西江流域环境河水地球化学研究

River is a major component of the global surface water and CO2 cycles. The chemistry of river waters reveals the nature of weathering on a basin-wide scale and helps us understand the exogenic cycles of elements in the continent-river-ocean system. In particular, geochemical investigation of large river gives important information on the biogeochemical cycles of the elements, chemical weathering rates, physical erosion rates and CO2 consumption during the weathering of the rocks within the drainage basin. Its importance has led to a number of detailed geochemical studies on some of the world's large and medium-size river systems. Flowing in the south of China, the Xijiang River is the second largest river in the China with respect to its discharge, after the Yangtze River. Its headwaters drain the YunGui Plateau, where altitude is approximately 2000 meters. Geologically, the carbonate rocks are widely spread in the river drainage basin, which covers an area of about 0.17xl06 km2, i.e., 39% of the whole drainage basin. This study focuses on the chemistry of the Xijiang river system and constitutes the first geochemical investigation into major and trace elements concentrations for both suspended and dissolved loads of this river and its main tributaries, and Sr isotopic composition of the dissolved load is also investigated, in order to determine both chemical weathering and mechanical erosion rates. As compared with the other large rivers of the world, the Xijiang River is characterized by higher major element concentration. The dissolved major cations average 1.17, 0.33, 0.15, and 0.04 mmol I"1 for Ca, Mg, Na, and K, respectively. The total cation concentrations (TZ+) in these rivers vary between 2.2 and 4.4 meq I'1. The high concentration of Ca and Mg, high (Ca+Mg)/(Na+K) ratio (7.9), enormous alkalinity and low dissolved SiO2/HCO3 ratio (0.05) in river waters reveal the importance of carbonate weathering and relatively weak silicate weathering over the river drainage basin. The major elements in river water, such as the alkalis and alkaline-earths, are of different origins: from rain water, silicate weathering, carbonate and evaporite weathering. A mixing model based on mass budget equation is used in this study, which allows the proportions of each element derived from the different source to be calculated. The carbonate weathering is the main source of these elements in the Xijiang drainage basin. The contribution of rainwater, especially for Na, reaches to approximately 50% in some tributaries. Dissolved elemental concentration of the river waters are corrected for rain inputs (mainly oceanic salts), the elemental concentrations derived from the different rock weathering are calculated. As a consequence, silicate, carbonate and total rock weathering rates, together with the consumption rates of atmospheric CO2 by weathering of each of these lithologies have been estimated. They provide specific chemical erosion rates varying between 5.1~17.8 t/km2/yr for silicate, 95.5~157.2 t/km2/yr for carbonate, and 100.6-169.1 t/km2/yr for total rock, respectively. CO2 consumptions by silicate and carbonate weathering approach 13><109and 270.5x10 mol/yr. Mechanical denudation rates deduced from the multi-year average of suspended load concentrations range from 92-874 t/km2/yr. The high denudation rates are mainly attributable to high relief and heavy rainfall, and acid rain is very frequent in the drainage basin, may exceed 50% and the pH value of rainwater may be <4.0, result from SO2 pollution in the atmosphere, results in the dissolution of carbonates and aluminosilicates and hence accelerates the chemical erosion rate. The compositions of minerals and elements of suspended particulate matter are also investigated. The most soluble elements (e.g. Ca, Na, Sr, Mg) are strongly depleted in the suspended phase with respect to upper continent crust, which reflects the high intensity of rock weathering in the drainage basin. Some elements (e.g. Pb, Cu, Co, Cr) show positive anomalies, Pb/Th ratios in suspended matter approach 7 times (Liu Jiang) to 10 times (Nanpan Jiang) the crustal value. The enrichment of these elements in suspended matter reflects the intensity both of anthropogenic pollution and adsorption processes onto particles. The contents of the soluble fraction of rare earth elements (REE) in the river are low, and REE mainly reside in particulate phase. In dissolved phase, the PAAS-normalized distribution patterns show significant HREE enrichment with (La/Yb) SN=0.26~0.94 and Ce depletion with (Ce/Ce*) SN=0.31-0.98, and the most pronounced negative Ce anomalies occur in rivers of high pH. In the suspended phase, the rivers have LREE-enriched patterns relative to PAAS, with (La/Yb) SN=1 -00-1 .40. The results suggest that pH is a major factor controlling both the absolute abundances of REE in solution and the fractionation of REE of dissolved phase. Ce depletion in river waters with high pH values results probably from both preferential removal of Ce onto Fe-Mn oxide coating of particles and CeC^ sedimentation. This process is known to occur in the marine environment and may also occur in high pH rivers. Positive correlations are also observed between La/Yb ratio and DOC, HCO3", PO4", suggesting that colloids and (or) adsorption processes play an important role in the control of these elements.

黄东海及朝鲜海峡冰后期陆架沉积物的环境磁学研究

There are four chapters in this dissertation. The first chapter briefly synthesizes the basic theories, methods and present-day applying situation of environmental magnetism. The second chapter probes into the magnetic mineral diagenesis in the post-glacial muddy sediments from the southeastern South Yellow Sea and its response to marine environmental changes, using the muddy sediment of Core YSDP103 formed in the shelf since about 13 ka BP. The third chapter illustrates the high-resolution early diagenetic processes by investigating the rapidly deposited muddy sediments during the last 6 ka in Cores SSDP-102 and SSDP-103 from the near-shore shelf of Korea Strait. The fourth chapter presents the results of detailed rock magnetic investigation of the surface sediments from the fine-grained depositional area on the outer shelf of the East China Sea in an attempt to provide environmental magnetic evidence for the provenance of the fine-grained deposit. Core YSDP103 was retrieved in the muddy deposit under the cold eddy of the southeastern South Yellow Sea, and the uppermost 29.79 m core represents the muddy sediments formed in the shelf since about 13 ka BP. The lower part from 29.79 to 13.35 m, called Unit A2, was deposited during the period from the post-glacial transgression to the middle Holocene (at about 6 ~(14)C ka BP) when the rising sea level reached its maximum, while the upper part above 13.35 m (called Unit Al) was deposited in a cold eddy associated with the formation of the Yellow Sea Warm Current just after the peak of post-glacial sea level rise. For the the uppermost 29.79 m core, detailed investigation of rock-magnetic properties and analyses of grain sizes and geochemistry were made. The experimental results indicate that the magnetic mineralogy of the core is dominated by magnetite, maghemite and hematite and that, except for the uppermost 2.35 m, the magnetic minerals were subject to reductive diagenesis leading to significant decline of magnetic mineral content and the proportion of low-coercivity component. More importantly, ferrimagnetic iron sulphide (greigite) is found in Unit A2 but absent in Unit Al, suggesting the control of marine environmental conditions on the magnetic mineral diagenesis. Magnetic parameters show abrupt changes across the boundary between the Unit Al and A2, which reflects a co-effect of environmental conditions and primary magnetic components of the sediments on the diagenesis. Alternating zones of high and low magnetic parameters are observed in Unit A2 of Core YSDP103, which is presumably due to periodic changes of the concentration and/or grain size of magnetic minerals carried into the study area. Cores SSDP-102 and SSDP-103, two studied sediment cores from the Korea Strait contain mud sequences (14 m and 32.62 m in thickness) that were deposited during the last 6,000 years. Analyses of grain sizes and geochemistry of the cores have demonstrated that the sediments have uniform lithology and geochemical properties, however, marked down-core changes in magnetic properties suggest that diagenesis has significantly impacted the magnetic properties. An expanded view of early diagenetic reactions that affect magnetic mineral assemblages is evident in these rapidly deposited continental shelf sediments compared to deep-sea sediments. The studied sediments can be divided into four descending intervals, based on magnetic property variations. Interval 1 is least affected by diagenesis and has the highest concentrations of detrital magnetite and hematite, and the lowest solid-phase sulfur contents. Interval 2 is characterized by the presence of paramagnetic pyrite and sharply decreasing magnetite and hematite concentrations, which suggest active reductive dissolution of detrital magnetic minerals, the absolute minimum abundance of magnetite is reached at the end of this interval. Interval 3 is marked by a progressive loss of hematite with depth, and at the base of this interval, 82% to 88% of the hematite component was depleted and the bulk magnetic mineral concentration was reduced to the lowest value in the entire studied mud section. Interval 4 has an increasing down-core enhancement of authigenic greigite, which is interpreted to have formed due to arrested pyritization resulting from consumption of pore water sulfate with depth. This is the first clear demonstration from an active depositional environment for a delay of thousands of years for acquisition of a magnetization carried by greigite. This detailed view of diagenetic processes in continental shelf sediments suggests that studies of geomagnetic field behavior from such sediments should be conducted with care. Paleoceanographic and paleoclimatic studies based on the magnetic properties of shelf sediments with high sedimentation rates like those in the Korea Strait are also unlikely to provide a meaningful signature associated with syn-depositional environmental processes. The rock magnetic properties of the surface sediments from the fine-grained depositional area on the outer shelf of the East China Sea, an area surrounded by sands, are investigated with a view to providing information on the sediment provenance. Multiple magnetic parameters such as magnetic susceptibility (%), anhysteretic remanent magnetization (ARM), saturation rernanent magnetization (SIRM), coercivities of SIRM (Her), and S ratios (relative abundance of low-coercivity magnetic minerals) are measured for all 179 surface samples, and partial representative samples are examined for their magnetic hysteresis parameters, temperature-dependence of magnetic susceptibility and x-ray diffraction spectra. Our research indicates that the magnetic mineralogy is dominated by magnetite with a small amount of hematite and is primarily of pseudo-single domain (PSD) to multidomain (MD) nature with a detrital origin. In the surface sediments, the granulometry of magnetic fractions is basically independent of grain sizes of the sediment containing the magnetic grains, and the composition of magnetic minerals remains almost homogeneous, that is, with a relatively constant ratio of low to high coercivity fraction throughout the area. The magnetic concentration in the study area generally decreases to the east or southeast accompanied by magnetic-particle fining to the east or to the northeast. The geographic pattern of magnetic properties is most reasonably explained by a major source of sediment jointly from the erosion of the old Huanghe River deposit and the discharge of the Changjiang River. The rock magnetic data facilitate understanding of the transport mechanism of fine-grained sediments in the outer shelf of the East China Sea.

胜利油田低渗透砂岩油藏非均质地质建模

Guided by geological theories, the author analyzed factual informations and applied advanced technologies including logging reinterpretation, predicting of fractal-based fracture network system and stochastic modeling to the low permeable sandstone reservoirs in Shengli oilfield. A new technology suitable for precious geological research and 3D heterogeneity modeling was formed through studies of strata precious correlation, relation between tectonic evolution and fractural distribution, the control and modification of reservoirs diagenesis, logging interpretation mathematical model, reservoir heterogeneity, and so on. The main research achievements are as follows: (1) Proposed four categories of low permeable reservoirs, which were preferable, general, unusual and super low permeable reservoir, respectively; (2) Discussed ten geological features of the low permeable reservoirs in Shengli area; (3) Classified turbidite fan of Es_3 member of the Area 3 in Bonan oilfield into nine types of lithological facies, and established the facies sequences and patterns; (4) Recognized that the main diagenesis were compaction, cementation and dissolution, among which the percent compaction was up to 50%~90%; (5) Divided the pore space in ES_3 member reservoir into secondary pores with dissolved carbonate cement and residual intergranular pores strongly compacted and cemented; (6) Established logging interpretation mathematical model guided by facies- control modeling theory; (7) Predicted the fracture distribution in barriers using fractal method; (8) Constructed reservoir structural model by deterministic method and the 3D model of reservoir parameters by stochastic method; (9) Applied permeability magnitudes and directions to describe the fractures' effect on fluid flow, and presented four different fractural configurations and their influence on permeability; (10) Developed 3D modeling technology for the low permeable sandstone reservoirs. The research provided reliable geological foundation for the establishment and modification of development plans in low permeable sandstone reservoirs, improved the development effect and produced more reserves, which provided technical support for the stable and sustained development of Shengli Oilfield.

济阳坳陷及其南缘奥陶系碳酸盐岩潜山储集性及控制因素

The main research area of this thesis is Jiyang Depression in the Bohaiwan Basin and its southern margin. The object formation is Ordovician carbonate. The research is based on the outcrop observation and measurement of Ordovician carbonate and the drilling data of the oilfield. The internal reservoir characteristics of carbonate buried hill and its distribution were studied by comprehensive methods of sedimentology, reservoir geology and structural geology and technics of cathodoluminescence(CL)3electron microprobe,casting and C O isotope analysis etc. The influence depth of paleokarst facies formed during the Paleozoic is discriminated as 36-84m. The sollution porosity is well developed in paleokarst facies of Ordovician carbonate and is an important type of internal reservoir of buried hill. It may be infered that the fractures may be formed mainly during the Mesozoic and Cenozoic, they were not developed during the early Paleozoic when only micro-fractures might be created. The carbon and oxigen isotope analysis shows that the calcite cements in the fractures of Ordovician carbonate and secondary solution pores were related with meteoric water and three stages of fractures were divided. The reservoir space of Ordovician carbonate are mainly secondary porosity, cavern and fracture. The development of structural fracture was controlled by the lithology and tectonic background. More fractures exist in dolomite than that in limestone. There are also more fractures near the fault and the axis of fold. The development of porous reservoir is mainly controlled by the lithology and diagenesis, especially dolomitization and dissolution. It also results in the heterogeneity vertically. So the lithology is the basic factor for the forming of internal reservoir of buried hill and the tectogenesis and diagenesis are key factors to improve it. The porosity in carbonate might experienced solution-cementation-resolution or recementation. The porosity evolution history was a kind of historical dynamic equilibrium. The internal reservoir of Ordovician carbonate is the comprehensive result of constructive and/or destructive diagenesis. The worm's eye maps of the early Paleozoic and middle-upper Proterozoic were plotted. It was inferred that the paleostress field evoluted from NNW to NW during the Mesozoic and Cenozoic. Three types of buried hills can be divided: C-P/Pzi, Mz/ Pzi and E/ Pzi. The unconformity of the buried hill of E/ Pzi type, comparatively, was formed and reconstructed latestly, t he p orous r eservoir c ould b e w ell p reseved. T his c ondition w as v ery favorable t o t he migration and accumulation of oil and gas and could form upstanding association of source-reservoir-cap rocks. The buried hills of Mz/ Pzi and C-P/Pz] type were took second place.

表生条件下铊矿物的氧化溶解动力学及其反应性迁移实验研究

贵州省兴仁县滥木厂铭矿床是世界上唯一的铭的独立矿床。多年来，由于对蛇矿产资源的开发，大量未及时提取和利用的含佗矿石堆积于地表，经过风化淋滤作用，进入当地的水源和土壤，并通过食物链进入人体。20世纪60-70年代，滥木厂地区有近1000名村民患有不同程度的铂中毒，轻者脱发、视力减退，重者失明、丧失劳动力，至今在该地区仍可见到铭中毒患者。该区成为世界上唯一爆发过大规模馆中毒的病发区。馆又是人体的非必需元素，体内任何含量的馆都会对人体造成危害。饮用水的安全标准中，铭的含量不得超过1μg／L。因此对表生条件下，含铂矿物的氧化溶解动力学以及反应性迁移的实验研究具有重要的现实意义。通过对滥木厂铭矿床中的主要含铭矿物（红铭矿）在酸性矿水条件下的氧化溶解过程、光照旧光照射和汞弧灯照射）对铭价态改变的影响，以及酸性矿水条件下铁对蛇吸附的实验研究，得到如下几点认识：1．红铭矿的氧化溶解动力学实验表明：红铂矿的氧化溶解速率受到温度、氧化剂中阴离子种类及氧化剂浓度的影响。随着温度的升高，红蛇矿的氧化速率增高；Cl-离子的存在更有助于红锭矿的氧化溶解，表现为氧化溶解速率的增高；随着氧化剂浓度的升高，红铭矿的氧化速率逐渐降低，这主要是由于高铁浓度下，红佗矿表面形成了一层厚约2nm的铁硫化合物的膜，减缓了红铭矿进一步溶解。红铭矿表面形态和成分的电镜分析表明，红铭矿表面具有较多的活性点，因此含铭矿石在初露地表时对环境的污染比较强烈，经过风化淋滤作用后，红铭矿表面的活性点减少，加之硫铁化合物膜的形成，阻止了其对环境的进一步污染。但这并不排除一旦环境介质改变，红铭矿表面氧化形成的膜被破坏，红铭矿的新鲜表面暴露出来，活性点增多，溶解性加强，继续对周围环境造成强烈的污染。从红蛇矿24小时溶解的总馆量来看，酸性矿水条件下红佗矿的氧化溶解是贵州省兴仁县滥木厂地区佗污染的一个重要来源。2．铭的光致氧化实验结果表明：无论日光还是汞弧灯照射，水溶液中的T1（I）均可被氧化成T1（III）。州值越低、光照强度越大，铭的光氧化速率越快，UVB区的紫外光对铭的光氧化起着主要作用，微生物作用在本实验条件下，相对于光氧化作用并不明显。3．铁对铭的吸附实验表明：铁的水合氧化物对水溶液中铭的吸附除受溶液的pH值和吸附剂的阴离子种类的影响外，主要与佗的价态有直接关系。铁的水合氧化物对Tl（I）具有一定的吸附能力，阴离子种类对T1（I）吸附的作用稍有差别，C1-离子存在时，铁对Tl（I）的吸附更强一些吸附率达到50％左右，而S叮一离子存在条件下，铁对Tl（I）的吸附率小于20％。碱性（pH＝10左右）条件下，铁对T1（I）的吸附较中胜条件更明显一些。T1（III）由于自身的水解作用很强，在不同pH值和不同阴离子存在条件下，与Fe（III）均可发生共沉淀作用而被完全从水溶液中脱除。利用光照将Tl（I）氧化成Tl（III），再利用T1（III）易被沉淀或共沉淀吸附的特性，将Tl以Tl（OH）3，的形式吸附固定下来，降低了铭的活动性，进而可以减少铭对环境的影响，为锭污染的环境治理提供了重要的理论依据。