扬子地区上奥陶－下志留统黑色岩系形成机理

The black rock series of the Upper Ordovician - Lower Silurian in Yangtze area are important source rocks and have exceptional characteristics of sediment, biology, element geochemistry, carbon and oxygen isotope, organic geochemistry and etc. These characteristics are the reflection of important geology events. Due to scarce system research, many problems that relate to the development mechanism of source rocks are not solved. And this restricts the exploration of Oil and gas in South China. In this paper, author studied the palaeo-climate, palaeo-structure and palaeo-environment of the Upper Ordovician - Lower Silurian in Yangtze area by sedimentology, palaeobiology and geochemistry, especially the element geochemistry and isotope geochemistry. The environment model of source rocks is established and some conclusions are drawn. The Upper Ordovician - Lower Silurian sediment types in Yangtze area are mostly black shales, next, mudstone, shell limestone and siltystone. During the Late Ordovician and Earily Silurian periods, a series of big upheaval and depressed are distributed in Yangtze area, and the strata pattern of interphase upheaval and depressed led to Yangtze palaeosea isolated with outside sea. So the stagnant and anoxic environment that are the favorable factor of rich organic black shales sediment is formed in Yangtze area. That Chemical Index of Alteration (CIA) values of the lower Wufeng formation and Longmaxi formation exhibits moderate chemistry weathering suggests they were deposited under the circumstances of the warm and humid climate. However, the large difference of the CIA values of N.extraordinarius-N.ojsuensis biozone suggests that climate is changeful. Therefore, there were two different kinds of climates in the course of the deposition of the Wufeng formation and Longmaxi formation. During the Late Ordovician - Earily Silurian periods, in Yangtze palaeosea, the surface water which is full of rich nutriment and abundant bacterium - algae has high palaeo-productivity that is obvious difference in the different space – time. The content of sulphate changes gradually from the surface water columns to the deep water columns. That is, salinity in the surface water columns is serious low and the salinity in deep water columns is normal. Salinity delamination is favor of the forming of deep anoxic environment. During Wufeng period, the oxidated and low sulfate environment exists in the upper Yangtze palaeosea, while the anoxic and normal salinity environment occurs in the lower Yangtze palaeosea. During the Late Wufeng and Guanyinqiao periods, the steady anoxic environment is replaced by oxidated environment. During the Longmaxi period, layered and anoxic environment recur. In Yangtze area, studies of δ13C of sedimentary organic carbon show a positive δ13C excursion up to 4‰ in the Guanyinqiao stage and then, acute negative excursion in the earily Longmaxi stage. These organic carbon isotopes curve are not only efficient measure of carving up strata borderline, but also reflected the change of originality productivity. These organic carbon isotopes curves showed the process of the enhanced embedding of the global organic carbon. Anoxic event is the main factor of increasing organic carbon embedding speed. And the reduced organic carbon embedding in Hirnantian stage is due to the water column with abundant oxygen. The δ34S values are gradually positive excursion from P.pacificus biozone to N.extraordinarius biozone, and reach the maximum in the Upper Hirnantian stage. Then, the δ34S values are negative excursion. The excursions of δ13C and δ34S reflect the acute change of environment. The formation of source rocks is largely dependent on the nature of organisms from which kerogen is derived and the preservation conditions of organic matter, which are fundamentally dependent on a favourable combination of various elements in which organisms live and are subsequently buried. These elements include palaeoclimate, palaeostructure and palaeoenvironmental conditions. Based on above mentioned circumstance, the coupling connection of source rock and the palaeoclimate, and of palaeostructure and palaeoenvironmental conditions are confirmed, and the “anoxic-marginal depression-photosynthesis” environemental model is established. It is indicated that anoxic played important role in production of organic matter. The produced organic matter was accumulated in marginal depression of the Yangtze area. The photosynthesis is favor of the high productivity. Source rocks have a good perspective, like that of “hot shale” deposited in North Africa.

陕西关中盆地地热水循环的同位素研究

Geothermal resource is rich in Guanzhong Basin, but as to its cycle characteristic, there has been lack of systematic study so far. Blind exploitations lead to water-temperature reducing, the decrease of spring flow rate and so on. Based on groundwater system and hydrogeological and hydrological geochemical theory, this paper studied the recycling type of geothermal water and analyzed the resources of dissolved inorganic carbon (DIC) and sulfate. The origin of the internal geothermal water is ice and snow in Qinling Mountain and Liupan Mountain above 1400m. The precipitation and surface water entered the deep part of the basin along piedmont faults, heated and water-expansion increased. The karst groundwater comes from meteoric water of the bare carbonate rock area in the North Mountains. Geothermal-water DIC mainly came from the dissolution of carbonate rock in the deep part of Guanzhong Basin, sulfate of Xi’an depression and Lishan salient came from the dissolution of continental evaporate , and sulfate of Gushi depression and Xianli salient came from co-dissolution of continental and marine evaporate. The above results supply science basis for reasonable exploitation and sustainable utilization of the geothermal water in Guanzhong Basin.

新元古代陡山沱期古海洋的氧化还原环境演变

High resolution geochemical analysis of Ediacaran Doushantuo Formation deposits in eastern Gorges area, including carbon and sulfur isotope compositions, trace elements, rare earth elements, and so on, show a whole panorama of the oceanic environment in Ediacaran Doushantuo Formation. The deposits of Doushantuo II recorded consistent δ13Corg values and variable δ13Ccarb values, which suggets that it is strongly redox stratified in Doushantuo ocean, and there is a large DOC reservior in the deep ocean. The redox state of Doushantuo ocean in Yangtze area was not steady. The movement of chemocline was concerned with the transgression and/or regression. During the transgression, raising sea level and upwelling with anoxic deep water would cause the ocean anoxic; during the regression, declining sea level and weathered sulfate input would cause the suface ocean becoming oxic. The oxidations of this DOC reservior would caused negative δ13C excurions in Doushantuo Formation. Comparing with oceanic redox states and fossils productivity, we found that the stratum with high biologic productivity and diversity did not indicated oxic conditions. In the opposite, these stratum recorded anoxic conditions. We suggeste that it would be relatived to burial and preservation of fossils, because anoxic conditions are in favor of burial and preservation of fossils. It is proved that methane seep occurred at the base of Duoshantuo cap carbonate. However, comparing cap carbonate with seep carbonate, we found that oxidation of methan and the post-diagenesis could not derictely result in cap carbonate deoposition. Cap carbonate would be derived from the high level CO2 in atomosphere.

华南埃迪卡拉纪末期硅质岩和深海的氧化还原状态

A suit of cherts deposited in deep-ocean basin of South China during terminal Ediacaran and the beginning of Early Cambrian (about 550～540Ma). The origin of these cherts are controversial, and contrary standpoints exist for the redox state of the terminal Ediacaran deep-ocean because of poor study. In this paper, a detailed sedimentology, element and stable isotope geochemistry study were conducted for cherts of Liuchapo Formation in Anhua County, Hunan Province, Laobao Formation in Sanjiang County, Guangxi Province, and Piyuancun Formation in Xiuning County, Anhui Province. Some conclusions were drawn: (1) These cherts were mainly formed through chemical deposition of dissolved silica derived from chemical weathering in continent. Biological processes played a part in the cherts formation, however, the influence of hydrothermal fluids and detritus materials were trivial. (2) The terminal Ediacaran deep-ocean was anoxic and gradually oxidized. (3) Intense bacterial sulfate reduction decreased sulfate concentration in the ocean and the water column became euxinic during Ediacaran-Cambrian transition period. (4) Due to a high CO2 concentration in the terminal Ediacaran atmosphere, chemical weathering in continent dramatically increased and huge amounts of nutrimental material were transferred into ocean. The biota bloomed because of the nutrimental material. Degradation of huge amounts of organic matter maintained dissolved organic carbon reservoir in the ocean, and prolonged the deep-ocean anoxia.

湘西地区上震旦统上部－下寒武统底部黑色岩系沉积学及地球化学

Widespread black chert-shales occur in the Ediacaran-Cambrian(E-C) boundary successions along the flank of Yangtze Platform, South China, remarkable changes in sedimentology, geochemistry and biology were recorded. Although extensive studies were carried out upon this boundary succession, the origin of black chert-shales still remain controversial. This paper focuses on the E-C black chert-shales in western Hunan, South China, upon which detailed depositional and geochemical changes are documented, accordingly a depositional model for black chert-shales is proposed. Stratigraphic anatomy across the depositional strike demonstrates that the shallow-water Dengying dolostone along the platform margin sharply pass basinward into the Liuchapo chert successions, which indicate syndepositional extensional faulting at depth could have occurred along the platform margin. The deep-water Niutitang phosphorite-rich black shales are either underlain by the Dengying dolostones on the platform margin toward platform interior or directly by the Liuchaopo chert successions farther basinwards. By detailed investigation, silica chimneys are firsly identified approximately in the chert along platform margin; two types of silica chimneys, including mounded and splayed/funnelized chert(generally brecciated) bodies are further sorted out. The mounded chert are exitbited by domed or hummocky surfaces on the top and irregular spongy to digitiform internal fabrics; within the silica mounds, abundant original vesicles/voids and/or channels were mostly plugged by initial chalcedony, quartze crystals with minor dolomite and bladed barite crystals. Splayed/funnelized brecciated chert “intrusion” cross-cut the uppermost dolostones capping to the horizon underneath, and are directly overlain by the Niutitang phosphorite-rich black shales. Their similarities to the silica chimneys reported from the oceanic spreading centres suggest a similar origin responsible for these unique silica bodies which is also supported by the microthermonmetric data and element geochemistry. High P, Ba, Fe contents and positive correlation between Fe and TOC concentrations in the Niutitang black shales indicate a high palaeo-productivity in the Early Cambrian ocean. The low Th/U and the high V/Cr, V/Sc, V/(V+Ni) ratios in the black shales suggest an anoxic water condition during this interval. Furthermore, Positive Eu anomalies and high Ba contents in the sediments also imply a hydrothermal influence on the formation of Niutitang black shales. To better constrain the placement of deep-water successions straddling the E-C boundary and the timing of hydrothermal silica chimneys, sensitive high-resoluton ion microprobe(SHRIMP) U-Pb dating of zircon grains from tuffs within the chert succession of Liuchapo Formation at Ganziping was conducted and yields a weighted-mean 206Pb/238Pb age at 536.6±5.5Ma, younger than E-C boundary age(542.0±0.3Ma). This age combined with carbon isotopic data is then proposed to correspond to the U-Pb age of zircons(538.2±1.5Ma) from the Zhongyicun member of Meishucun Formation at Meishucun in eastern Yunna, thus, the E-C boundary in Gazngziping was placed between the Dengying formations and Liuchapo formatioms. therefore, the silica chimneys took place at the beginning of the Cambrian period. The temporal coincidence of silica chimneys and negative excursions of δ13C and δ34Spy pairs suggest hydrothermal activities were likely responsible for the isotopic changes. Under such a circumstance, vast amounts of greenhouse gases(CO2, CH4, H2S), with highly 13C-depleted carbon and 34S-depleted sulfur would be released into the ocean and atmosphere. A positive shift in δ34Scas and Δ34S values from the late Ediacaran to the Early Cambrian could be a reflection of enhanced bacterial sulfate reduction(BSR), strengthened by the intensified oceanic anoxia stimulated by hydrothermal activities. Based on the analyses of sedimentology and geochemistry, a model- “oceanic anoxia induced by hydrothermal–volcanic activies” was proposed to responsible for the formation of black chert-shales during this E-C transition. Under this case, hydrothermal-volcanic activies could release large large amount of greenhouse into atmosphere and metal micronutrients into the ocean, which may lead to global warming, stratified ocean, thereby a high palaeoproductivity; on the other hand, the massive releasing of reduced hydrothermal fluids with abundant H2S, could have in turn enhanced the ocean anoxia. All of these were favourable the for preservation of organic matter, and subsequent extensive deposition of black silica-shales.

流体地球化学：成因、流动和流体-岩石相互作用及塔里木盆地实例研究

Geofluid in sedimentary basins is related to petroleum generation, migration, accumulation and preservation, and is a topic of geological frontier. By integrating the multi-discipline methods of petroleum geochemistry, sedimentology, hydrogeology, petroleum geology and experimental geochemistry, the thesis has carried out experiments of microcline dissolution in solutions with organic acids, crude oil, brines with high total dissolved solids (TDS), and has dealt with Al distribution between the crude oil and the brines after the experiments. Cases for study includes Central Tarim, Hetianhe Gas Field and Kucha forland basin with data containing fluid chemistry and isotopic compositions, thin sections of sandstones and carbonates, homogenization temperatures and salinities of fluid inclusions, isotopic compositions of bulk rock and autigenic minerals. The aims are to elucidate fluid origin and flow in the three areas, effect of hydrocarbon emplacement on diagenesis, and to show occurrence of microbe-mediated, and thermochemical sulfate reduction in the Tarim Basin. Microcline dissolution experiments show that after 100 hour, part of the dissolved Al distributes in the crude oil, and the Al concentrations in the crude oil rise when organic acids are added. The result can be used to explain that most oilfield waters in the Tarim Basin are characterized by less than 3mg/L Al. Crude oil added to the solutions can enhance microcline dissolution, which is also observed in the case - Silurian sandstones with early crude oil emplacement in the Central Tarim. Al and Si have higher concentrations in the experiments of oxalic acid than of acetic acid under the same pH conditions, suggesting that there exist Al-oxalate and Si-oxalate complexes. Presence of acetate can enhance the activity of Ca and Al, but Al concentrations have not been increased significantly due to formation of small Al-acetate complex during the experiments. Relationships between δD and δ~(18)O in conjunction with chemistry of oilfield waters show that the waters are evaporated connate waters, which subsequently mixed with meteoric water, and were influenced by water-rock interactions such as salt dissolution, dolomitization of calcite, albitization of feldspar. In the Hetianhe Gas Field where salt dissolution took place, δD and δ~(18)O values can be used to trace nicely meteoric water recharge area and flow direction, but TDS can not. Part of the waters have high TDS but very light δD and δ~(18)O. When combined with paleo-topography, or fluid potentials, meteoric water is suggested to flow eastward in the Hetianhe Gas Field, which is the same with the Central Tarim. Whist in the Kuche forland basin, meteoric water may have permeated Cambrian-Ordovician strata. Relationship between ~(87)Sr/~(86)Sr and 1/Sr can be used to indicate migration and mixing of brines from carbonate strata (low ~(87)Sr/~(86)Sr ratio but high Sr content), clastic strata (high ~(87)Sr/~(86)Sr ratio but low Sr content) and crystalline basement (high ~(87)Sr/~(86)Sr ratio and heavy δ~(18)O value). Using this approach, it can be found that ~(87)Sr-depleted brine from Ordovician carbonates have migrated up to and mixed with ~(87)Sr-enriched waters from Silurian and Carboniferous sandstones, and that Silurian brines have mixed with meteoric water. In the Kuche forland basin, brines from the Cambrian and Ordovician carbonates have higher ~(87)Sr/~(86)Sr ratios than those from the overlying sandstones, when combined with chemistry, δ~(15)N and ~3He/~4He ratios of the coexisting natural gases, suggesting that the brines were derived from the basement. There exists some debate on the effect of hydrocarbon emplacement on mineral diagenesis. Case-study from Silurian sandstones in the Central Tarim show that quartz has kept overgrowing secondarily when oil saturation was decreased by meteoric water flushing subsequently to hydrocarbon emplacement. Silicon precipitates on the water-wet quartz surface, leading to decreased Si concentration close to the surface. A Si grads can result in Si diffusion, which supplies Si for quartz overgrowth. Hydrocarbon oxidation-sulfate reduction is an important type of organic-inorganic interaction. Not only can it make secondary alteration of hydrocarbons, but generate H_2S and CO_2 gases which can improve reservoir property. Thermochemical sulfate reduction took place at the temperatures more than 125 ℃ to 140 ℃ in the Cambrian-Ordovician carbonates, the products - H_2S and CO_2 gases migrated up to the Silurian, and precipitated as pyrite and calcite, respectively. The pyrite has an average δ~(34)S value close to those of Ordovician seawater and anhydrite, and calcite has δ~(13)C value as low as -21.5‰. In the Hetianhe Gas Field, sulfate reduction bacteria carried by meteoric water flowing eastward may have preferentially depleted ~(12)C of light hydrocarbon gases, and results in heavier δ~(13)C values of the residual hydrocarbon gases and higher molar CO_2 in the natural gases in the west than in the east. Coexisting pyrite has δ~(34)S values as low as -24.9‰.

东南极格罗夫山地区的土壤特征及其环境研究

The Grove Mountains, including 64 nunataks, is situated on an area about 3200km2 in the inland ice cap of east Antarctica in Princess Elizabeth land (72o20'-73°101S, 73°50'-75o40'E), between Zhongshan station and Dome A, about 450km away from Zhongshan station (69°22'S, 76°22'E). Many workers thought there was no pedogenesis in the areas because of the less precipitation and extreme lower temperature. However, during the austral summer in 1999-2000, the Chinaer 16 Antarctic expedition teams entered the inland East Antarctica and found three soil spots in the Southern Mount Harding, Grove Mountains, East Antarctica. It is the first case that soils are discovered in the inland in East Antarctica. Interestingly, the soils in this area show clay fraction migration, which is different from other cold desert soils. In addition, several moraine banks are discovered around the Mount Harding. The soil properties are discussed as below. Desert pavement commonly occurs on the three soil site surfaces, which is composed of pebbles and fragments formed slowly in typical desert zone. Many pebbles are subround and variegated. These pebbles are formed by abrasion caused by not only wind and wind selective transportation, but also salt weathering and thaw-freezing action on rocks. The wind blows the boulders and bedrocks with snow grains and small sands. This results in rock disintegration, paved on the soil surface, forming desert pavement, which protects the underground soil from wind-blow. The desert pavement is the typical feature in ice free zone in Antarctica. There developed desert varnish and ventifacts in this area. Rubification is a dominant process in cold desert Antarctic soils. In cold desert soils, rubification results in relatively high concentrations of Fed in soil profile. Stained depth increases progressively with time. The content of Fed is increasing up to surface in each profile. The reddish thin film is observed around the margin of mafic minerals such as biotite, hornblende, and magnetite in parent materials with the microscope analyzing on some soil profiles. So the Fed originates from the weathering of mafic minerals in soils. Accumulations of water-soluble salts, either as discrete horizons or dispersed within the soil, occur in the soil profiles, and the salt encrustations accumulate just beneath surface stones in this area. The results of X-ray diffraction analyses show that the crystalline salts consist of pentahydrite (MgSO4-5H2O), hexahydrite (MgSO4-6H2O), hurlbutite (CaBe2(PO4)2), bloedite (Na2Mg(S04)2-4H2O), et al., being mainly sulfate. The dominant cations in 1:5 soil-water extracts are Mg2+ and Na+, as well as Ca2+ and K+, while the dominant anion is SO42-, then NO3-, Cl- and HCO3-. There are white and yellowish sponge materials covered the stone underside surface, of which the main compounds are quartz (SiO2, 40.75%), rozenite (FeSOKkO, 37.39%), guyanaite (Cr2O3-1.5H2O, 9.30%), and starkeyite (MgSO4-4H2O, 12.56%). 4) The distribution of the clay fraction is related to the maximum content of moisture and salts. Clay fraction migration occurs in the soils, which is different from that of other cold desert soils. X-ray diffraction analyses show that the main clay minerals are illite, smectite, then illite-smectite, little kaolinite and veirniculite. Mica was changed to illite, even to vermiculite by hydration. Illite formed in the initial stage of weathering. The appearance of smectite suggests that it enriched in magnesium, but no strong eluviation, which belongs to cold and arid acid environment. 5) Three soil sites have different moisture. The effect moisture is in the form of little ice in site 1. There is no ice in site 2, and ice-cement horizon is 12 cm below the soil surface in site 3. Salt horizon is 5-10 cm up to the surface in Site 1 and Site 2, while about 26cm in site 3. The differentiation of the active layer and the permafrost are not distinct because of arid climate. The depth of active layer is about 10 cm in this area. Soils and Environment: On the basis of the characteristics of surface rocks, soil colors, horizon differentiation, salt in soils and soil depth, the soils age of the Grove Mountains is 0.5-3.5Ma. No remnants of glaciations are found on the soil sites of Mount Harding, which suggests that the Antarctic glaciations have not reached the soil sites since at least 0.5Ma, and the ice cap was not much higher than present, even during the Last Glacial Maximum. The average altitude of the contact line of level of blue ice and outcrop is 2050m, and the altitude of soil area is 2160m. The relative height deviation is about 110m, so the soils have developed and preserved until today. The parental material of the soils originated from alluvial sedimentary of baserocks nearby. Sporepollen were extracted from the soils, arbor pollen grains are dominant by Pinus and Betula, as well as a small amount Quercus, Juglans, Tilia and Artemisia etc. Judging from the shape and colour, the sporepollen group is likely attributed to Neogene or Pliocene in age. This indicates that there had been a warm period during the Neogene in the Grove Mountains, East Antarctica.

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.

中-新元古代海洋的硫和碳同位素的演化

Data on seawater carbon isotope in the Mesoproterozoic and Neoproterozoic is abundant. However, the sulfur isotopic age curve of seawater sulfates determined through the analysis of sulfur isotopic composition of marine evaporite is uncertain in the Mesoproterozoic and Neoproterozoic since evaporites are generally rare in Precambrian. The Mesoproterozoic and Neoproterozoic Carbonate Formations preserve not only the carbon isotopic records, but also the sulfur isotopic records of coeval seawater in the Huabei Platform and the Yangtze Platform, China. Sulfur isotopic composition can be determined by the extraction of trace sulfate from carbonate samples. Successive measurements of sulfur and carbon isotopic compositions of carbonate samples from the Mesoproterozoic and Neoproterozoic strata in the Huabei Platform and the Yangtze Platform was accomplished through the extracting of trace sulfate from carbonates. Sulfur and carbon isotopic compositions of coeval seawater were obtained from analytical results of sulfur and carbon isotopes of the same sample without diagenetic alteration. The high-resolution age curve of sulfur isotope given in this paper may reflect the trend of variations in sulfur isotope composition of seawater sulfates during the Mesoproterozoic and Neoproterozoic. It can be correlated with the characteristics of variation in age curve of carbon isotope of coeval seawater carbonates. The δ34S values of seawater varied from +10.3-37.0‰ during the Mesoproterozoic, which took on oscillated variation on the whole. The δ34S values took on high values in the Mesoproterozoic Chuanlinggou stage, Tuanshanzi stage Tieling stage and in Neoproterozoic Jing'eryu stage. The average of those was about +30‰. The sulfates have low δ34S values in the Mesoproterozoic Yangzhuang stage and Hongshuizhuang stage, The average of those was all lower than +20‰. There occured large-amplitude changs in δ34S values of seawater during the Mesoproterozoic. Large-amplitude oscillate of 534S values occured in the intervals of 1600~1400Ma and 1300~1200Ma. The δ13C values of seawater are mostly negative in Changcheng stage of late Paleoproterozoic, -0 ± 1‰ range in Jixian stage of Mesoproterozoic , and the positive 2±2‰ commonly in early Neoproterozoic Jing'eryu stage. From 1000 Ma to 900 Ma, about 108 years interval of oceanic 513C record is shortage. At the end of Paleoproterozoic (1700 - 1600 Ma), the oceanic 813C values change from -3‰ to 0‰, but strongly oscillate near 1600 Ma. Two larger variations of seawater 513C values occur in the Mesoproterozoic: one is a cycle of about 4%o happens at ca. 1400 Ma; another is rise from >2‰ to>5‰ at ca. 1250 Ma and then become stable at the near 1000 Ma. There appears a large positive excursion over +20‰ in 534S value of ancient seawater sulfates in the early Doushantuo stage. Simultaneously, 8 C values of ancient seawater occur a positive excursion reaching 10‰. These allow δ4S values and 513C values to reach high values of+51.7‰ and +6.9‰, respectively. The range of variation in 834S values of seawater is relatively narrow and 513C values are quite high in the middle Doushantuo stage. Then, δ34S values of seawater become oscillating, the same happens in δ13C values. Negative excursions in 834S values and 813C values occur simultaneously at the end of the Doushantuo stage, and the minimum of δ34S values and δ13C values dropped to -11.3‰ and -5.7‰, respectively. The ancient seawater in the Dengying stage has high δS values and δ13C values. Most of the δ34S values of the trace sulfate samples varied between +23.6‰ and +37.9‰ except two boundaries of the Dengying Formation, and the S13C values of the carbonate samples of the Dengying Formation varied between +0.5‰ and +5.0‰. There appeared large negative excursion in 834S values and δ13C values of ancient seawater at the bounder of Precambrian-Cambrian. The isotopic characteristics of sulfur and carbon implicated that the organic productivity and isotopic fractionation caused by biology were low and the palaeoceanic environment was quite unstable during the Mesoproterozoic. The increase and subsequent oscillation of seawater δ13C value occurred from 1700 to 1600 Ma and near 1300 Ma may be responsible to the two global tectonic events happened at coeval time. The characteristics of variation in sulfur and carbon isotopes of ancient seawater imply strong changes in oceanic environment, which became beneficial to inhabitation and propagation of organism. The organic production and the burial rate of organic carbon once reached a quite high level during the Doushantuo stage. However, the state of environment became unstable that means the global climate and the environment possibly were fluctuating and reiterating after the global glaciation. The negative excursions of S34S values and δ13C values occurring at the end of the Doushantuo stage represent a global event, which might be relative to the oxidation of deep seawater. The isotopic characteristics of sulfur and carbon implicated that there were a high organic productivity and a high burial rate of organic carbon in the Dengying stage. It is obvious that the palaeoceanic environment in Dengying stage was stable corresponding and beneficial for biology to inhabit and propagate except for the two boundaries. The tendency of sulfur and carbon isotopic variations maybe resulted from the gradual oxygenation of ocean environment during the Dengying stage. It has been reported that the secular variations of the sulfur isotopic compositions in seawater was negative correlated with that of carbon isotopic compositions. However, our results show that it is not the case. They were negatively correlated in some intervals and positively in some other intervals of the Mesoproterozoic and Neoproterozoic. The difference in correlation may be associated with the changes in conditions of redox in oceanic environment, e.g. sharp change of the oxidation-reduction interface. The strong changes in global environment may induce the abnormality to occur in the biogeo chemical S and C cycles in the ocean and accordingly sharp Variations in isotopic composition of seawater sulfur and carbon during the Mesoproterozoic and Neoproterozoic. Simultaneously, the global tectonism caused large changes of 87Sr/86Sr ratios. The leading factor that causes the variation in isotopic composition is different in the different intervals of the Mesoproterozoic and Neoproterozoic. Thus, there may exist different models of the biogeochemical S and C cycles in the ocean during the Mesoproterozoic and Neoproterozoic.

Ozonation of the purified hydrolyzed azo dye Reactive Red 120 (CI)

The combination of chemical and biological water treatment processes is a promising technique to reduce recalcitrant wastewater loads. The key to the efficiency of such a system is a better understanding of the mechanisms involved during the degradation processes. Ozonation has been applied to many fields in water and wastewater treatment. Especially for effluents of textile finishing industry ozonation can achieve high color removal, enhance biodegradability, destroy phenols and reduce the COD. However, little is known about the reaction intermediates and products formed during ozonation. This work focuses on the oxidative degradation of purified (>90%), hydrolyzed Reactive Red 120 (Color Index), a widely used azo dye in the textile finishing processes with two monochlorotriazine anchor groups. Ozonation of the dye in ultra pure water was performed in a laboratory scale cylindrical batch reactor. Decolorization, determined by measuring the light absorbance at the maximum wavelength in the visible range (53 5 nm), was almost complete after 150 min with an ozone concentration of 12.8 mg/l. The TOC/TOC0 ratio was about 74% and the COD was diminished to 46% of the initial value. The BOD5/COD ratio increased from 0.01 to 0.14. To obtain detailed information on the reaction processes during ozonation and the resulting oxidation products organic and inorganic anions were analyzed. Oxidation and cleavage of the azo group yielded nitrate. Cleavage of the sulfonic acid groups of aromatic rings caused an increase in the amount of sulfate. Formic acid and oxalic acid were identified as main oxidation products by high performance ion chromatography (HPIC). The concentrations of these major products were monitored at defined time intervals during ozonation.

Effects of organic modifiers on solute retention and electrokinetic migrations in micellar electrokinetic capillary chromatography

Influences of seven organic modifiers, including urea, methanol (MeOH), dioxane (DIO), tetrahydrofuran (THF), acetonitrile (ACN), 1-propanol (1-PrOH) and 2-propanol (2-PrOH), on the solute retention and the electrokinetic migrations in micellar electrokinetic capillary chromatography (MEKC) are investigated with sodium dodecyl sulfate (SDS) micelle as pseudostationary phase. It is observed that in the limited concentration ranges used in the MEKC systems the effect of organic modifier concentration on the retention can be described by the equation logk'=logk'(w)-SC for most binary aqueous-organic buffer, but deviations from this retention equation are observed at ACN and particularly THF as organic modifiers. With parameter S as a measure of the elutropic strength, the elutropic strength of the organic modifiers is found to follow a general order urea

The surface sites of sulfated zirconia studied in situ by laser-induced fluorescence spectroscopy

The surface sites of sulfated zirconia were investigated in situ by laser-induced fluorescence spectroscopy using aniline as the probe molecule. Different from the cases for many other oxides, the aniline adsorbed on the unique active sites of sulfated zirconia at r.t. is changed into another species, which emits a characteristic fluorescence band at 422 nm. The results illustrate that the sulfate groups in sulfated zirconia are favorable for the generation of these unique active sites, which also rarely exist on pure zirconia composed of tetragonal and monoclinic phases but do not exist on pure zirconia composed of monoclinic phase. (C) 2004 Elsevier B.V. All rights reserved.

An investigation into the tropospheric chemistry of acidic aerosols and ammonia in the laboratory

This thesis describes a broad range of experiments based on an aerosol flow-tube system to probe the interactions between atmospherically relevant aerosols with trace gases. This apparatus was used to obtain simultaneous optical and size distribution measurements using FTIR and SMPS measurements respectively as a function of relative humidity and aerosol chemical composition. Heterogeneous reactions between various ratios of ammonia gas and acidic aerosols were studied in aerosol form as opposed to bulk solutions. The apparatus is unique, in that it employed two aerosol generation methods to follow the size evolution of the aerosol while allowing detailed spectroscopic investigation of its chemical content. A novel chemiluminescence apparatus was also used to measure [NH4+]. SO2.H2O is an important species as it represents the first intermediate in the overall atmospheric oxidation process of sulfur dioxide to sulfuric acid. This complex was produced within gaseous, aqueous and aerosol SO2 systems. The addition of ammonia, gave mainly hydrogen sulfite tautomers and disulfite ions. These species were prevalent at high humidities enhancing the aqueous nature of sulfur (IV) species. Their weak acidity is evident due to the low [NH4+] produced. An increasing recognition that dicarboxylic acids may contribute significantly to the total acid burden in polluted urban environments is evident in the literature. It was observed that speciation within the oxalic, malonic and succinic systems shifted towards the most ionised form as the relative humidity was increased due to complete protonisation. The addition of ammonia produced ammonium dicarboxylate ions. Less reaction for ammonia with the malonic and succinic species were observed in comparison to the oxalic acid system. This observation coincides with the decrease in acidity of these organic species. The interaction between dicarboxylic acids and ‘sulfurous’/sulfuric acid has not been previously investigated. Therefore the results presented here are original to the field of tropospheric chemistry. SHO3-; S2O52-; HSO4-; SO42- and H1,3,5C2,3,4O4-;C2,3,4O4 2- were the main components found in the complex inorganic-organic systems investigated here. The introduction of ammonia produced ammonium dicarboxylate as well as ammonium disulfite/sulfate ions and increasing the acid concentrations increased the total amount of [NH4+].

Optimised crystal morphologies for active pharmaceutical ingredients and related studies

The majority of active pharmaceutical ingredients (APIs) are crystalline solids in their pure forms. Crystalline solids have definable morphologies, i.e. shape and size. Crystal morphology is determined by both the internal structure of the crystals and external factors during growth from solution. The morphology of a crystal batch can affect key processes during manufacturing. Companies generally accept whatever morphology the manufacturing process provides and deal with any subsequent problems by costly trouble‒shooting. Rational design of optimised morphologies for crystalline pharmaceutical solids would be a very significant technical and commercial advance. Chapter one introduces the concept of crystal nucleation and growth. The phenomenon of polymorphism alongside the causes and impact is discussed. A summary of the scope of instrumentation used in the investigation of crystal polymorphism and morphology, including crystal size distribution (CSD), is also included. Chapter two examines the research carried out during an exploration of the optimum crystallisation parameters of phenacetin. Following a morphological study, the impact this induces on particle density and flow properties is examined. The impact of impurities on the crystallisation properties of phenacetin is investigated. Significantly, the location of impurities within individual crystals is also studied. The third chapter describes an industrial collaboration looking at the resolution and polymorphic study of trometamol and lysine salts of ketoprofen and 2‒phenylpropionic acid (2‒PPA). Chapter four incorporates a solid state study on three separate compounds: 2‒chloro‒4‒nitroaniline, 4‒hydroxy‒N‒phenylbenzenesulfonamide and N‒acetyl‒D‒glucosamine‒6‒O‒sulfate. 2‒Chloro‒4‒nitroaniline and 4‒hydroxy‒N‒phenylbenzenesulfonamide both produced interesting, extreme morphologies which warranted further investigation as part of a collaborative study. Following a summarisation of results in chapter five, chapter six contains the full experimental details, incorporating spectral and other analytical data for all compounds synthesised during the course of the research.

Geochemistry, mineralogy, and chemical modeling of the acid crater lake of Kawah Ijen volcano, Indonesia

The Kawah Ijen volcano-with a record of phreatic eruptions-has its 1000 m wide crater filled with a lake that has existed for at least one century. At present, the lake waters are hot (T ≈ 37°C), strongly mineralized (TDS = 105 g/L) and extremely acidic (pH ≈ 0.4). By its volume, the Javanese lake is probably the largest accumulation in the world of such acidic waters. Mineralogy of the suspended solids within the lake waters suggests that concentrations of Si, Ca, Ti, and Ba are controlled by precipitation of silica, gypsum, anatase, and barite. Lake sediment is composed of chemical precipitates with composition similar to the suspended solids. Thermodynamic calculations predict that the lake waters have reached equilibrium with respect to α-cristobalite, barite, gypsum, anglesite, celestite, and amorphous silica, in agreement with the analytical observations. Significant concentrations of ferric iron suggest that the current lake waters are fairly oxidized. Sulfides are absent in the water column but are always present in the native S spherules that form porous aggregates which float on the lake. The presence of native S provides direct evidence of more reduced conditions at the lake floor where H2S is probably being injected into the lake. With progressive addition of H2S to the acid waters, native S, pyrite, and enargite are theoretically predicted to be saturated. Reactions between upward streaming H2S-bearing gases discharged by subaqueous fumaroles, and metals dissolved in the acidic waters could initiate precipitation of these sulfides. A model of direct absorption of hot magmatic gases into cool water accounts for the extreme acidity of the crater lake. Results show that strongly acidic, sulfate-rich solutions are formed under oxidizing conditions at high gas/water ratios. Reactions between the acidic fluids and the Ijen andesite were modeled to account for elevated cation concentrations in lake water. Current concentrations of conservative rockforming elements are produced by dissolution of approximately 60 g of andesite per kg of acid solution. Complete neutralization of the acid lake waters by reaction with the wallrock produces a theoretical alteration assemblage equivalent to that observed in volcano-hosted, acid-sulfate epithermal ore deposits. © 1994.