潮波模型的优化开边界方法研究

数值模式是潮波研究的一种有利手段，但在研究中会面临各种具体问题，包括开边界条件的确定、底摩擦系数和耗散系数的选取等。数据同化是解决这些问题的一种途径，即利用有限数量的潮汐观测资料对潮波进行最优估计，其根本目的是迫使模型预报值逼近观测值，使模式不要偏离实际情况太远。本文采用了一种优化开边界方法，沿着数值模型的开边界优化潮汐水位信息，目的是设法使数值解在动力约束的意义下接近观测值，获得研究区域的潮汐结果。边界值由指定优化问题的解来定，以提高模拟区域的潮汐精度，最优问题的解是基于通过开边界的能量通量的变化，处理开边界处的观测值与计算值之差的最小化。这里提供了辐射型边界条件，由Reid 和Bodine（本文简称为RB）推导，我们将采用的优化后的RB方法（称为ORB）是优化开边界的特殊情况。 本文对理想矩形海域（ E- E， N- N， 分辨率 ）进行了潮波模拟，有东部开边界，模式采用ECOM3D模式。对数据结果的误差分析采用，振幅平均偏差，平均绝对偏差，平均相对误差和均方根偏差四个值来衡量模拟结果的好坏程度。 需要优化入开边界的解析潮汐值本文采用的解析解由方国洪《海湾的潮汐与潮流》（1966年）方法提供，为验证本文所做的解析解和方文的一致，本文做了其第一个例子的关键值a,b,z,结果与其结果吻合的相当好。但略有差别，分析的可能原因是两法在具体迭代方案和计算机保留小数上有区别造成微小误差。另外，我们取m=20，得到更精确的数值，我们发现对前十项的各项参数值，取m=10,m=20各项参数略有改进。当然我们可以获得m更大的各项参数值。 同时为了检验解析解的正确性讨论m和l变化对边界值的影响，结果指出，增大m，m=20时，u的模最大在本身u1或u2的模的6%；m=100时，u的模最大在本身u1或u2的模的4%；m再增大，m=1000时，u的模最大在本身u1或u2的模的4%，改变不大。当l<1时， =0处u的模最大为2。当l=1时， =0处u的模最大为0.1，当l>1时，l越大，u的模越小，当l=10时，u的模最大为0.001，可以认为为0。 为检验该优化方法的应用情况，我们对理想矩形区域进行模拟，首先将本文所采用的优化开边界方法应用于30m的情况，在开边界优化入开边界得出模式解，所得模拟结果与解析解吻合得相当好，该模式解和解析解在整个区域上，振幅平均绝对偏差为9.9cm,相位平均绝对偏差只有4.0 ，均方根偏差只有13.3cm，说明该优化方法在潮波模型中有效。 为验证该优化方法在各种条件下的模拟结果情况，在下面我们做了三类敏感性试验： 第一类试验：为证明在开边界上使用优化方法相比于没有采用优化方法的模拟解更接近于解析解，我们来比较ORB条件与RB条件的优劣，我们模拟用了两个不同的摩擦系数，k分别为：0,0.00006。 结果显示，针对不同摩擦系数，显示在开边界上使用ORB条件的解比使用RB条件的解无论是振幅还是相位都有显著改善，两个试验均方根偏差优化程度分别为84.3%，83.7%。说明在开边界上使用优化方法相比于没有采用优化方法的模拟解更接近于解析解，大大提高了模拟水平。上述的两个试验得出， k=0.00006优化结果比k=0的好。 第二类试验，使用ORB条件确定优化开边界情况下，在东西边界加入出入流的情况，流考虑线性和非线性情况，结果显示，加入流的情况，潮汐模拟的效果降低不少，流为1Sv的情况要比5Sv的情况均方根偏差相差20cm,而不加流的情况只有0.2cm。线性流和非线性流情况两者模式解相差不大，振幅，相位各项指数都相近, 说明流的线性与否对结果影响不大。 第三类试验，不仅在开边界使用ORB条件，在模式内部也使用ORB条件，比较了内部优化和不优化情况与解析解的偏差。结果显示，选用不同的k,振幅都能得到很好的模拟，而相位相对较差。另外，在内部优化的情况下，考虑不同的k的模式解， 我们选用了与解析解相近的6个模式解的k,结果显示，不同的k,振幅都能得到很好的模拟，而相位较差。 总之，在开边界使用ORB条件比使用RB条件好，振幅相位都有大幅度改进，在加入出入流情况下，流的大小对模拟结果有影响，但线形流和非线性流差别不大。内部优化的结果显示，模式采用不同的k都能很好模拟解析解的振幅。

Effect of H2S on stress corrosion cracking and hydrogen permeation behaviour of X56 grade steel in atmospheric environment

Susceptibility to stress corrosion cracking of X56 steel and its relationship with hydrogen permeation behaviour in atmospheric environment containing H2S was investigated by hydrogen permeation tests at a slow strain rate. The results show that: the fracture strain decreases with the decrease of strain rate under the same experimental conditions; the fracture strain also decreases with the increase of H2S concentration under the same strain rate, and the increased concentration of H2S has no significant effect on the hydrogen permeation in the first wet, etc. dry cycle, however has lead to increased hydrogen permeation in the later cycles. The SEM images of the fractured surfaces show clear evidences of enhanced stress corrosion cracking susceptibility by H2S.

青海歧穗大黄及其生长土壤中9种无机元素含量特征

为对比青海高原境内不同生境歧穗大黄中9种无机元素含量特征,用原子吸收光谱法分析了其宏量元素K、Na、Ca、Mg、P及微量元素Cu、Zn、Fe、Mn含量.结果表明,青海歧穗大黄植物与其土壤环境呈现出不同的无机元素含量特征,但一致表现为Ca和P在植物的富集,且植物中P含量随海拔升高而明显增加,Zn含量随海拔升高而增加.

荧光衍生试剂1-[2-（对甲苯磺酸醋）乙基]2-苯基咪唑[4,5-f]9,10-菲的合成及其在长链脂肪酸分析中的应用

合成了新的荧光衍生试剂1-[2-（对甲苯磺酸酯）乙基]-2-苯基咪唑[4,5-f]9,10-菲（TsEPIP），并将其作为柱前衍生化试剂，在Eclipse XDB-C：色谱柱上采用梯度洗脱实现了11种长链（C_(20)～C_(30)）游离脂肪酸（FFA）衍生物的基线分离。利用柱后在线的串联质谱并以大气压化学电离源（APCI）的正离子模式实现了各组分的质谱定性。对土壤及3种苔醉（东亚毛灰鲜、锦丝鲜、羽平鲜）中FFA组分的定量结果表明，苔鲜植物从土壤中富集了大量的长链游离脂肪酸。荧光检测的激发波长和发射波长分别为260 nm和380 nm。线性回归系数大于0.9996，检测限为26.19～76.67 fmol。所建立的方法具有良好的重现性，对实际样品的测定结果令人满意。

9种“藏茵陈”原植物中的7种有效化学成分研究

目的 研究藏药市场上9种“藏茵陈”植物中有效化学成分，根据所含成分的差异及其生理活性，确定这些植物的药用价值。方法 采用HPLC法测定7种成分的量。结果 9种植物的有效成分差异很大。结论 针对不同的化学成分用途，选择不同的植物，有效利用资源。[著者文摘]

青海青甘韭9个居群的核型

本文研究了青海葱属青甘韭 9个居群的染色体数目和核型。其中分布于湟源、西宁和共和海拔相对较低的地区的居群为 2倍体 ,核型公式为 2n =2x =16 =14m +2st (2SAT) (湟源居群和西宁居群 ) ,2n =2x =16 =12m +2sm +2st (2SAT) (共和居群 ) ;分布于玛沁、玉树、囊谦等高海拔地区的居群为 4倍体 ,核型公式为 2n =4x =32 =2 8m +4st (2SAT) (玉树居群 1和囊谦居群 1) ,2n =4x =32 =2 4m +4sm +4st (玛沁居群和玉树居群 3)和 2n =4x =32 =2 6m +2sm+4st (玉树居群 2 ) ;囊谦一个生长在林下的居群为8倍体，2n =8x =64 =54m +2sm +8st.讨论了居群间的核型分化和倍性与分布的关系。

CE determination of 2-(9-carbazole)ethyl chloroformate-labeled oligopeptides

A pre-column derivatization method for sensitive determination of oligopeptides, using the tagging reagent 2-(9-carbazole)ethyl chloroformate (CEOC-Cl) followed by capillary electrophoresis (CE) with diode-array detection, has been developed. Maximum yield close to 100% were observed when a three to fourfold molar excess of reagent was used at pH 9.0-10.0. Excess reagent was extracted with n-hexane-ethyl acetate 9:1-10:1 (v/v); this enabled direct analysis using CE with no significant disturbance from the major fluorescent reagent degradation by-products. The effects on the results of buffer pH and of SDS and organic modifier concentrations were examined. Good baseline resolution in the separation of five CEOC-peptides was achieved with a 48.5-cm total length (effective length 40 cm) 50-mu m inner diameter capillary column.

Pre-column derivatization of amines with 1,2-benzo-3,4-dihydrocarbazole-9-isopropyl chloroformate followed by LC-fluorescence and LC-APCI-MS

A pre-column derivatization method for the sensitive determination of amines using the labeling reagent 1,2-benzo-3,4-dihydrocarbazole-9-isopropyl chloroformate (BCIC-Cl) followed by high-performance liquid chromatography with fluorescence detection has been developed. Identification of derivatives is carried out by high performance liquid chromatography/atmospheric pressure chemical ionization (LC-APCl-MS-MS). The chromophore of 2-(9-carbazole)-ethyl chloroformate (CEOC) reagent is replaced by 1,2-benzo-3,4-dihydrocarbazole-9-isopropyl functional group, which results in a sensitive fluorescence derivatizing reagent BCIC-Cl. BCIC-Cl can easily and quickly label amines. Derivatives are stable enough to be efficiently analyzed by high-performance liquid chromatography and show an intense protonated molecular ion corresponding m/z [MH](+) under APCl in positive-ion mode. The collision-induced dissociation of protonated molecular ion formed a product at m/z 260 corresponding to the cleavage of CH2-OCO bond. Studies on derivatization demonstrate excellent derivative yields over the pH 9.0-10.0. Maximal yields close to 100% are observed with a 3 to 4-fold molar reagent excess. In addition, the detection responses for BCIC derivatives are compared with those obtained using CEOC and FMOC as derivatization reagents. The ratios of l(BCIC)/l(CEOC) and l(BCIC)/l(FMOC) are, respectively, 1.23-3.14 and 1.25-3.08 for fluorescent (FL) responses (here, l is relative fluorescence intensity). Separation of the derivatized amines had been optimized on reversed-phase Eclipse XDB-C-8 column. Detection limits are calculated from 1.0 pmol injection, at a signal-to-noise ratio of 3, are 10.6-37.8 fmol. The mean interday accuracy ranges from 94 to 105% for fluorescence detection with the largest mean %CV < 7.5. The mean interday precision for all standards is < 6.0% of the expected concentration. Excellent linear responses are observed with coefficients of > 0.9997.

2-(2-Phenyl-1H-phenanthro-[9,10-d]imidazole-1-yl)-acetic acid (PPIA) and its application for determination of amines by high performance liquid chromatography with fluorescence detection and identification with mass spectroscopy/atmospheric pressure chemical ionization

A simple, sensitive, and mild method for the determination of amino compounds based on a condensation reaction with 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide hydrochloride (EDC-HCI) as the dehydrant with fluorescence detection has been developed. Amines were derivatized to their acidamides with labeling reagent 2-(2-phenyl-1H-phenanthro-[9,10-d]imidazole-1-yl)-acetic acid (PPIA). Studies on derivatization conditions indicated that the coupling reaction proceeded rapidly and smoothly in the presence of a base catalyst in acetonitrile to give the corresponding sensitively fluorescent derivatives with an excitation maximum at lambda(ex) 260nm and an emission maximum at lambda(em) 380nm. The labeled derivatives exhibited high stability and were enough to be efficiently analyzed by high-performance liquid chromatography. Identification of derivatives was carried out by online post-column mass spectrometry (LC/APCI-MS/MS) and showed an intense protonated molecular ion corresponding m/z [MH](+) under APCI in positive-ion mode. At the same time, the fluorescence properties of derivatives in various solvents or at different temperature were investigated. The method, in conjunction with a gradient elution, offered a baseline resolution of the common amine derivatives on a reversed-phase Eclipse XDB-C-8 column. LC separation for the derivatized amines showed good reproducibility with acetonitrile-water as mobile phase. Detection limits calculated from 0.78 pmol injection, at a signal-to-noise ratio of 3, were 3.1-18.2 fmol. The mean intra- and inter-assay precision for all amine levels were < 3.85% and 2.11%, respectively. Excellent linear responses were observed with coefficients of > 0.9996. The established method for the determination of aliphatic amines from real wastewater and biological samples was satisfactory. (c) 2006 Elsevier B.V. All rights reserved.

Development of a sensitive fluorescent derivatization reagent 1,2-benzo-3,4-dihydrocarbazole-9-ethyl chloroformate (BCEOC) and its application for determination of amino acids from seeds and bryophyte plants using high-performance liquid chromatography with fluorescence detection and identification with electrospray ionization mass spectrometry

A pre-column derivatization method for the sensitive determination of amino acids and peptides using the tagging reagent 1,2-benzo-3,4dihydrocarbazole-9-ethyl chloroformate (BCEOC) followed by high-performance liquid chromatography with fluorescence detection has been developed. Identification of derivatives was carried out by liquid chromatography/electrospray ionization mass spectrometry (LC/ESI-MS/MS). The chromophore of 2-(9-carbazole)-ethyl chloroformate (CEOC) reagent was replaced by 1,2-benzo-3,4-dihydrocarbazole functional group, which resulted in a sensitive fluorescence derivatizing reagent BCEOC. BCEOC can easily and quickly label peptides and amino acids. Derivatives are stable enough to be efficiently analyzed by high-performance liquid chromatography. The derivatives showed an intense protonated molecular ion corresponding m/z (M + H)(+) under electrospray ionization (ESI) positive-ion mode with an exception being Tyr detected at negative mode. The collision-induced dissociation of protonated molecular ion formed a product at m/z 246.2 corresponding to the cleavage of C-O bond of BCEOC molecule. Studies on derivatization demonstrate excellent derivative yields over the pH 9.0-10.0. Maximal yields close to 100% are observed with a 3-4-fold molar reagent excess. Derivatives exhibit strong fluorescence and extracted detzvatization solution with n-hexane/ethyl acetate (10:1, v/v) allows for the direct injection with no significant interference from the major fluorescent reagent degradation by-products, such as 1,2-benzo-3,4-dihydrocarbazole-9-ethanol (BDC-OH) (a major by-product), mono- 1,2-benzo-3,4-dihydrocarbazole-9-ethyl carbonate (BCEOC-OH) and bis-(1,2-benzo-3,4-dihydrocarbazole-9-ethyl) carbonate (BCEOC)(2). In addition, the detection responses for BCEOC derivatives are compared to those obtained with previously synthesized 2-(9-carbazole)-ethyl chloroformate (CEOC) in our laboratory. The ratios AC(BCEOC)/AC(CEOC) = 2.05-6.51 for fluorescence responses are observed (here, AC is relative fluorescence response). Separation of the derivatized peptides and amino acids had been optimized on Hypersil BDS C-18 column. Detection limits were calculated from 1.0 pmol injection at a signal-to-noise ratio of 3, and were 6.3 (Lys)-177.6 (His) fmol. The mean interday accuracy ranged from 92 to 106% for fluorescence detection with mean %CV < 7.5. The mean interday precision for all standards was < 10% of the expected concentration. Excellent linear responses were observed with coefficients of > 0.9999. Good compositional data could be obtained from the analysis of derivatized protein hydrolysates containing as little as 50.5 ng of sample. Therefore, the facile BCEOC derivatization coupled with mass spectrometry allowed the development of a highly sensitive and specific method for the quantitative analysis of trace levels of amino acids and peptides from biological and natural environmental samples. (c) 2005 Elsevier B.V. All rights reserved.

中国北方表沙无机碳储量及次生碳酸盐固碳潜力研究

This paper selected the Taklamakan Desert and the Badain Jaran Desert as the research areas, tested the carbonate content of surface-sand samples of dunes using Eijkelkamp carbonate goniophotometer, and analyzed the spatial-distribution characteristics of carbonate and estimated the carbonate-stock and secondary carbonate-stock in 1m depth of surface sand in the Taklamakan Desert and the Badain Jaran Desert. In addition, the paper test XRD, SEM, TDA, stable carbon isotope and radioactive strontium isotope of lacustrine deposits in the Taklamakan Desert and carbonates, such as kunkar, root canal, lacustrine deposits, sinter and calcrete, in the Badain Jaran Desert. Resting on the achievements by our predecessors, it analyzed the mineral-composition differences of the carbonates, calculated the contents of secondary carbonate and, furthermore, evaluated their potential of sequestration of CO2 in the atmosphere. The overall goal of this study was to increase our understanding of soil carbonate in the context of carbon sequestration in the arid region in China. That is, to advance our understanding about whether or not secondary carbonate in desert is a sink for atmospheric CO2. The following viewpoints were obtained: 1 Carbonate contents of surface-sand samples decend from the south to the north of the Taklamakan Desert. The minimum lies in the south and the maxmum in the mid. Carbonate content of surface-sand of megadunes in the Badain Jaran Desert has low value generally in the dune-crest and the base of slope, and large value in the mid. The average of Carbonate contents of all sorts of collected samples in the same area of the Taklamakan Desert has small diffetences. The average is about 9%. 2 Using carbonate contents as key parameters, calculate the carbon-stock of carbonates in 1m depth of surface sand in the Taklamakan Desert and the Badain Jaran Deser.They are 1.13Pg and 0.19 Pg respectively. There are 0.53Pg and 0.088Pg carbon-stock of secondary-carbonates in 1m depth of surface sand in the Taklamakan Desert and the Badain Jaran Desert. 3 Through testing data from XRD （X-ray diffraction）and TAD ( Thermal Analysis Data), the most significant conclusion derived from is that the main mineral ingredient is calcite in different carbonate substances in arid regions, From the SEM(Scanning electron microscopy ) images, can obtains the information about the micro environment of different carbonate forms in which they can grow. 4 Selected gas by termal cracking and traditional phosphoric acid method, their δ13C show that δ13C is a good parameter to indicate the micro environment in which different secondary carbonate forms. From the δ13C of the same type samples, if the redeposit degree is hard, theδ13C is light, the redeposit degree is weak, the δ13C is heave. and the δ13C of the different type samples, δ13C is mainly controlled by the micro environment in which secondary formed. if the procedure is characterized by redeposit and dissolve of marine facies carbonate, δ13C is heavy, it is characterized by CO2 which produced by plant respiration,δ13C is light. 5 From the δ13C of lacustrine deposit in the different grain size, there exsit certain differences in their micro environment and secondary degree among different grain size in the same grade. 6 The secondary carbonate content of lacustrine deposits in Taklimakan Desert is 47.26%. And those of root canal, sinter, calcrete, kunkar, lacustrine deposit and surface sand in Badain Jaran Desert are 91.74%, 78.46%, 76.26%, 87.87%, 85.37%and 46.49%, respectively. Of different grain size samples, the secondary carbonate contents of coarse fraction (20-63μm), sub-coarse fraction (5-20μm) and fine fraction (<5μm) are 80.10%, 47.2%and 50.07%, respectively. 7 There is no obvious relevance betweenδ13C of secondary carbonate and the content of secondary carbonate,theδ13C of secondary carbonate mainly reflects the parameters of secondary process, the content of secondary carbonate reflects difference of secondary degree.. 8 Silicates potentially supply 3.4 pencent calcium source during forming process of lacustrine deposits in Taklimakan Desert. If calcium source is mainly supplied by goundwater, it can be calculated that about 5.18 %, 6.13%, 5.68%, 5.64 % and 6.82% silicates supply calcium source respectively for root canal, kunkar, lacustrine deposit, calcrete and sinter, during the forming process of different kinds of carbonates in Badain Jaran Desert.

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.

荣成基底片麻岩原岩岩石成因及其构造意义

Extensive high to ultrahigh pressure metamorphic rocks are outcropped in the the Dabie-Sulu UHP orogenic belt. Disputes still exist about for protolith nature of metamorphic rocks, petrogenesis, tectonic setting, and influence on upper mantle during the Triassic deep subduction. In this study, a combined study of petrology, geochemistry, isotope geochemistry and zircon chronology was accomplished for high-grade gneisses in the basement of the ultrahigh-pressure metamorphic Rongcheng terrane to reveal protolith nature and petrogenesis of the gneisses and to disucss the magmatic succession along the northern margin of the Yangtze block in Neoproterozoic. Gneisses in the Rongcheng terrane are characterized by negative Nb, Ta, P and Ti anomalies, relatively low Sr/Y ratios and relatively high Ba/La, Ba/Nb and Ba/Zr ratios, mostly displaying geochemical affinity to Phanerozoic volcanic arc. Neoproterozoic protolith ages (0.7 ~ 0.8 Ga) and Paleoproterozoic average crustal residence time (1.92 ~ 2.21 Ga) favour a Yangtze affinity. The gneisses mostly display characteristics of enrichment of LREE, flat heavy rare earth elements (REE) patterns, moderately fractionation between LREE and HREE and slight negative or positive Eu anomalies, probably reflecting that melting took place in the middle to low crust (26 ~ 33 km), where amphibole fractionated from the melts and/or inherited from source material as major mineral phases in the source area. Sr-Nd isotopic composition of the gneisses supports this conclusion. According to εNd(t) and εHf(t) values, the gneisses can be divided into three groups. Gneisses of group I have the highest εNd(t) and εHf(t) values, corresponding to the range of -6 ~ -3 and -2.9 ~ 13.4, respectively. This suggests obvious influx of depleted mantle or juvenile crust in the formation of protoliths. Gneisses of group II have medium εNd(t) (-9 ~ -7) and εHf(t) values (-15.8 ~ -1.4), corresponding to relatively high TDM2(Nd) (1.99 ~ 2.31 Ga) and TDM2(Hf) (1.76 ~ 2.67 Ga) , respectively. This suggests these gneisses were formed by partial melting of Paleoproterozoic crust. Gneisses of group III have the lowest εNd(t) (-15 ~ -10) and εHf(t) values (-15.8 ~ -1.4), corresponding to the largest TDM2(Nd) (1.99 ~ 2.31 Ga) and TDM2(Hf) ( 1.76 ~ 2.67 Ga), respectively. This indicates that gneisses of group III were formed by remelting of Archean crustal material and further demonstrates existence of an Archean basement probably of the Yangtze affinity beneath the Rongcheng terrane. Gneisses of three groups have also certain different geochemical characteristics. Contents of REEs and trace elements reduce gradually from group I to group III. Zirconium saturation temperatures also show similar tendency. Compared to gneisses of group II and group III, gneisses of group I display geochemical feature similar to extensional tectonic setting, having relatively little influence by the source area. Therefore, geochemical characteristics for gneisses of group I can indictate that the protoliths of the Rongcheng gneisses formed in an extensional rifting tectonic setting. This conclusion is supported by the results of eclogites and gabbros previously reported in the Dabie-Sulu orogenic belt. Statistical results of the protolith ages of the Rongcheng gneisses show two age peaks around ~728 Ma and ~783 Ma with an about 50 Ma gap. Extensive magatism in abou 750 Ma along the northern margin of the Yangtze block can hardly be observed in the Rongcheng terrane. This phenomenon likely suggests discontinuous Neoproterozoic magmatism along the northern margin of the Yangtze block.