indicates that the amount of orange CL correlates closely with the abundance of carbonates within the chert. Previous studies have shown that macroquartz characteristically gives off a weak and transient blue CL. Thermoluminescence studies concentrated on the shape of the radiation induced TL glow curve. The results seem to indicate all of the cherts sampled fall into one of four glow curve categories. The TL categories correspond to quartz crystallinity as measured by X-ray diffraction, which is probably a reflection of quartz grain size. Application of these techniques is somewhat new to chert studies, but may provide a useful criterion in establishing the number of chert varieties or sourcing chert provenience locations for artefacts collected from archaeological sites. Calcite and dolomite are expected to leach from chert surfaces upon exposure to weathering agents, thus making CL a helpful tool for the detection of fake stone artefacts with fresh fracture surfaces. Quartz crystallinity is an important factor in determining chert cleavage characteristics and TL appears to be a useful measure of this property.     

ANALYSIS OF ROMAN WALL PAINTINGS FROM THE THERMAE OF ‘IULIA CONCORDIA’

Twenty‐six wall painting fragments and some plaster, ‘intonachino’ and stucco samples, discovered at Iulia Concordia, have been studied by different analytical techniques to gain information about the pigment nature and the composition of the materials. The presence of calcite, dolomite and aragonite allow the distinction of four groups of wall samples varying in the nature of pigments and in the application technique. These differences can be attributed to different execution times or, more probably, to the arrangement of the rooms in the building structure. The nature of the pigments found in the Thermae of Iulia Concordia appears similar to that found in other Roman villas of Venetia et Histria, with the use of precious pigments such as Egyptian blue and cinnabar.     

南响堂石窟石雕岩表面模拟溶蚀实验

为了对南喃堂石窑石雕表面风化进程作定量,半定量的讨论,采用了岩溶动力学方法,模拟大气酸性降水对石雕样品进行溶蚀实验。根据实验数据,计算出该出雕的实验溶蚀速度和溶蚀溶度,同时提出,要减缓碳酸盐岩石雕的风化速度,不仅对窟区大气中SO2含量要进行监测,而且在工业区大气中的CO2也是一个应该进行监测的重要指标。     

冻融作用对古青砖宏观性能及微观结构劣化的影响

砖质文物建筑多数处于室外工作环境,其损伤呈现出冻融循环条件下的物理风化和材料水解条件下的化学风化联合作用破坏形态,致使古青砖文物面临着严重的环境侵蚀风化问题。为此,以古建筑青砖为研究对象,通过对6组试样分别进行0,15,30,45,60和75次冻融循环试验,分析冻融循环次数对古青砖的孔洞率、质量、抗压强度的影响规律。在此基础上,通过TEM(透射电子显微镜)扫描探讨了冻融作用对古青砖微观结构的损伤过程及劣化机理。结果表明:随着冻融循环次数的增加,古青砖的孔洞率、质量损失率以及强度损失率均增大;TEM扫描发现冻融对古青砖造成了明显的微观孔隙结构损伤,特别是75次冻融循环后该损伤明显激增。同时,利用XPS(X射线光电子能谱仪)测试古青砖化学成分的组成,说明青砖体内碳酸盐等可溶性盐类的晶体水解造成青砖的微观孔隙结构损伤,是其遭受化学风化作用的主要原因。     

Geo-archeological interpretation of Acheulian calc-pan sites at Doornlaagte and Rooidam (Kimberley,South Africa)

Two Acheulian occupation sites of the Kimberley District, Doornlaagte and Rooidam, are found geologically sealed and in semi-primary context within complex sequences of calcareous and arenaceous sediments. The sedimentary columns are analyzed and interpreted in terms of sedimentology and stratigraphy, indicating major occupation along the margins of shallow, seasonal lakes; sporadic visits to the fluctuating shoreline are also indicated thereafter, until the Doornlaagte playa began to dry out, and at Rooidam until the whole depression was submerged. The evolution of the related calcareous pans is discussed and attributed to cycles of alternating erosion (aeolian, chemical and fluvial) and deposition (lacustrine and colluvial, including reworked aeolian components). In addition to pedogenetic “calcretes,” most of the limestones of the pan sedimentary sequences are lacustrine in origin. Palaeosols also include fersiallitic soils. The various geomorphologic events indicate repeated and appreciable environmental changes during the mid-Pleistocene. The detailed climatic oscillations recorded at Doornlaagte and Rooidam cannot be correlated, and the latter site is appreciably younger, with a provisional $\text{Th}\text{U}$ date of 115,000 BP for the late Acheulian (“Fauresmith”) occupation.     

Patterns of Diagenesis in Bone II: Effects of Acetic Acid Treatment and the Removal of Diagenetic CO3

Archaeological bones of varying preservation have been treated with 0·1 M acetic acid in order to investigate the effect on structural and chemical alterations caused by diagenesis. Acetic acid is commonly used as a “cleaning agent” for removing diagenetic carbonate from bone and enamel, in an attempt to recover original, biogenic signals for use in dietary and¹⁴C dating studies.Diagenetic parameters were measured before and after treatment on a range of archaeological bones with good and bad preservation. Histological preservation defined the behaviour of the correlating parameters, where correlation coefficients between carbonate content and crystallinity, microporosity and macroporosity increased significantly after treatment. For histologically well preserved material, acetic acid is effective at returning carbonate content to around that of modern bone. Where bone is extensively damaged by micro-organisms, “loose” diagenetic material can be removed, but a fraction largely composed of hypermineralized bioapatite remains, which, we believe, cannot be reliably used to obtain accurate biological signals.