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。

栽培川西獐牙菜中6种药用成分的测定方法和动态积累研究

采用反相高效液相色谱法对川西獐牙菜中6种药用成分不同生长期的含量进行了测定.色谱柱为Kromasil C18(250 mm×4.60 mm,5 μm),流动相为甲醇-0.02%的磷酸水溶液,检测波长260 nm.该方法具有很好的线性关系和回收率.结果显示,川西獐牙菜全草的最佳采收期为9月中旬(花果期).

川西獐牙菜与抱茎獐牙菜中酮的高效液相色谱分析

采用反相高效液相色谱法同时分离和测定了龙胆科獐牙菜属的川西獐牙菜和抱茎獐牙菜中几种酮的含量.色谱柱为Kromasil C_(18)(250 mm * 4.60 mm i.d., 5 μm),流动相为甲醇-0.1%的磷酸水溶液(体积比为73∶27),流速1 mL/min,检测波长260 nm,柱温20 ℃.实验结果表明,该方法具有很好的线性关系与精密度,方法简单、准确、实用性强.

Determination of 30 free fatty acids in two famous Tibetan medicines by HPLC with fluorescence detection and mass spectrometric identification

A simple and sensitive high-performance liquid chromatographic (HPLC) method with fluorescence detection and mass spectrometric identification has been developed for analysis of 30 long-chain and short-chain free Fatty acids (FFAs). The fatty acids were derivatized to their esters with 1-[2-(p-toluenesulfonate)ethyl]-2-phenylimidazole-[4,5-f]-9,10-phenanthrene (TSPP) in N,N-dimethylformamide (DMF) at 90 degrees C with anhydrous K2CO3 as catalyst. A mixture Of C-1-C-30 fatty acids was completely separated within 60 min by gradient elution on a reversed-phase C-8 column. Qualitative identification of the acids was performed by atmospheric-pressure chemical ionization mass spectrometry (APCI-MS) in positive-ion mode. The fluorescence excitation and emission wavelengths were 260 and 380 nm, respectively. Quantitative determination of the 30 acids in two Tibetan medicines Gentiana straminea and G. dahurica was performed. The results indicated that the medicines contained many FFAs. Linear correlation coefficients for the FFA derivatives were > 0.9991. Relative standard deviations (RSDs, n = 6) for the fatty acid derivatives were < 3%. Detection limits (at a signal-to-noise ratio of 3:1) were 3.1-38 fmol. When the fatty acid derivatives were determined in the two real samples results were satisfactory and the sensitivity and reproducibility of the method were good.

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.

博兴洼陷新生代构造-沉积演化及其对鲁西隆起的响应

The West Shandong Uplift and its adjacent basins, with same evolutional history before Mesozoic, are an important basin-orogenic systems in North China. After late Mesozoic, tectonic differentiation between basin and orogenic belt gradually displayed in the study area. The Boxing sag is a part of Jiyang Depression near to West Shandong Uplift, in which the whole Mesozoic and Cenozoic strata are preserved. Based on the analysis of sedimentary records in the Boxing sag, the Cenozoic structural and sedimentary evolutions in Boxing Sag and its response to Western Shandong uplift are discussed in this dissertation. The main conclusions in this research are presented as follows. Based on Seismic and well logging profile interpretation, fault growth index, thickness difference between bottom wall and top wall and fault activity rate from Eocene to Pliocene are studied. Boxing sag had three main faults, NE, NW and NEE trending faults. Research shows that the activity of the NW trending fault in the Boxing sag became weaken from E1-2S4 to N2m gradually. The evolution of NE and the NEE trending fault can be divided into three episodes, from E1-2k to E2s4, from E2s3 to E3s1, from N2m to E3d. The analysis of Paleogene samples of heavy mineral assemblages shows that metamorphic rocks represented by garnet, intermediate-acid igneous rocks represented by the assemblage of apatite, zircon and tourmaline became less from E1-2k to N2g, and sedimentary rocks represented by the assemblage of pyrite, barite and limonite also became less. Intermediate-basic igneous rocks represented by the assemblage of leucoxene, rutile and ilmenite and metamorphic rocks represented by epidote became more and more. Electronic microprobe analysis shows that glaucophane and barroisite are existed in Kongdian Formation and the 4th member of Shahejie Formation, and they demonstrate that Western Shandong and Eastern Shandong are all the source regions of the Boxing Sag, and they also indicate that oceanic crust existed before the collision between the Yangtze and North China continent. The fact that Eastern Shandong is the source region of Boxing Sag also indicates that Western Shandong was not high enough to prevent sediment from Eastern Shandong at E1-2k and E2s4. The results of the dating of five detrital zircons of Boxing Sag show Kongdian Formation and the 4th member of Shahejie Formation have the age peaks of 2800Ma and 700-800. It means that Eastern Shandong is the source region of Boxing Sag at early Paleogene and Western Shandong is not high enough to prevent the sediment from Eastern Shandong. The ages of 160-180 and 220-260 Ma, which exist in the Guantao Formation and Paleogene, are common in Eastern Shandong and rare in Western Shandong,and it implied that Western Shandong is a low uplift at 24Ma. The Paleogene strata have almost same age groups, while the Guantao Formation has significant variations of age groups, and this indicates that Boxing Sag and Western Shandong uplift had taken place tremendous changes. The results of apatite fission track in Boxing sag show that three times uplifts happened at the source region at 60 Ma, 45Ma and 15Ma respectively, and the Boxing sag experienced two subsidences at 60Ma, 45Ma and one uplift at 20Ma.

甘肃西峰晚第三纪红粘土地层中的蜗牛化石记录及其古环境意义

In this study, 260 mollusk fossil samples from a Red Clay sequence at Xifeng, Gansu province, in the northern China were analyzed quantitatively. 12 fossil species and four fossil zones have been identified. Three main ecological groups were determined based on ecological requirement of each mollusk taxon. According to fossil composition and succession of three ecological groups, the author discussed the origin and sedimentary environment of the red clay deposits, and the process of ecological environmental changes as well as the variations of the East Asia monsoons during 6.2-2.4 Ma in the Loess Plateau. A preliminary study on periodicity of paleoclimatic changes was also conducted by using spectral analysis method. The main results and conclusions are presented as follows:A continuous land mollusk fossil sequence of 6.2-2.4 Ma from Xifeng Red Clay Formation has been established, which provided a basic data for studying the environmental changes during late Miocene to Pliocene.The study of composition and preservation condition of mollusk fossils reveals a terrestrial in situ ecological population in the Red Clay Formation. All of identifiable mollusk species are composed of terrestrial taxa, which support the view that the Red Clay is an eolian origin, similar to the overlying Quaternary loess deposits.The mollusk record reveals the processes of ecological and environmental changes during 6.2-2.4 Ma in the Loess Plateau. Climatic changes experienced cold and dry from 6.2-5.4 Ma, warm and wet during 5.4-4.5 Ma, mild and moderate from 4.5-3-4 Ma, to rapid cooling and drying after 3.4 Ma. From '5.4- 2.4 Ma, climate was stepwise cooling. The cooling trend is in good agreement with a general1 0global cooling trend during this period, as documented by marine 5 0 records.4. Three remarked ecological shifts took place in mollusk assemblages from 6.2-2.4 Ma, focused on about 5.4, 4.5 and 3.4 Ma. The warming shift around 5.4 Ma was probably related to the rising of the global temperature. The cooling shifts around 4,5 and 3.4 Ma however might be closely linked to the uplift of Tibet Plateau and the development of Northern Hemisphere ice sheet.The succession in mollusk ecological groups also recorded the variability of the East Asian winter and summer monsoon. The winter monsoon dominated two periods from 6.2-5.4 Ma and from 3.4-2.4 Ma, while the summer monsoon was strong during 5.4-4.5 Ma. The variations in winter and summer monsoons were in phase during 4.5-3.4 Ma. Monsoon regimes changed with the duration about 1 Ma, which roughly corresponds to the cycle driven by tectonic activity on the time scales of ICP-IO7 years. In addition, mollusk fossils recorded the large amplitude and high frequency fluctuations overlapped on 105-107 years climate cycle.The maximum entropy spectral analysis and filter-band analysis of total mollusk individuals and three typical ecological groups suggest that the climate changes controlled mainly by solar insolation had periods about 70 ka and 40 ka on the time scales of 105 during late Miocene-Pliocene. Climatic periodicity intensified from 4.0 Ma, which reflected strengthened forcing by high latitude ice volume.

上地幔橄榄石电导率影响因素及高压相变初探

人们对上地幔标志性矿物橄榄石的认识，基本上是经历一个从直流到交流，又从交流到阻抗谱的认识过程．本文主要通过对橄榄石电导率的影响因素出发，包括温度、压力、铁镁比值、氧逸度等因素的影响和制约．用目前国际高温高压学术界公认的阻抗谱技术探讨了橄榄石在高压下的相变，并在此基础上，进一步研究地球物理学家非常关心的热点问题-冷地幔的实验室的模拟，并作了充分的论证．

贵州水银洞卡林型金矿床首次发现大量次显微-显微可见自然金颗粒

在贵州水银洞卡林型金矿床原生富矿石的一条含砷黄铁矿细脉中发现有100余粒次显微-显微自然金颗粒（0．1～6μm），并具有清晰的显微岩相学结构。提出了该类型金矿次显微-显微可见自然金颗粒的形成过程可能与含Au热液-岩石相互作用过程中含Fe碳酸盐矿物溶解释放Fe的大量硫化物化而导致热液中Au的过饱和有关，含Fe碳酸盐赋矿围岩是形成高品位大型卡林型金矿床最重要的控制因素之一。

云南省墨江金矿床成矿时代探讨

在系统研究墨江金矿床地质事件的基础上，以富金石英脉中的石英流体包裹体为测定对象，获得RbSr等时线年龄为(135±3)Ma。上三叠统地层中含金石英脉旁侧发育的铬水云母脉K-Ar法年龄为(109.5±1.7)Ma。结合前人的研究资料，认为墨江金矿床经历了多期次成矿作用，其中构成本矿床的主体——富金石英脉的形成时代可能为135～90Ma，相当于燕山晚期。

云南会泽铅锌矿床成矿流体性质和来源—来自流体包裹体和水岩反应实验的证据

位于扬子地块西南缘川、黔、滇铅锌多金属成矿区的中南部的云南会泽铅锌矿床是我国著名的Pb、Zn、Ge生产基地之一，近年来受到很多地质学家和地学工作者的关注。本文在自己研究成果和前人资料的基础上，以云南省会泽铅锌矿床为研究对象，从脉石矿物方解石和脉石矿物热液白云石中的流体包裹体入手，详细研究矿床成矿流体的物理化学条件变化；并结合高温高压实验和前人研究成果（成矿元素分析、同位素等），详细分析该矿床的成矿流体来源、迁移机制与成矿机制，解决矿床成矿流体与围岩、基底、峨眉山玄武岩三者之间的关系，并提出合理的矿床的成因模式；并通过该课题研究，揭示成矿流体随温度、压力变化而变化的规律，了解矿床成矿元素迁移、富集和沉淀的热力学、动力学作用机制，为区域内其他铅锌矿床的找矿和研究提供理论依据。通过系统的研究，获得以下结论和成果： ⑴矿物流体包裹体均一温度主要变化于150~250℃之间，部分包裹体大于300℃；矿床矿物包裹体的形成存在两个高峰期：第一个高峰期包裹体均一温度主要集中于150~220℃，第二个高峰期包裹体均一温度主要集中于300~350℃；包裹体的捕获温度位于150℃~401℃之间，其中大部分高于200℃；盐度变化范围5~21wt% NaCl，平均值为13.24wt% NaCl；密度0.546~1.129 g/cm3；均一瞬间压力145×105Pa ~754×105Pa；成矿过程中流体曾存在沸腾作用和不混溶现象；沸腾包裹体的证据表明，成矿的深度为当时地表以下2200~2450米。因此，矿床成矿流体总体属中温-中压-中等盐度性质。 ⑵H、O同位素计算、流体包裹体、Sr同位素和水-岩反应实验结果表明，矿床成矿流体为不同来源流体混合的产物，具有多源性。而地层成矿元素含量、Pb同位素和水-岩反应实验结果证明成矿物质同样也具有多源性。因此，会泽铅锌矿床的成矿流体、成矿物质都具有多种来源。 ⑶矿床成矿条件：成矿温度为131℃~491℃，平均值为260℃；矿化时间与峨眉山玄武岩岩浆活动的时代较为相近；成矿时流体pH值为4.2~7.5，呈中性~弱碱性；金属矿物的氧逸度主要变化范围为10-55—10-20，硫逸度主要变化范围为10-30—10-10。矿石的品位主要跟流体混合、沸腾作用和断裂带宽度受到限制有关。 ⑷在该矿床，中低温（100~250℃）环境下的铅锌迁移形式有所不同，锌主要以硫氢化物络合物形式进行迁移，兼有少量氯化物络合物；而铅主要以氯化物络合物形式进行迁移，但有部分硫氢化物络合物。而在中高温条件下铅、锌基本都以氯化物络合物的形式进行迁移。影响矿物沉淀的因素很多，但流体混合作用和沸腾作用是引起会泽铅锌矿床金属矿物沉淀的主要原因。 ⑸肉红色白云岩形成的原因可能跟较为封闭的潮坪—泻湖的原始蒸发环境有关；而灰色白云岩则可能来自肉红色白云岩的淋滤交代；白色白云岩的形成则与灰岩、白云质灰岩的热液交代有关。

滇东南老君山变质核杂岩地球化学和年代学初步研究

本文通过对滇东南老君山变质核杂岩各组成单元的地质特征、地球化学、热年代学等详细而系统的研究，得到了如下结论： （1）老君山地区存在古元古代结晶基底和中、新元古代岩浆活动，其中新元古代岩浆活动与华南（超级）地幔柱侵入、罗德里亚大陆裂解有关。 （2）南捞片麻岩与南温河花岗岩同属加里东期扬子板块与华夏板块同碰撞造山环境产物，两者同属变质泥岩、砂岩及中基性岩上壳岩部分熔融的S型花岗岩。 （3）老君山变质核杂岩基本形成时限在印支期260-160Ma，之后经历了不断隆升并在第三纪末出露剥蚀的过程。 （4）在老君山变质核杂岩韧-脆性基底拆离断层系和韧性核部剥离断层系各存在一次大规模的成矿作用，前者形成了南秧田、新寨等大型矿床，后者形成了都龙超大型矿床。时代分别为晚印支期的220-200Ma左右和晚燕山期80Ma左右。 （5）越北古陆的构造属性属于扬子和华夏板块拼贴前的华夏板块，即属于华南板块构造单元而非印支板块构造单元；Song Ma和Day Nui Con Voi剪切带之间的部分是从扬子板块西缘走滑剪切600km的杂岩体，亦非印支板块构造单元。 （6）较为详细论证了老君山地区的构造演化过程，并对滇东南泥盆纪-三叠纪末的构造演化提出了新的模式，即Song Ma古缝合线是印支板块与华南板块陆陆碰撞的残留形迹，八布蛇绿岩是大陆边缘前陆盆地局部海盆化的产物，其构造位置在俯冲期位于弧后盆地位置，在陆陆碰撞其位于前陆褶皱冲断带位置。 此外，本文还对利用都龙锡锌多金属矿床矿石中的锡石TIMS U-Pb定年方法进行了探索，确定了行之有效的锡石溶解的实验流程及方法，并首次获得都龙锡锌多金属矿床矿石中锡石TIMS U-Pb年龄为79.1±1.6Ma，证实了锡矿化主要与燕山晚期岩浆热液活动有关。

甘肃阳山金矿同位素地球化学特征及矿床成因

甘肃文县阳山金矿的探明黄金储量已达308t，平均品位4.74g/t，是我国地质勘查储量最大的金矿床。该矿床产于西秦岭造山带，是一个同碰撞形成的类卡林型金矿床，矿体受EW向韧脆性剪切带控制，赋矿围岩为泥盆系碳质千枚岩-板岩-碳酸盐-硅质岩和侵入其中的花岗斑岩脉。流体成矿过程包括：形成石英-绢云母-黄铁矿组合的早阶段，形成石英-黄铁矿-毒砂-方铅矿等多金属组合的主成矿阶段，形成碳酸盐-辉锑矿-石英网脉的晚阶段。 与矿体关系较为密切的花岗斑岩富集LILE 和 LREE, 亏损 Ba, Sr, Nb, Ta, P 和Ti，ΣREE＝54.35～124.01 μg/g ，(La/Yb)N=9.72～27.80，δEu=0.70～0.89， ISr值为0.70806～0.71756，平均0.71107；εNd(t)平均-3.4；Nd模式年龄（T2DM）平均1.34（Ga）。表明花岗斑岩岩浆应源自成熟度较低的中元古代基底地壳物质。花岗斑岩的(206Pb/204Pb)220Ma、(207Pb/204Pb)220Ma和(208Pb/204Pb)220Ma的平均值分别为17.875、15.604和38.296，与秦岭微陆块的中元古代基底和碧口地体碧口群的Pb同位素组成一致。考虑到前人获得碧口群的年龄为1.235～1.367Ga，而秦岭微陆块沿勉略缝合带向南仰冲到碧口地体之上，我们认为由碧口群等组成的俯冲板片的变质脱水熔融作用导致了阳山金矿带花岗斑岩的形成。因此，阳山金矿带的花岗斑岩是扬子与华北大陆中生代碰撞造山过程中形成的同碰撞花岗岩类。 最新的S，Sr和Pb同位素研究表明：热液成矿早阶段的黄铁矿的34S值范围介于-15.5‰~6.59‰之间，总体离散性比较大，显示沉积地层来源的特征，硫同位素组成属离散型，不具有岩浆主导的成矿的塔式效应。花岗岩中黄铁矿硫同位素范围很集中，34S值处于-1.47‰～2.12‰之间，本区花岗斑岩不可能为成矿物质的主要来源。矿石硫化物的初始锶同位素比值范围较大（0.70877～0.71697，平均为0.71258），显示成矿物质并非单一来源，考虑到花岗斑岩先于矿床形成，只在后期构造作用的岩体部分成矿的地质事实，少量矿石中的低锶同位素比值黄铁矿有可能来自作为围岩的花岗斑岩，也可能来自基底物质。矿石硫化物Pb同位素206Pb/204Pb=17.552～18.853，平均18.260；207Pb/204Pb=15.574～15.928，平均15.685；208Pb/204Pb=37.894～39.293，平均38.680，变化范围比较大。μ=9.46~10.06，平均为9.65，ω值介于36.96～42.21，显示了铅源的物质成熟度较高，要求最佳物源是浅变质化学-碎屑沉积建造，恰好与本区泥盆构造层为浅变质细碎屑岩夹薄层灰岩系的特征一致，部分低Sr和Pb同位素比值的成矿物质可能来自于作为围岩的花岗斑岩和/或者基地物质。 总结前人阳山金矿床的H-O-C同位素体系的研究得出，初始成矿流体来源于碳酸盐地层或相似岩石建造的变质或/和改造脱水，成矿流体系统从早到晚、从深到浅，由变质热液演变为大气降水热液。与本文得出的结论一致。 总而言之， 阳山金矿矿成矿流体的来源早期具有变质水特征，应来自赋矿地层或相似岩性组合的改造或变质脱水作用，晚阶段大气水为主的流体性质。成矿物质主要来自于赋矿围岩。流体经过作为部分围岩的花岗斑岩时从中萃取少部分成矿物质，而导致了少部分的低锶、铅同位素的矿石硫化物组成。 在中生代扬子板块北缘（包括碧口地块）向南秦岭陆陆碰撞过程中，扬子北缘板片沿勉略断裂向北俯冲到南秦岭之下，下插板片增温增压，发生变质、脱水和部分熔融。碰撞中期，构造背景由挤压向伸展转变，减压增温的环境导致大量变质流体沿深大断裂向上运移，不断萃取围岩中大量成矿元素，并将成矿元素搬运至有利于流体聚集、成矿物质卸载的空间，使成矿物质富集成矿。阳山金矿床定位于泥盆系构造层中，成矿时代为190Ma左右，紧随花岗斑岩侵入作用（220Ma左右），主成矿作用发生于碰撞作用由挤压-伸展转变期的减压增温环境。成岩、成矿模式与CMF模式吻合。 阳山超大型金矿是世界罕见的碰撞造山带内类卡林型金矿床，其地质地球化学特征复杂、独特，流体性质主要与造山型金矿一致，矿床地质主要与卡林型金矿一致，部分特征兼与造山型和卡林型两类矿床之间，花岗斑岩本身成矿的特点又为阳山所特有，总体具有造山型向卡林型金矿过渡的性质。因此建议以“秦岭式”或“阳山式”类卡林型金矿床代表与阳山金矿具有类似成矿背景及地球化学性质的矿床。

云南大红山层状铜矿床地球化学及成矿机制研究

云南省大红山铁铜矿床位于康滇地轴南端西缘，介于红河深断裂与绿汁江深断裂所夹持的滇中台坳内，赋存于中元古代大红山群海相火山喷流-沉积岩系中，是我国典型的火山岩型块状硫化物（VHMS）矿床之一。该矿床包括一系列与火山喷发-岩浆侵入活动相关但成因有一定差别的矿床，被统称为“大红山式”铁铜矿床。该矿床经济价值巨大，铁、铜储量均达超大型矿床规模，但其研究程度较低，多停留在矿区地质特征层面上，地球化学研究较为薄弱。本次工作系统地研究了大红山层状铜矿床中各类岩石的岩相学特征，对特征矿物做了电子探针定性和定量分析，挑选火山质岩石中锆石做定年分析，系统分析了岩石的主量元素和微量元素，测定了硫化物的硫和铅同位素，并选取了与富集型硫化物相关的石英脉矿物和碳酸盐矿物分别做流体包裹体和碳、氧同位素研究。论文取得的主要认识如下： 1．红山群曼岗河组火山喷流-沉积年代约为1687±8Ma，即形成于早-中元古代，因此不可能遭受如前人所说的吕梁运动改造作用。在700 ~ 800Ma左右，即晋宁运动期本区遭受了强烈的变质变形以及流体蚀变改造作用。 2．层状铜矿中岩石类型主要为黑云母片岩、白云石钠长石岩和白云石大理岩。黑云母片岩中主要矿物为黑云母、钠长石、铁白云石和石榴子石；白云石钠长石岩中主要矿物为钠长石、铁白云石、石榴子石及少量的黑云母；白云石大理岩中主要矿物为铁白云石，含少量的钠长石和黑云母。岩石原岩恢复表明，三类岩石原岩为火山物质、泥质沉积物和喷流热水沉积混合组成，其中黑云母片岩以泥质为主，包含火山质物质和喷流热水沉积物质；白云石钠长石岩以火山物质和喷流热水为主，含少量的泥质；白云石大理岩以热水喷流沉积为主。 3．本区至少遭受过三期变质作用：区域高温变质作用、流体蚀变改造作用和变形变质作用。区域高温变质作用变质温度最高可达可达660℃，主要集中在600 ~ 630℃之间，形成压力约为4.9 ~ 5.0Kbar。三期变质改造使原岩发生了绿帘-角闪岩相的变质作用，变质过程中，稀土元素（特别是轻稀土元素）和部分高场强元素发生了迁移；流体蚀变改造富集了早期的贫铜矿胚，使之形成工业矿床。 4．硫化物硫同位素研究显示，其δ34S值为-0.6 ~ +10.9‰，主要集中在+5.0 ~ +10.9‰之间。这一组成表明富集型硫化物大体继承了早期硫化物硫源特征，并在改造过程中富集重硫。早期硫化物硫源主要来自岩浆硫和海水无机还原硫。硫化物铅同位素范围为：206Pb/204Pb＝ 18.985 ~ 23.318，均值为21.222；207Pb/204Pb＝15.581 ~ 15.904，均值为15.747；208Pb/204Pb＝39.803 ~ 45.652，均值为42.540。显然，本区硫化物具有极高含量的放射性成因铅，部分放射性成因铅含量稍低的样品与前人所圈定的改造型矿床的硫化物铅同位素范围较为吻合。分析认为，本区硫化物铅同位素代表了两种不同铅源的混合，即早期硫化物的普通铅和围岩中的放射性成因铅。硫铅同位素示踪以及矿相学研究表明，本区早期铜质来源于海底火山喷流-沉积，而晚期富集型铜矿铜质继承了早期铜质，同时也不排除晚期流体中所带来的铜质。 5．流体包裹体研究表明，本区改造型流体中包括三种流体体系：①中-低盐度H2O-NaCl±KCl±FeCl3 ±CaCl2流体，盐度范围为0.53 ~ 24.59 % NaCl equiv.，密度为0.80 ~ 1.16 g/cm3；②高盐度高密度H2O-NaCl±CaCl2流体，盐度为31.2 ~ >59.76% NaCl equiv，密度为1.14 ~ 1.45 g/cm3；③纯液相CO2流体，流体密度为0.77 ~ 1.09 g/cm3。流体包裹体均一温度在100 ~ 456℃之间，主要集中在150 ~ 260℃和260 ~ 456℃两个温度区间。方解石碳、氧同位素范围分别为-5.6 ~ -3.1‰和12.4 ~ 15.5‰。综合分析表明，流体主要来自海底下伏岩浆房的出溶或喷流的高温高盐度流体，部分与海水混合。流体在热液改造过程中活化富集了早期硫化物，经过短距搬运而沉积形成了晚期富集型硫化物。 6．本次研究确定该矿床的成矿机制为：早-中元古代，本区的陆内裂谷作用为火山喷发提供了构造条件，海底火山喷流-沉积形成了早期的贫铜矿胚。元古代末期，本区遭受了强烈的区域变质、变形和流体蚀变改造作用，使原先的贫铜矿胚得到活化富集，形成了工业矿床。

河南小秦岭大湖金－钼矿床地球化学及其矿床成因

秦岭造山带是华北与扬子两大古板块的接合带，在空间上，自北而南，秦岭造山带可分为华北板块南缘（华熊地块）、北秦岭造山带、南秦岭造山带和扬子板块北缘等4个构造单元。小秦岭金矿田位于华熊地块北缘，是国内外学者共识的造山型金矿田，河南灵宝大湖金－钼矿床位于小秦岭金矿田，属断控脉状矿床。大湖金－钼矿床最先正是以金矿床进行勘查的，其黄金储量28t，平均品位8.7g/t。随着开采深度的加大，部分含金石英脉向深部转变为辉钼矿－石英脉，目前探明钼资源量已达中型规模。 本论文主要从区域地质背景、矿床地质特征、元素地球化学、同位素地球化学、流体包裹体地球化学、矿床年代学及成矿机理等角度对大湖金－钼矿床进行了较为系统的研究，主要获得如下认识： 成矿过程经历3个阶段：早阶段为黄铁矿-石英脉，遭受变形、破碎，应形成于挤压或压剪过程；中阶段为细粒的辉钼矿-黄铁矿-石英网脉，贯入到早阶段黄铁矿或石英矿物的裂隙（可呈共轭状），应形成于剪切环境；晚阶段石英-碳酸盐细脉具梳状构造，充填于张性或张扭性裂隙。 大湖金-钼矿床的金属硫化物ISr=0.70470-0.71312，平均0.70854；(143Nd/144Nd)i=0.51143-0.51215，平均0.51162；(206Pb/204Pb)i=17.033-17.285，(207Pb/204Pb)i=15.358-15.438，(208Pb/204Pb)i = 37.307-37.582。其围岩太华群样品平均值ISr＝0.72294，(143Nd/144Nd)i=0.51107，(206Pb/204Pb)i=17.127-18.392，(207Pb/204Pb)i =15.416-15.604，(208Pb/204Pb)i=37.498-37.814，它们的平均值分别是17.547，15.470，37.616。通过金属硫化物及围岩太华群的对比，可以看出，成矿物质具有太华群和深部地幔混合的特征。 通过对不同阶段的含矿石英脉中的流体包裹体特征研究表明，早阶段只发育CO2-H2O型流体包裹体；中阶段流体包裹体类型复杂，有纯CO2型、CO2-H2O型、H2O-NaCl型和含子晶包裹体，指示流体沸腾作用强烈；而晚阶段只发育水溶液包裹体。早、中、晚3个阶段的流体包裹体均一温度分别集中在400-500℃、290-470℃、220-260℃；估计的早、中阶段流体的最低捕获压力分别为138-331MPa和78-237MPa，对应于成矿深度分别为13.8-11.0km和7.8-8.0km。早、中阶段的压力反应出静岩压力到静水压力的转变。成矿温度和压力明显高于浅部含金石英脉的成矿温度120-310℃，成矿压力100-150MPa。与野外观察到的“上金下钼”的空间关系一致。 大湖金－钼矿床辉钼矿－石英脉Re-Os同位素模式年龄较集中，介于215.4±5.4－255.6±9.6Ma，Re-0s等时线年龄为218±41Ma(MSWD=38，2σ误差)，表明大湖金－钼矿的辉矿化形成于印支期。 三叠纪末，随着古秦岭洋的逐渐封闭，处在弧后转换带的深部岩石在挤压作用下发生变质脱水而形成初始成矿流体，成矿流体沿断裂带（韧性剪切带）向上迁移而引起大湖钼矿床成矿系统的发育。随着区域构造环境由挤压转为伸展，区域的变质脱水更强，形成大量成矿流体，变质流体上侵为浅层流体循环提供了的热能，而浅层构造也因减压扩容而为流体循环提供了通道，这无疑有利于浅层流体循环和混入成矿系统。同时，增温和减压也有利于成矿流体发生沸腾。因此，充足的流体、热以及强烈的流体沸腾等，势必导致发生最为强烈的成矿物质快速沉淀作用。随着挤压作用的减弱，伸展作用的增强，区域热异常消失，地壳深部组分发生亏损，流体以浅源大气降水占主导，成矿作用迅速衰竭，形成石英-碳酸盐网脉，对成矿作用贡献减弱。总之，通过对大湖金钼矿床研究表明，大湖金钼矿床形成于由挤压转向伸展的构造背景，这与矿床地质的特征一致。