Long-Term Evolution Of Delayed Ettringite And Gypsum In Portland Cement Mortars Under Sulfate Erosion

The magnitude evolution of ettringite and gypsum in hydrated Portland cement mortars due to sulfate attack was detected by X-ray powder diffraction. The influences of sulfate concentration and water-to-cement ratio on the evolution of ettringite and gypsum were investigated. Experimental results show that the magnitude of ettringite formation in sodium sulfate solution follows a three-stage process, namely, the 'penetration period', 'enhance period of strength', and 'macro-crack period'. The cracking of concrete materials is mainly attributed to the effect of ettringite. The gypsum formations occurred in two stages, the 'latent period' and the 'accelerated period'. The gypsum formation including ettringite formation was relative to the linear expansion of mortars to some extend. Both water-to-cement ratio and sulfate concentration play important roles in the evolution of ettringite and gypsum. (C) 2008 Elsevier Ltd. All rights reserved.

盐岩地层套管蠕变荷载试验及其数值分析

中原油田在钻遇盐岩层的油水井中,某些区块套管的损坏率高达65%,盐岩层蠕变是套管损坏的一个重要原因.通过对6块盐岩岩心进行地下条件的蠕变模拟试验,得出了盐岩层的蠕变规律和特征参数,建立了套管承受外载的有限元计算模型,并编制了计算程序.利用所编制的软件对中原油田某口井的套管蠕变载荷进行了数值模拟计算.结果表明,作用在套管上的径向载荷与相位角和蠕变时间有关,并且蠕变条件下套管的最大载荷超过原地应力10%左右.

广西合山固体废弃物制备地质聚合物胶凝材料

Geopolymer gelatinous material was prepared by ferroalloy slag (signed with NKT in laboratory) and circulating fluidization bed slag (CFB slag, signed with NM in laboratory) produced from Heshan city, Guangxi zhuang autonomous region, China. The mechanical properties of the geopolymer made of high content ferroalloy slag can reach the standard of 42.5# portland blastfurnace-slag cement, and it’s processing technology is more simple and not need of mill and burn and will not produce harmful gas. By means of chemical and XRD analyses, it is concluded that NKT is a kind of acidity water-granulated slag with better activation and fit to be activated by alkali activators. Low-cost industrial gypsum (signed with NG in laboratory), analytic reagent oxide(signed with NH in laboratory) and sulfate(signed with NS in laboratory) were selected as alkali activation in the experiment. The results showed NH is a good alkali activator for NKT. Both NH and NG can activate ferroally slag’s activities, but NS can’t alone. The activation effect of superimposing activation of NH and NG excel by separateness. Based on those experiments, optimization compounds were carried out: (1) NKT: NH: NG = 80: 10: 10 and (2) NM: NKT: NS: NG: NH = 10: 70: 2: 8: 10。. The soundness of the test blocks is good by boiling examination. Through XRD, SEM, IR, NMR analyses of geopolymer, the reaction mechanism of geopolymer prepared by alkalescent activating in solid wastes was discussed in the thesis first. It is point out, there is difference in reaction mechanism between traditional geopolymer preparation and the preparation of alkalescent activating solid wastes because NG is a industry product. There is the similar process of depolymerization and reunion of Si-O bond. The latter preparation process generate new subtance but the former doesn’t. In the experiment, we found a performance of NKT that the water requirement of normal consistency of geopolymer reduces with increasing content of NKT. The result shows NKT has some ability to reduce water requirement. The performance is worthy of further research and utilization. Making use of solid wastes to prepare geopolymer, not only can settle environment problem caused by a great deal of dump of NKT, but also settle the shortage of natural resources. Moreover it could take economic, environmental and social benefits and settle thoroughly contradiction in the environment protection and regional economy development and promote circulation economy development.

班公湖带多不杂超大型富金斑岩铜矿床的成岩成矿年代学、岩石学及高氧化岩浆¬流体-成矿作用

Duobuza copper deposit, newly discovered typical gold-rich porphyry copper deposit with superlarge potential, is located in the Tiegelong Mesozoic tectonic -magmatic arc of the southern edge of Qiangtang block and the northern margin of Bangonghu-Nujiang suture. Quartz diorite porphyrite and grandiorite porphyry, occurred in stock, are the main ore-bearing porphyries. As the emplacement of porphyry stock, a wide range of hydrothermal alteration has developed. Within the framework of the ore district, abundant hydrothermal magnetite developed, and the relationship between precipitation of copper and gold and hydrothermal magnetite seems much close. Correspondingly, a series of veinlets and network veinlets occurred in all alteration zones. Therefore, systematic research on such a superlarge high-grade Duobuza gold-rich porphyry copper deposit can fully revealed the metallogenic characteristics of gold-rich porphyry copper deposits in this region, establish metallogenetic model and prospecting criteria, and has important practical significance on the promotion of regional exploration. In addition, this research on it can enrich metallogenic theory of strong oxidation magma-fluid to gold-rich porphyry copper deposit, and will be helpful to understand the metallogenic characteristics in early of subduction of Gangdese arc stages and its entire evolution history of the Qinghai-Tibet Plateau, the temporal and spatial distribution of ore deposits and their geodynamics settings. Northern ore body of Duobuza copper deposit have been controlled with width (north-south) about 100 ~ 400 m, length (east-west) about 1400 m, dip of 200 °, angle of dip 65 °~ 80 °. And controlled resource amount is of 2.7 million tons Cu with grade 0.94% and 13 tons Au with 0.21g/tAu. Overall features of ore body are large scale, higher grade copper, gold-rich. Ore occurred in the body of granodiotite porphyry and quartz diorite porphyrite and its contact zone with wall rock. Through the detailed mapping and field work studies, some typies of alteration are identificated as follows: albitization, biotititation, sericitization, silication, epidotization, chloritization, carbonatization, illitization, kaolinization and so on. The range of alteration is more than 10km2. Wall alteration zone can be divided into potassic alteration, moderate argillization alteration, argillization, illite-hydromuscovite or propylitization from ore-bearing porphyry center outwards, but phyllic alteration has not well developed and only sericite-quartz veins occurred in local area. Moreover, micro-fracture is development in ore district , and correspondingly a series of veinlets are development as follows: biotite vein (EB type), K-feldspar-biotite-chalcopyrite-quartz vein, magnetite-antinolite-K-feldspar vein, quartz-chalcopyrite-magnetite veins (A-type), quartz-magnetite-biotite-K-feldspar vein, chalcopyrite veinlets in potassic alteration zone; (2) chalcopyrite occurring in the center vein–quartz vein (B type), chalcopyrite veinlets, chalcopyrite-gypsum vein in intermediate argillization alteration; (3) chalcopyrite- pyrite-quartz vein, pyrite-quartz vein, chalcopyrite-gypsum veins, quartz-gypsum- molybdenite-chalcopyrite vein in argillization alteration; (4) gypsum veins, quartz-(molybdenite)-chalcopyrite vein, quartz-pyrite vein, gypsum- chalcopyrite vein, potassium feldspar veinlets, Carbonate veins, quartz-magnetite veins in the wall rock. In short, various veins are very abundant within the framework of the ore district. The results of electronic probe microscopy analysis (EMPA) indicate that Albite (Ab 91.5~99.7%) occurred along the rim of plagioclase phenocryst and fracture, and respresents the earliest stages of alteration. K-feldspar (Or 75.1~96.9%) altered plagioclase phenocryst and matrix or formed secondary potassium feldspar veinlets. Secondary biotite occurred mainly in phenocryst, matrix and veinlets, belong to magnesium-rich biotite formed under the conditions of high-oxidation magma- hydrothermal. Chloritization developed in all alteration zones and alterd iron- magnesium minerals such as biotite and hornblende and then formed chlorite veinlets. As the temperature rises, Si in the tetrahedral site of chlorite decreased, and chlorite component evolved from diabantite to ripiolite. The consistent 280℃~360℃ of formation temperature hinted that chlorite formed on the same temperature range in all alteration zones. However, formation temperature range of chlorite from the gypsum-carbonate-chlorite vein was 190℃~220℃, and it may be the product of the latest stage of hydrothermal activity. The closely relationship between biotite and rutile indicate that most of rutiles are precipitated in the process of biotite alteration and recrystallization. In addition, the V2O3 concentration of rutile from ore body in Duobuza gold-rich porphyry copper deposit is >0.4％, indicate that V concentration in rutile has important significance on marking main ore body of porphyry copper deposit. Apatites from Duobuza deposit all are F-rich. And apatite in the wall rock contained low MnO content and relatively high FeO content, which may due to the basaltic composition of the wall rocks. The MnO in apatite from altered porphyry show a strong positive correlation with FeO. In addition, Cl/F ratio of apatite from wall rock was highest, followed by the potassic alteration zone and potassic alteration zone overprinted by moderate argillization alteration was the lowest. SO2 in Apatite are in the scope of 0 to 0.66%, biotite in the apatite has the highest SO2, followed by the potassic alteration zone, potassic alteration zone overprinted by moderate argillization alteration, and the lowest in the surrounding rocks, which may be caused by the decrease of oxygen fugacity of hydrothermal fluid and S exhaust by sulfide precipitation in potassic alteration. Magnetite in the wall rock have higher Cr2O3 and lower Al2O3 features compared with altered porphyry, this may be due to basalt wall rock generally has high Cr content. And magnetites have higher TiO2 content in potassic alteration than moderate argillization alteration overprinted by potassic alteration, argillization and wall rock, suggested that its formation temperature in potassic alteration was the highest among them. The ore minerals mainly are chalcopyrite and bornite, and Au contents of chalcopyrite, bornite, and pyrite are similar with chalcopyrite slightly higher. The Eu* negative anomaly of disseminated chalcopyrite was relatively lower than chalcopyrite in veinlets. Within a drill hole, the Eu* negative anomaly of disseminated chalcopyrite was gradually larger from bottom to top. Magnetite has the same distribution model, with obvious negative Eu* abnormal, and ΣREE in great changes. The gypsum has the highest ΣREE content and the obvious negative anomaly, and biotite obviously has the Eu* abnormal. Based on the petrographic and geochemical characteristics, five series of magmatic rocks can be broadly classified; they are volcanic rocks of the normal island arc, high-Nb basaltic rocks, adakites, altered porphyry and diorite. The Sr, Nd, Hf isotopes and geochemistry of various series of magmatic rock show that they may be the result of mixing between basic magma and various degrees of acid magma coming from lower crust melted by high temperature basic underplating from partial melting of the subduction sediment melt metasomatic mantle wedge. Furthermore S isotope and Pb isotope of the sulfide, ore-bearing porphyries and volcanic rocks indicated ore-forming source is the mantle wedge metasomatied by subduction sediment melt. Oxygen fugacity of magma estimated by Fe2O3/FeO of whole rock and zircon Ce4+/Ce3+ indicated that the oxidation of basalt-andesitic rocks is higher than ore-forming porphyry, and might imply high-oxidation characteristics of underplated basic magma. Its high oxidative mechanism is likely mantle sources metasomatied by subduction sediment magma, including water and Fe3+. And such high oxidation of basaltic magma is conducive to the mantle of sulfides in the effective access to melt. And the An component of dark part within plagioclase phenocryst zoning belong to bytownite (An 74%), and its may be a result of magma composition changes refreshment by basaltic magma injection. SHRIMP zircon U-Pb and LA-ICP-MS zircon U-Pb geochronology study showed that the intrusions and volcanic rocks from Duobuza porphyry copper deposit belong to early Cretaceous magma series (126~105Ma). The magma evolution series are as follows: the earliest diorite and diorite porphyrite → ore-bearing porphyry and barren grandiorite porphyry →basaltic andesite → diorite porphyrite → andesite → basaltic andesite, and magma component shows a evolution trend from intermediate to intermediate-acid to basic. Based on the field evidences, the formation age of high-Nb basalt may be the latest. The Ar-Ar geochronology of altered secondary biotite, K-feldspar and sericite shows that the main mineralization lasting a interval of about 4 Ma, the duration limit of whole magma-hydrothermal evolution of about 6 Ma, and possibly such a long duration limit may result in the formation of Duobuza super-large copper deposit. Moreover, tectonic diagram and trace element geochemistry of volcanic rocks and diorite from Duobuza porphyry copper deposit confirm that it formed in a continental margin arc environment. Zircon U-Pb age of volcanic rocks and porphyry fall in the range of 105~121Ma, and Duobuza porphyry copper deposit locating in the north of the Bangonghu- Nujiang suture zone, suggested that Neo-Tethys ocean still subducted northward at least early Cretaceous, and its closure time should be later than 105 Ma. Three major inclusion types and ten subtypes are distinguished from quartz phenocrysts and various quartz veins. Vapor generally coexisting with brine inclusions, suggest that fluid boiling may be the main ore-forming mechanism. Raman spectrums of fluid inclusions display that the content of vapor and liquid inclusion mainly contain water, and vapor occasionally contain a little CO2. In addition, the component of liquid inclusions mainly include Cl-, SO42-, Na+, K+, a small amount of Ca2+, F-; and Cl- and Na+ show good correlation. Vapor mainly contains water, a small amount of CO2, CH4 and C2H6 and so on. The daughter minerals identified by Laman spectroscopy and SEM include gypsum, chalcopyrite, halite, sylvite, rutile, potassium feldspar, Fe-Mn-chloride and other minerals, and ore-forming fluid belong to a complex hydrothermal system containing H2O-NaCl-KClFeCl2CaCl2. H and O isotopic analysis of quartz phenocryst, vein quartz, magnetite, chlorite and gypsum from all alteration zones show that the ore-forming fluid of Duobuza gold-rich porphyry copper deposit consisted mainly of magmatic water, without addition of meteric water. Duobuza gold-rich porphyry copper deposit formed by the primary magmatic fluid (600-950C), which has high oxidation, ultra-high salinity and metallogenic element-rich, exsolution direct from the magma, and it is representative of the typical orthomagmatic end member of the porphyry continuum. Moreover, the fluid evolution model of Duobuza gold-rich porphyry copper deposit has been established. Furthermore, two key factors for formation of large Au-rich porphyry copper deposit have been summed up, which are ore-forming fluids earlier separated from magma and high oxidation magma-mineralization fluid system.

鄂尔多斯盆地东部地区奥陶系马家沟组沉积相与储层特征研究

Ordos Basin is one of the primary bases for petroleum exploration in our country. A series of Ordovician large gas fields were discovered, which suggest that the Lower Paleozoic carbonate, especiallly for Ordovician carbonate rocks, preserve plenty of hydrocarbon resources. Well Longtong 1 is studied as the typical exploration well. Acorrding to the specific research on the type of lithology, texture, structure and sedimentary sequence in Ordovician Majiagou Formation as well as additional data from another 20 wells, the sedimentary model has been built in Majiagou Formation. The sedimentary characteristics for each Member in Majiagou Formaiton and the feature of distribution are well understood as below: It suggests that period of Member 1, Member 3 and Member 5 in Majiagou Formation characterize with dry and hot climate as well as drop of the sea level. The area of Well Longtan 1 in the eastern basin is abundant of platform evaporite lithofacies with the depositional anhyrock and salt rock, whereas yield a suite of dolomite intercalated by the thin layers of anhyrock from the anhyrcok-dolomite platform sediment. It deposits muddy dolomite, dolomitic limestone and fine-grain dolomite in limestone-dolomite platform and restricted sea. During the stage of Member 2 and Member 4 in Majiagou Formation, the climate is wet and hot with increasing sea level. The study region occurs limestone with little dolomite in the open sea environment; but the margin area is the restricted sea settings with interbeding dolomite and limestone. Based on the thin section identification, element and isotope analysis as well as the study of texture and structure, it sugguests that the main reserviors are dolomite while the gypsum are major cap rocks. The Member 2 in Majiagou Formation is both the source rocks and the resveroirs; gypsum rocks widely occur in Member 3 as the better cap; similar to the Member 2, the Member 4 in Majiagou Formation is both the source rocks and the resveroirs; there are two source-reservoir-cap assemblages in the Member 5 alone and the cap is gypsum with high quality and great thickness, which is a favorite source-reservoir-cap assemblage.

东濮凹陷文－桥－白地区异常高压储层沉积成岩特征及成因初探

In Dongpu depression, there are obviously overpressure phenomena below 2000-3200m. Research to the relationship between sedimentation-diagenesis and overpressure of reservoirs is in great need. In this paper, after analyzing and simulating the overpressure in Wendong, Qiaokou and Baimiao regions, we draw a conclusion that the fast sedimentation since Low Tertiary is one of the most important mechanisms for the formation of overpressure in Dongpu Depression. The gypsum in northern part of Dongpu Depression is the good seal for the development of overpressure. On the base of detailed work to the distribution and magnitude of overpressure in Wen-qiao-Bai regions, we selected several wells that have different overpressure to find the sedimentary and diagenetic differences of these wells. We find that compaction is obviously inhibited in overpressured reservoirs, which results in the linear relation between physical properties of reservoirs and sedimentary parameters, such as sorting coefficient, the content of matrix, etc. Reservoirs with great magnitude of overpressure have undergone more extensive erosion than the ones with low magnitude of overpressure, which probably is the result of the great solubility of CO_2 under high pressure. The great burial depth, the high content of matrix and the extensively developed cement of carbonate are the most important factors that influence the physical properties of reservoirs in Dongpu depression. Overpressure plays a constructive role in the physical properties of reservoirs. the overpressured reservoirs of Es_3~3 subsection in Wendong region are probably the ones that have good physical properties. From homogenetic temperatures that obtained form the fluid inclusions in quartz overgrowth, we find that there were 4 episodes of fluid flows in Dongpu depression. In conjunction with the analysis of the burial history of overpressured reservoirs, we draw conclusions that the first, second and third episodes of fluid flows took place in the extensive rifting stage of Dongpu Depression, the burial depth when the first episode of fluid flow took place was about 1500m, the age was about 36 my; the burial depth of the second and third episodes of fluid flow was between 1800-3000m at that time, the age was between 35-28my. The fluid flows of the second, third, and fourth episodes were in close relation to the overpressure and maybe were the results of the episodic hydrofracturing of overpressured mudstones and shales. The episodic fluid flow of overpressured mudstones and shales probably facilitates the cementation of carbonate, which decreases the physical properties of overpressured reservoirs. The dolomites and ferrodolomites maybe the products of the episodic hydrofracturing of overpressured mudstones and shales.

黄土中可溶盐含量及意义

The concentrations of K~+,Na~+,Ca~(2+),Mg~(2+),F~-,Cl~-,NO_3~-,SO_4~(2-) and HCO_3~- in Lantian, Binxian, Ningxian, Qingyang, Mubo and Jiyuan loess sections by last interglacial on China Loess Plateau and its conductance are determinated. The results are: According to the average ions concentration in different sections, the soluble salts in south sections are mainly transported from land dusts which fall with rain, but the most salts in north sections are released from minerals by soil formation. The spatial changes of dominating soluble salts ,gypsum in south sections and Glauber'salt and fluorite in north sections, indicates the different arid degrees on Loess Plateau. The north sections are more arid than south, so that the diffluent ions become the main component in soluble salts. The salts enriched in Stage2 and 4, the arid and cold paleoclimate period, in south loess sections because that the soluble ions were swept by water, although they sedimented in warm period. On north Loess Plateau, as evaporation became the determinative factor on salts sediment, the soluble matter enriched in Stage 1,3 and 5, the warm and humid paleoclimate period. According to the conductance of different oxygen isotope period in loess sections, on Stage 1 and 5, the salts enrichment were charged by temperature and participate at the same time, so its concentrations are high on central Loess Plateau; on Stage2,3 and 4, the salts concentrations in south sections are higher than north because their weak movement. The diffluent ions are not sensitive to climate changes on China Loess Plateau, but Ca~(2+), Mg~(2+), NO_3~-SO_4~(2-) are sensitive.

亚洲地形和海陆分布变化对东亚环境格局形成演化的作用：数值模拟与地质记录对比

Earlier studies on the distribution of geological environmental indicators in China revealed drastic changes from a zonal climate pattern (planetary-wave-dominant pattern) in the Paleogene to a monsoon-dominant one in the Neogene, which suggested an inception of the initial East-Asian summer monsoon. However, there are different views about the time and causes of the changes.Here, we attempt to compile a series of paleoenvironmental maps based on newly collected climate indicators from the literatures and chronologically constrained evidence of geological maps in order to re-examine the temporal and spatial evolution of climate belts in China during the Cenozoic with special emphasis on the changes of the arid belt. These indicators include mammalian fauna, coal, carbonate concretions, jarosite, salt, gypsum deposits and pollen assemblages etc, with chronological controls that we believe reliable. Pollen assemblages and mammalian fauna have been classified into three categories (arid, semi-arid/sub-humid, humid) to reflect the intensity of aridity/humidity. Salt, jarosite and gypsum deposits are classified as the arid indicators. Carbonate concretions and coal are classified into the semi-arid/sub-humid and humid one respectively. Paleoenvironmental maps at 8 time slices have been reconstructed. They are the Paleocene, Eocene, Oligocene, Miocene, Early Miocene, Middle Miocene, Late Miocene and Pliocene.And furthermore, we attempt to use IAP^AGCM to simulate the evolution of climate belts in emphasizing on the changes of the rain band, and compare the results with the paleoenvironmental maps in order to examine the causes of the drastic paleoenvironmental changes near the Oligocene/Miocene boundary. 36 sensitive numerical experiments are carried out using the IAP__AGCM to analyze the impacts of the uplift of the Himalayan-Tibetan complex, shrinkage of the Paratethys Sea, expansion of the South China Sea and the development of the polar ice sheets on rain band in China.The main conclusions are as follows:The obtained results essentially confirm the earlier conclusions about a zonal climate pattern in the Paleogene and a different pattern in the Neogene, and illustrate that a monsoon-dominant environmental pattern with inland aridity formed by the Early Miocene, which is temporally consist with the onset of eolian deposits in China.Cenozoic cooling and the formation of polar ice sheets are unlikely the main causes to the changes of environmental patterns mentioned above in China. But northern hemispheric cooling and the ice-sheets can intensify the Siberian High Pressure, and strengthen the winter monsoon circulations and enhance the aridity in the west part of China. These results support the earlier studies.Shrinkage of the Paratethys Sea and uplift of the Himalayan-Tibetan complex played important roles in strengthening the East Asian monsoon and induceing the above changes of environmental pattern, which is consistent with the earlier studies. Furthermore, "the monsoon-dominant pattern" appears when the Himalayan-Tibetan complex reaches to about 1000-2000 meters high and the Paratethys Sea retreats to the Turan Plate.4) Expansion of the South China Sea is another significant factor that drives the evolution of environmental patterns. We believe that the above three factors co-act and drive the change of the environmental patterns from a planetary-wave-dominant one to a monsoon-dominant one. However, the impacts of each factor vary by regions. The uplift mainly increases the humidity in Southwestern China and the aridity in northwestern country. The shrinkage mainly increases the humidity in Northern China and also enhances the aridity in the northwestern country. The expansion greatly increases the humidity in the south part of China.