大别山硬玉石英岩带中的水

The Dabie Mountains is a collisional orogenic belt between the North China and Yantze Continental plates. It is the eastern elongation of the Tongbai and Qingling orogen, and is truncated at its east end by the Tan-Lu fault. Jadeite-quartzite belt occurs in the eastern margin of UHPMB from the Dabie Mountains. Geochemical features indicate that the protoliths of the jadeite-quartzite and associated eclogite to be supracrustal rocks. The occurrence of micro-inclusions of coesite in jadeite and garnet confirmed that the continental crust can be subducted to great depth (8 0-100km) and then exhumed rapidly with its UHP mineral signature fairly preserved. Therefore, study of UHP jadeite-quartzite provides important information on subduction of continental crustal rocks and their exhumation histories, as well as the dynamics of plate tectonic processes at convergent margins. The purpose of this paper is to investigate the presence of hydrous component in the jadeite-quartzite belt, significant natural variations in the hydrous component content of UHP minerals and to discuss the role of water in petrology, geochemistry and micro-tectonic. On the basis of our previous studies, some new geological evidences have been found in the jadeite-quartzite belt by researches on petrography, mineralogy, micro-tectonic, hydrous component content of UHP minerals and combined with the study on rheology of materials using microprob, ER, TEM. By research and analysis of these phenomenona, the results obtained are as follows: 1. The existence of fluid during ultra-high pressure metamorphic process. Jadeites, omphacite, garnet, rutile, coesite and quartz from the jadeite-quartzite belt have been investigated by Fourier transform infrared spectrometer and TEM. Results show that all of these minerals contain trace amount of water which occur as hydroxyl and free-water in these minerals. The two-type hydrous components in UHP minerals are indicated stable in the mantle-depth. The results demonstrated that these ultra-high pressure metamorphic minerals, which were derived from continental crust protoliths, they could bring water into the mantle depth during the ultra-high pressure metamorphism. The clusters of water molecules within garnet are very important evidence of the existence of fluid during ultra-high pressure metamorphic process. It indicated that the metamorphic system was not "dry"during the ultra-high pressure stage. 2.The distribution of hydrous component in UHP minerals of jadeite-quartzite. The systematic distribution of hydrous components in UHP minerals are a strong indication that water in these minerals, are controlled by some factors and that the observed variations are not of a random nature. The distribution and concentration of hydrous component is not only correlated with composition of minerals, but also a function of geological environment. Therefore, the hydrous component in the minerals can not only take important part in the UHP metamorphic fluid during subduction of continental crustal rocks, but also their hydroxyl transported water molecules with decreasing pressure during their exhumation. And these water molecules can not only promote the deformation of jadeite through hydrolytic weakening, but also may be the part of the retrograde metamorphic fluid. 3.The role of water in the deformed UHP minerals. The jadeite, omphacite, garnet are strong elongated deformation in the jadeite-quartzite from the Dabie Mountains. They are (1) they are developed strong plastic deformation; (2) developed dislocation loop, dislocation wall; (3) the existence of clusters of water molecular in the garnet; and (4) the evolution of micero-tectonic from clusters of water molecular-dislocation loop in omphacite. That indicated that the water weakening controlled the mechanism of deformed minerals. Because the data presented here are not only the existence of clusters of water molecular in the garnet, but also developed strong elongation, high density of dislocation and high aspect ratios, adding microprobe data demonstrate the studied garnet crystals no compositional zoning. Therefore, this indicates that the diffusion process of the grain boundary mobility did not take place in these garnets. On the basis of above features, we consider that it can only be explained by plastic deformation of the garnets. The clusters of water molecules present in garnet was directly associated with mechanical weakening and inducing in plastic deformation of garnet by glissile dislocations. Investigate of LPO, strain analysis, TEM indicated that these clinopyroxenes developed strong elongation, high aspect ratios, and developed dislocation loop, dislocation wall and free dislocations. These indicated that the deformation mechanism of the clinopyroxenes plastically from the Dabie Mountains is dominant dislocation creep under the condition of the UHP metamorphic conditions. There are some bubbles with dislocation loops attached to them in the omphacite crystal. The bubbles attached to the dislocation loops sometimes form a string of bubble beads and some loops are often connected to one another via a common bubble. The water present in omphacite was directly associated with hydrolitic weakening and inducing in plastic deformation of omphacite by dislocations. The role of water in brittle deformation. Using microscopy, deformation has been identified as plastic deformation and brittle deformation in UHP minerals from the Dabie Mountains. The study of micro-tectonic on these minerals shows that the brittle deformation within UHP minerals was related to local stresses. The brittle deformation is interpreted as being caused by an interaction of high fluid pressure, volume changes. The hydroxyl within UHP minerals transported water molecules with decreasing pressure due to their exhumation. However, under eclogite facies conditions, the litho-static pressure is extreme, but a high fluid pressure will reduce the effective stress and make brittle deformation possible. The role of water in prograde metamorphism. Geochemical research on jadeite-quartzite and associated eclogite show that the protoliths of these rocks are supracrustal rocks. With increasing of temperature and pressure, the chlorite, biotite, muscovite was dehydrous reaction and released hydrous component during the subduction of continental lithosphere. The supracrustal rocks were transformed UHP rocks and formed UHP facies assemblage promotely by water introduction, and was retained in UHP minerals as hydrous component. The water within UHP minerals may be one of the retrograde metamorphic fluids. Petrological research on UHP rocks of jadeite-quartzite belt shows that there was existence of local fluids during early retrograde metamorphism. That are: (1) coronal textures and symplectite around relict UHP minerls crystals formed from UHP minerls by hydration reactions; (2) coronal textures of albite around ruitle; and (3) micro-fractures in jadeite or garnet were filled symplectite of Amp + PI + Mt. That indicated that the reactions of early retrograde metamorphism dependent on fluid introduction. These fluids not only promoted retrograde reaction of UHP minerals, but also were facilitate to diffuse intergranular and promote growth in minerals. Therefore, the hydrous component in the UHP minerals can not only take important part in the UHP metamorphic fluid during subduction of continental crustal rocks, but also their hydroxyl transport water molecules with decreasing pressure and may take part in the retrograde metamorphic fluid during their exhumation. 7. The role of water in geochemistry of UHP jadeite-quartzite. Geochemical research show that there are major, trace and rare earth element geochemical variations in the jadeite-quartzite from the Changpu district of Dabie Mountains, during retrograde metamorphic processes from the jadeite-quartzite--gneiss. The elements such as SiO_2、FeO、Ba、Zr、Ga、La、Ce、PTN Nd% Sm and Eu increase gradually from the jadeite-quartzite to retrograded jadeite-quartzite and to gneiss, whilst TiO_2. Na_2CK Fe2O_3、Rb、Y、Nb、Gd、Tb、Dy、Ho、Er、Tm、Yb decrease gradually. And its fO_2 keep nearly unchanged during early retrograde metamorphism, but decreased obviously during later retrograde metamorphism. These indicate that such changes are not only controlled by element transformation between mineralogical phases, but also closely relative to fluid-rock interaction in the decompression retrograde metamorphic processes.

内陆湖沼相和近海沼泽相沉积环境煤中微量元素和矿物的对比研究—以辽宁北票、江西建新和桥头煤研究为例

Using knowledge of geology, geochemistry, coal petrology, mineralogy, by means of a variety of advanced measuring methods such as inductively coupled plasma mass spectrometry (ICP-MS), inductively coupled atomic emission spectrometry (ICP-AES), X-ray powder diffraction (XRD), scanning electron microscopy with energy-dispersive spectrometer(SEM-EDS), sequential chemical extract and density fractions, the characteristics of trace elements and minerals in Jurassic Beipiao coal mine under inland limnetic sedimentary environment and in late Permian Jianxin and Qiaotou coal mines under paralic swamp sedimentary environment were studied. Compared with the average concentration in the world bituminous coals, the Beipiao coal was characterized by relatively high contents of Sc, Ti, Cr, Co, Ni, Zn, Se, Sr, Zr, Y, Ba, REE and Th, and lower contents of V, Rb, Cd, Sn, Pb, Bi and U; while the Jianxin coal was relatively enriched in Li, Sc, Ga, Sr, Y, Nb, Sb, Th and U, with low concentration of Be, Co, Ni, Cu, Ge, Zr, Mo, Cd, Cs, Ba, Pb and Bi; and the Qiaotou coal was enriched in Li, Sc, Sr, Nb, Ta, Zr, REE, Hf, Th and U, with low concentration of Be, V, Co, Ni, Cu, Ge, Mo, Cd, Cs, Ba, Tl, Pb and Bi. The concentrations of Ca, Mg and K in Beipiao coal are higher than those in Jianxin coal and Qiaotou coal, while Fe, S and Ti in Beipiao coal are lower than those in Jianxin coal and Qiaotou coal. The proximate analysis of coal samples was carried out, which indicated that Beipiao coal was medium- to high- ash (5.92-60.68%) with low sulphur coal, and Jianxin coal and Qiaotou coal was medium to high ash (8.85-46.33%) with high sulphur. The reflectivity was measured, which explained that Beipiao coal belonged to high volatile bituminous coal, Jianxin coal was low volatile bituminous coal and Qiaotou coal was low volatile anthracite. Quantitative maceral analyses were studied. The characteristics of rare earth elements (REE) were investigated, which showed that the total contents of REE were higher than that of the world's average content. With the increase of coal's metamorphic grade, the total contents of REE decreased from 98.5 X 10"6 of Beipiao coal to 94.2 X 10"6 of Jianxin coal, and to 75.9 X 10"6 of Qiaotou coal, and 5Eu reduced which indicated that the element Eu depleted. The characteristics of REE was controlled by the metamorphic grade of coal. And REE were mainly absorbed in clay minerals in Beipiao coal samples, while in Jianxin and Qiaotou coal mines, REE were primarily related to clay mineral and pyrite. The variation of trace elements in vertical direction of coal seams was studied, and the results showed that different trace elements differed greatly. The correlation between trace elements and ash were determined. Four major trace elements (aluminium-silicates, sulphide, carbonate and phosphate) accounted for the occurrence and distribution of most elements studied were determined. Coal samples were separated by density fraction, which showed that Cr, Cu, Mo and Pb were closely related to inorganic matters mainly distributed in P >2.6 and dropped remarkably in the density fractions P <2.3 . The occurrences of Co, Cr, Ni, As, Se, Mo, U were studied directly and quantitatively using sequential chemical extract with six steps, which showed that Co. Ni, Mo and U were mainly in the form of mineral, and As, Se chiefly in the form of organic state, while Cr mostly in the form of organic state and mineral. Major mineral phases presented in the Beipiao coal were Kaolinite, illite, quartz, calcite, and small amount of siderite, barite. While major mineral phases in Jianxin and Qiaotou coal were pyrite, kaolinite, and small amount of marcasite, rutile, sphalerite. This is the first time that the chromite in the coal was discovered in China, which indicates that Cr occurrence appeared in the form of chromite. The ratio of Sr/Ba, Sr/Ca and V/Ni in Beipiao coal mine under inland limnetic is smaller than that of in Jianxin and Qiaotou coal mines under paralic swamp. The ratio of K/Na and Th/U of Beipiao coal mine is higher than that of Jianxin and Qiaotou coal mine, which proved that Beipiao coal was not affected by sea water and Jianxin and Qiaotou coal were affected by sea water. Trace elements such as Cr, Ni, Mo in minerals were analyzed by SEM-EDS. The factors controlling the enrichment of trace elements can be divided into syngenetic stage factors and epigenetic stage factors.

电厂燃煤中主要有害元素的种类、迁移及潜在环境影响

Distributions of elements especially hazard trace elements in coals and their wastes from a coal fired power plant have been studied in detail using knowledge of Geology, Mineralogy, Geochemistry and Environmental chemistry. The key work is on the small particle sizes of fly ashes which escaped from electric precipitator and discharged into atmosphere. By means of X-ray powder diffraction (XRD) and scanning electron microscopy with energy-dispersive spectrometer (SEM-EDS), the characteristics of minerals and morphologies were studied. Different types of fly ash were formed in different stages and processes. More than 50% of small fly ashes belonged to inhalable particles (PM10). The very fine fly ashes preferred to attach on surface of bigger fly ash or conglutinate with each other and this decreased the environmental impact of tiny fly ashes. The trace elements in coal, fly ashes, slags and small particle sizes of fly ashes had been analysed by means of Neutron Activation Analysis (INAA), inductively coupled plasma mass spectrometry (ICP-MS), inductively coupled plasma atomic emission spectrometry (ICP-AES). As particle sizes decreasing, distributions of most elements increased, but in contrary to most studies, this increasing trend was not very obviously because of the tendency of attachment of tiny fly ashes. The occurrence of 30 elements including hazard trace elements of Cd, Cr, Ni, Co, Pb, Zn, As, Se, Cu, V was studied by means of sequential chemical extract. The annual discharge of hazard trace elements of slag, fly ash, small fly ash (PM10), tiny fly ash (PM2.5) and air was calculated by mass balance. S, V, Cu, Pb, Se, Mo, Cd from power plant had potential impacts on environment. Hazard trace elements from the power plant had little effect on soil and aerosol comparing to those from other industrial sources and the effects were mostly on downwind direction. Both the high performance electric precipitator and high chimney made the hazard trace elements from power plant being transported far away but little environmental impacts.

矾山杂岩体成因及其与磷（铁）矿的成矿关系

The Fanshan complex consists of layered potassic ultramafic-syenite intrusions. The Fanshan apatite (-magnetite) deposit occurs in the Fanshan complex, and is an important style of phosphorus deposit in China. The Fanshan complex consists of three (First- to Third-) Phases of intrusion, and then the dikes. The First-Phase Intrusive contains ten typical layered rocks: clinopyroxenite, biotite clinopyroxenite, coarse-grained biotite clinopyroxenite, pegmatitic orthoclase-biotite clinopyroxenite, variegated orthoclase clinopyroxenite, interstitial orthoclase clinopyroxenite, biotite rock, biotite-apatite rock, biotite rock and magnetite-apatite rock. This layered intrusive consists of nine rhythmic units. Each rhythmic unit essentially comprises a pair of layers: clinopyroxenite at the bottom and biotite clinopyroxenite at the top. The apatite (-magnetite) deposit is situated near the top of rhythmic Unit no. 6 of the First-Phase Intrusive. The Second-Phase Intrusive contains three typical rocks: coarse-grained orthoclase clinopyroxenite, . coarse-grained salite syenite and schorlomite-salite syenite. The Third-Phase Intrusive includes pseudo-trachytic salite syenite, porphyritic augite syenite, fine-grained orthoclase clinopyroxenite and fine-grained salite syenite. The origin of the Fanshan complex is always paid attention to it in China. Because most layered igneous intrusion in the world not only have important deposit in it, but also carry many useful information for studying the formation of the intrusion and the evolvement of magma. Two sketch maps were drawn through orebodies along no. 25 cross-cut on 425 mL and no. 1 cross-cut on 491 mL in the Fanshan mine. Through this mapping, a small-scaled rhythmic layering (called sub-rhythmic layering in the present study) was newly found at the top of the rhythmic Unit no. 6. The concept of sub-rhythmic layering is defined in this article. The sub-rhythmic layering is recognized throughout this apatite-rich part, except for magnetite-apatite rock. Presence of the layered magnetite-apatite rock is one of the characteristics of the Fanshan apatite (-magnetite) deposit. Thus, from this layer downwards six units of sub-rhythmic layering are recognized in the present study. Each unit consists of biotite clinopyroxenite (or biotite rock and biotite-apatite rock) layer at the bottom and apatite rock layer at the top. To study this feature in detail is an important work for understanding the origin of the Fanshan complex and apatite (-magnetite) deposit. The origin of the Fanshan complex and the relation of the formation of the apatite(-magnetite)deposit will be interpreted by the study of sub-rhythmic layering on the basis of previous research works. The magma formed the Fanshan complex was rich in K2O, early crystallized pyroxene, and after this phase more biotite crystallized, but no amphibole appeared. This indicated that the activity of H2O in the magma was low. Major element compositions of biotite and clinopyroxene (on thin sections) in the sub-rhythmic layering were analyzed using electron microprobe analyzer. The analytical results indicate Mg/(Mg+Fe*+Mn) atomic ratios (Fe*, total iron) of these two minerals rhythmically changed in sub-rhythmic layering. The trends of Mg/(Mg+Fe*+Mn) atomic ratio (Fe*, total iron) of biotite and clinopyroxene indicate that the magma evolved markedly from relatively magnesian bottom layer to less magnesian top layer in each sub-rhythmic unit. A general trend through the sub-rhythmic layering sequence is both minerals becoming relatively magnesian upwards. The formation temperatures for sub-rhythmic layering yield values between 600 and 800 ℃, were calculated using the ratio of Mg/(Mg+Fe+Mn) in the salite and biotite assemblage. The equilibrium pressures in the rhythmic layers calculated using the contents of Al in the salite were plotted in the section map, shown a concave curve. This indicates that the magma formed the First-Phase Intrusive crystallized by two vis-a-vis ways, from its bottom and top to its centre, and the magnetite-apatite rock was crytallized in the latest stage. The values of equilibrium pressures in the sub-rhythmic layering were 3.6-6.8(xlO8) Pa with calculated using the contents of Al in the salite. The characteristics of geochemistry in various intrusive rocks and the rocks or apatite of sub-rhythmic layers indicated that the Fanshan complex formed by the comagmatic crystallization. The contents of immiscible elements and REEs of apatite rock at the top of one sub-rhythmic unit are more than biotite clinopyroxenite at the bottom. The contents of immiscible elements and REEs of apatite of biotite clinopyroxenite at the bottom of one sub-rhythmic unit are higher than apatite rock at the top. The curves of rocks (or apatite) in the upper sub-rhythmic units are between two curves of the below sub-rhythmic unit in the primitive mantle-normalized trace element abundance spider diagram and the primitive mantle-normalized REE pattern. The trend for the contents of immiscible elements and REEs inclines to the same contents from the bottom to the top in sub-rhythmic layering. These characteristics of geochemistry of rocks or apatites from sub-rhythmic layering indicate that the latter sub-rhythmic unit was produced by the residual magma after crystallization of the previous sub-rhythmic unit. The characteristics of petrology, petrochemistry, geochemistry in the Fanshan complex and sub-rhythmic layers and the trends of Mg/(Mg+Fe+Mn) atomic ratio of biotite and clinopyroxene in sub-rhytmic layering rejected the hypotheses, such as magma immiscibility, ravitational settling and multiple and pulse supplement of magma. The hypothesis of differentiation by crystallization lacks of evidences of field and excludes by this study. On the base of the trends of formation temperatures and pressures, the characteristics of petrology, petrochemistry, geochemistry for the Fanshan complex and the characteristics of geochemistry for the rocks (or apatites), the trends of Mg/(Mg+Fe+Mn) atomic ratio of biotite and clinopyroxene in sub-rhytmic layering, and the data of oxygen, hydrogen, strontium and neodymium isotopes, this study suggests that the magma formed the Fanshan complex was formed by low degree partial melting of mantle at a low activity of H2O, and went through the differentiation at the depth of mantle, then multiply intruded and crystallized. The rhythmic layers of the First-Phase Intrusive formed by the magma fractional crystallized in two vis-a-vis ways, from the bottom and top to the centre in-situ fractional crystallization. The apatite (-magnetite) deposit of the Fanshan complex occurs in sub-rhythmic layering sequence. The the origin of the sub-rhythmic layering is substantially the origin of the Fanshan apatite (-magnetite) deposit. The magma formed the rhythmic layers of First-Phase Intrusive was rich in H2O, F and P at the later stage of its in-situ fractional crystallization. The Fanshan apatite (-magnetite) deposit was formed by this residual magma in-situ fractional crystallization. The magnetite-apatite rock was crystallized by two vis-a-vis ways at the latest stage in-situ fractional crystallization in the rhythmic layers. The result was light apatite layer below heavy the magnetite-apatite layer, formed an "inversion" phenomenon.

Epoxidation of propylene with dilute H2O2 over titanium silicalite containing trace aluminum

Titanium silicalite (TS-1) was successfully synthesized by using TPABr as the template and silica sol as silicon source in a 100 l stainless steel autoclave. IR, XRD, UV--vis, elemental analysis, and (2)7Al and (3)1P MAS NMR were used to characterize the synthesized products. The results show that the synthesized material has an MFI structure with high crystallinity and large crystal size and two kinds of titanium species. Trace aluminum in silica sol is also incorporated into the zeolite framework. The synthesized TS-1 exhibits high activity in the epoxidation of propylene with dilute H2O2 with high selectivity to methyl mono-ethers and low selectivity to propylene oxide (PO). The low selectivity toward PO is due to the residual acidity onto TS-1. The selectivity of PO can reach up to 90% through adjusting the pH of the reaction mixture. Extra amounts of base decrease the H2O2 utilization and the H2O2 conversion. However, in over acid-treated TS-1 in which part removal of extra-framework titanium takes place, the utilization of H2O2 is quite different: for the low Si/Ti ratio of TS-1, the H2O2 utilization increases. But the utilization of H2O2 does not change for the high Si/Ti ratio TS-1. Thermal analysis shows that the as-synthesized TS-1 exhibits high activity and thermal stability in the calcined range 540-900 degreesC.