东太平洋海隆13°N附近沉积物中的热液活动记录

本文以东太平洋海隆13ºN附近E53沉积物岩芯为研究对象，进行了矿物学、全岩化学分析及连续提取分析，探讨了沉积物中的热液活动记录及元素存在形式，并结合已有的测年数据，对研究区域的热液活动过程进行了初步讨论。 E53岩芯分为三层，上层为红褐色沉积层，中层为棕黄色沉积层，下层为灰绿色沉积层。沉积物岩芯的X射线衍射结果显示，E53岩芯上层非晶质的铁锰氧化物含量较高，中下段方解石含量较高。根据元素在岩芯全岩及各相态间的存在状况，将常量及微量元素分组讨论。Fe、Mn元素以铁锰氧化物相为最重要的赋存相，且与全岩样品一致，呈现随深度下降趋势。Al、Ti、Ba主要存在于残留相中；K、Na、Mg主要赋存相为碳酸盐相；Ca、Sr同样主要存在于碳酸盐相中。微量元素Mo、Co、V、Cu、Zn、Ni、Y和Pb元素主要存在于铁锰氧化物相，且含量均随深度增加而下降。Th、Sc、Li和Zr的主要存在于残留相中；Cd、U主要存在于碳酸盐相中。稀土元素存在形式有以下三个特点：1、主要存在于铁锰氧化物相中，并且呈现出随深度增加含量下降的趋势；2、次要存在形式为碳酸盐相，随深度增加含量上升并一度超过残留相中的含量；3、在有机结合相和残留相中含量很低，且变化幅度不大。 根据本文讨论结果，结合前人年代数据，认为E53岩芯中记录的为程度逐步加强且在近期保持稳定的热液活动。

Assessment of metal contamination in surface sediments of Jiaozhou Bay, Qingdao, China

An assessment of metal contamination in surface sediments of the Jiaozhou Bay, Qingdao, one of the rapidly developing coastal economic zones in China, is provided. Sediments were collected from 10 stations and a total of 15 heavy metals were analyzed. Concentrations of metals show significant variability and range from 210 to 620 ppm for Ti, 2.7 to 23 ppm for Ni, 4.2 to 28 ppm for Cu, 5.2 to 18 ppm for Pb, 12 to 58 ppm for Zn, 0.03 to 0.11 ppm for Cd, 5 to 51 ppm for Cr, 1.5 to 9.9 ppm for Co, 5.3 to 19 ppm for As, 12 to 32 ppm for Se, and 19 to 97 ppm for Sr. Based on concentration relationships and enrichment factor (EF) analyses, the results indicate that sediment grain size and organic matter played important roles in controlling the distribution of the heavy metals in surface sediments of the Jiaozhou Bay. The study shows that the sediment of the Jiaozhou Bay has been contaminated by heavy metals to various degrees, with prominent arsenic contributing the most to the contamination. The analysis suggests that the major sources of metal contamination in the Jiaozhou Bay are land-based anthropogenic ones, such as discharge of industrial waste water and municipal sewage and run-off. Notably, the elevated heavy metal concentrations of the Jiaozhou Bay sediments could have a significant impact on the bay's ecosystem. With the rapid economic development and urbanization around the Jiaozhou Bay, coastal management and pollution control should focus on these contaminant sources, as well as provide ongoing monitoring studies of heavy metal contamination within the bay.

中国北方中新世风尘物质来源及古气候的地球化学指示

The most prominent tectonic and environmental events during the Cenozoic in Asia are the uplift of the Himalaya-Tibetan plateau, aridification in the Asian interior, and onset of the Asian monsoons. These caused more humid conditions in southeastern China and the formation of inland deserts in northwestern China. The 22 Ma eolian deposits in northern China provide an excellent terrestrial record relative to the above environmental events. Up to date, many studies have focused on the geochemical characters of the late Mio-Pleistocene eolian deposits, however, the geochemical characteristics of the Miocene loess and soils is still much less known. In this study, the elemental and Sr-Nd isotopic compositions of the eolian deposits from the Qinan (from 22.0 to 6.2 Ma) and the Xifeng (from 3.5 Ma until now) loess-soil sections were analyzed to examine the grain size effects on the element concentrations and the implications about the dust origin and climate. The main results are as follows: 1. The contents of Si, Na, Zr and Sr are higher in the coarser fractions while Ti and Nb have the highest contents in the 2-8 μm fractions. Al, Fe, Mg, K, Mn, Rb, Cu, Ga, Zn, V, Cr, Ni, LOI have clear relationships with grain-size, more abundant in the fine fraction while non significant relationship is observed for Y. Based on these features, we suggest that K2O/Al2O3 ratio can be used to address the dust provenance, and that VR (Vogt ratio = (Al2O3+K2O)/(MgO+CaO+Na2O)) can be used as a chemical weathering proxy for the Miocene eolian deposits because of their relative independence on the grain size. Meanwhile, SiO2/Al2O3 molar ratio is a best geochemical indicator of original eolian grain size, as suggested in earlier studies. 2. Analyses on the Sr and Nd isotope composition of the last glacial loess samples (L1) and comparison with the data from the deserts in northern China suggest that that Taklimakan desert is unlikely to be the main source region of the eolian dust. In contrast, these data suggest greater contributions of the Tengger, Badain Jaran and Qaidam deserts to the eolian dust during the last glacial cycle. Since the geochemical compositions (major, trace, REE and Sr, Nd isotope) of loess samples for the past 22 Ma are broadly similar with the samples from L1, these data trend to suggest relatively stable and insignificant changes of dust sources over the past 22 Ma. 3. Chemical weathering is stronger for Miocene paleosol samples than for the Plio-Pleistocene ones, showing warmer/more humid climatic conditions with a stronger summer monsoon in the Miocene. However, chemical weathering is typical of Ca-Na removal stage, suggesting a climate range from semiarid to subhumid conditions. These support the notion about the formation of a semi-arid to semi-humid monsoonal regime by the early Miocene, as is consistent with earlier studies.

晚中生代松辽盆地形成的大地构造环境及成因机制

Directed by the theory of "Collision Tectonic Facies", the tectonic setting and dynamic mechanism of the formation of Songliao basin in late Mesozoic (J_3-K_1) are studied in the present thesis with the methods of petrology, petrochemistry, geochemistry and isotopic geochronology. The research contents in this paper include as followings. Firstly, the general tectonic frame is made up of different tectonic facies formed from Mid-late Proterozoic to Mesozoic, which are Huabei plate, the Chengde-Siziwangqi melange (Pz_1), the Wenduermiao magmatic arc (Pz_1), the Hegenshan-Chaogenshan melange (Pz_2), the accretion arec (Pz_1-P), the Raohe-Hulin melange (Mz), the magmatic arc (Mz) and the pull-apart basin on the magmatic arc (Mz). Secondly, the volcanic rock assemblages of Songliao basin and its adjacent area in late Mesozoic is the typical calc-alkaline of the magmatic arc. The types of volcanic rocks in the study area include basalts, basaltic andesites, andesites, dacites and rhyolites, and basic-intermediate volcanic rocks have higher alkalinity. The volcanic rock series in this area is the high-K calc-alkaline series. Thirdly, the total REE of volcanic rocks in Songliao basin and its adjacent area is higher than that of the chondrite. The pattern of the REE normalized by the chondrite shows the characteristics similar to that of the typical island arcs or the active continental margins in the earth, that is enrichment of LREE and depletion of Eu. The spider-diagram of the trace element normalized by the primitive mantle also expresses the similar features to that of the typical island arcs or the active continental margins, it has distinctive valleies of Nb, Ta, Sr, P, and Ti, as well as the peaks of La, Ce, Th, U, and K. The incompatible elements show that the high field strength elements, such as Nb, Ta, Ti, and P, are depletion while the low field strength elements, such as K, U, Pb, and Ba, are enrichment. These features are similar to those of orogenic volcanic rocks and imply the formation of the volcanic rocks in this area is related to the subduction. The degrees of both the enrichment of the HFS elements and depletion of the LFS elements become more obvious from basic to acid volcanic rocks, which suggests crustal contamination enhances with the magmatic crystallization and fractionation. The concentration of the compatible elements is W-shape, and anomalies in Cr and Ni suggest there is the contamination during the magmatic crystallization and fractionation. Fourthly, the isotopic age data prove the volcanic activity in the Songliao basin and its adjacent area started in the early-middle Jurassic, and ended in the end of the early Cretaceous-the beginning of the Cretaceous. The volcanism summit was the late Jurassic-the early Cretaceous (100 - 150Ma). Finally, the tectonic setting of volcanism in the late Mesozoic was magmatic arc, which originated the subduction of Raohe-Hulin trench to the northwest Asian plate. The subduction began in the middle Jurassic, and the collision orogenesis between the Sikhote-Alin arc and Asian continent was completed in the end of the early Cretaceous-the beginning of the late Cretaceous. The results of above tectonic processes were finally to format Nadanhada orogenic belt symbolized by the Raohe-Hulin suture or melange belt. The violently oblique movement of the Izanagi plate toward Asian plate in the late Mesozoic was the dynamic mechanism of above tectonic processes. At the same tome, the left-lateral strike-slip shear caused by the oblique movement of the Izanagi plate produced a series of strike-slip faults in east Asian margin, and the large scale displacements of these strike-slip faults then produced the pull-apart basing or grabens on the magmatic arc. Conclusively, the tectonic setting during the formation of the grabens of Songliao basin in the late Mesozoic was magmatic arc, and its dynamic mechanism was the pull-apart. In a word, there was a good coupling relation among the oblique subduction of the oceanic plate, collisional orogene between island arc and continental plate, strike-slip shear of the faults and the formation of the grabens in Songliao basin and its adjacent area in late Mesozoic. These tectonic processes were completed in the unoin dynamic setting and mechanism as above description.

鲁西临朐地区中生代铁寨杂岩体的岩石化学与地球化学特征及其成因研究

The Tiezhai intrusive complex is located in the north of the Luxi block, Shandong province, eastern China. It lies ～30 km west of the Tanlu fault, and is at the cross of the Wujing and Jiushan faults. The Tiezhai complex was formed about 120～130 Ma, when large-scale magmatism was active in eastern part of North China. This paper carries out petrochemical and geochemical study on the Tiezhai intrusive complex, and discusses its genesis in detail. The Tiezhai intrusive complex can be subdivided into three rock series. The first is the gabbro-diorite series formed in early stage. Its composition variation shows 01 and Cpx fractional crystallization trend. The second is the porphyritic diorite and monzonite series, showing dominating Hb fractional differentiation. Their composition variation shows Hb fractional crystallization trend. The third is the porphyritic quartz monzonite with K-feldspar megacrysts, showing weakly Hb and Bi fractional crystallization trend. All types of rocks in the Tiezhai complex are belonging to the high-K cac-alkaline series. They have elevated Sr (450-1660 ppm), Ba (210-1780 ppm) and relatively low Rb (30-100 ppm). For the gabbro-dioritic rocks in the early stage, the abundances of Ni (20-250 ppm), Cr (50-350 ppm), V(l30-250 ppm) and Co (20-40 ppm) are high, indicating a mantle origin. All rocks have negative anormalies of Nb, Ta, Ti and P, and enriched LREE and strong differentiated REE patterns. The porphyritic monzonites and quartz monzonites have very low HREE, Yb and Y contents and positive Eu anormalies, similar to adakite. Most rocks have lowε_(Nd)(t) of-1.5～-10.9, and high (~(87)Sr/~(86)Sr)_i of 0.704～0.709. The data have characters of enriched lithosphere mantle (EMI). In summary, the Tiezhai intrusive complex was inferred to be generated by a mantle derived magma through fractional crystallization. When the primary magma gathered in some place between crust and mantle, the crystallization started and causing magma evolution. The remaining / evolved magma ascended and emplaced again and again in the upper crust in Tiezhai area. Then Tiezhai complex formed. The porphyritic monzonites and quartz monzonites have major and trace element characters of typical adakite, but they are likely to be generated by Hb fractional crystallization.

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.

安多地区早中侏罗世岩浆岩岩石地球化学和同位素年代学研究及其对构造演化的制约

Anduo area is located in the Central Tibet, the middle segment of the Bangonghu-Nujiang suture. Anduo Block is the northern part of Lhasa terrane. The relationships among the different geological bodies were determined during the 1: 250000 regional geological surveying. Petrography, petrologic geochemistry, isotopic geochemistry and geochronology of igneous rocks from the suture and granitoids from Anduo Block were analyzed systematically as a whole for the first time. Then, their tectonic setting and history are discussed.Anduo ophiolitic melange consists of metamorphic peridotites, cumulates, plagiogranites, sheeted dykes swarm, pillow lava and radiolarian cherts. The concentration of Cr and Ni in the metamorphic peridotites is very high, with Mg# about 0.94 ~ 0.97, higher 87Sr/86Sr and Pb isotopic ratios, and lower 143Nd/i44Nd ratio. LREE is enriched relative to HREE and positive Eu anomaly is very clear. The REE distribution curve is U shape. Nb and Ta anomalies from cumulate gabbro and sheeted dyke swarm are not clear, while that are slightly negative from pillow lava. Plagiogranite belongs to strong calc-alkaline series with high Si, middle Al, low Fe, Mg and low K contents. Eu anomaly (~ 1.23) from plagiogranites is slightly positive. The character of all components of ophiolite is similar to that of the MORB, while to some extent the ophiolite was influenced by crustal material. Anduo ophiolite formed in a mature back-arc basin. Additionally, intermediate acidity volcanic rocks within Anduo phiolite melange are island arc calc-alkline rocks related to ocean subduction.The early-middle Jurassic plutonic rocks are tonalite, granodiorite bearing-phenocryst, magaporphyritic hornblende monzogranite, magaporphyritic monzogranite, monzogranite bearing-phenocryst and syenogranite in turn. They belong to calc-alkaline series which developed from middle K to high K series temporally. REE distribution curves of all plutonic rocks are similar and parallel to each other. SREE and negative Eu anomaly values decrease. In the multi-element spider diagram, the curves of different plutons are similar to each other, but troughs of Nb, Sr, P and Ti from young plutons become more evident. This suggests that thereare some closely petrogenetic affinities among plutonic rocks which make up amagma plutonism cycle of the early-middle Jurassic. Magma source is mainly crustal,but abundant mafic microgranular enclaves within granitoids indicate that crastalmagma should be mixed with mantle-derived magma and the mantle-derived magmadecreased subsequently. Tonalite has features of I-type granite, magaporphyriticmonzogranite is transition type, and monzogranite bearing-phenocryst is S-typegranite. The characteristic of granitoids from Anduo Block suggest that the formingtectonic setting is active continental margin.Reliable zircon U-Pb SHRIMP ages are obtained in the study area firstly. Plagiogranite from the Anduo ophiolite of the Bangonghu-Nujiang suture is 175.1 Ma, and granitoids from Anduo Block is 172.6-185.4 Ma. Additionally, plagioclase from the plagiogranite dates a 40Ar/39Ar age of 144 Ma, while biotite and hornblend from granitoids of Anduo Block give a 163-165 Ma.Similar cooling ages of plagiogranite from the Anduo ophiolitic melange and granitoids from Anduo Block and the spatial distribution of the ophiolitic rocks between Anduo, Naqu, and Shainzha area suggest that bilateral subduction of the Bangonghu-Nujiang oceanic basin took place in the early-middle Jurassic. During this subduction, Anduo ophiolitic rocks were related to north subduction of the Bangonghu-Nujiang oceanic basin and Anduo back-arc basin spreading, while granitoids from Anduo Block were related to south subduction.

重庆城口地区早前寒武系黑色岩系研究：（3）巴山组硅质岩中PGE异常的地球化学研究

以猪草河剖面和羊儿坝剖面为例，进行硅质岩的PGE与微量元素等地球化学分析，结果表明：槽区硅质岩中的PGE异常受控于硅质岩中火山物质（蚀变成粘土矿物）的多少，PGE与Se、Rb、Cs、Ti、Cr、Zr等具有良好的相关性；猪草河剖面远离陆源区，沉积厚度大，更靠近火山活动区域，接受火山粗碎屑物质的量多；羊儿坝剖面远离火山活动中心，主要接受了火山灰等细碎屑物质，更接近陆源区，受一定量的陆源碎屑物质影响。根据Cr／Co、Nb／Ta、Pd／Ir-Ni／Cu及Ni／Pd-Cu／h对岩浆性质的约束，当时岩浆性质为基性玄武岩。根据La-Y-Nb图解和Th-Hf-Ta图解的进一步约束，表明当时的火山岩浆性质为钙碱性的火山弧玄武岩。

渔塘坝硒矿硅质岩的地球化学特征及成因

渔塘坝硒矿床是目前我国发现含硒量（8590×10^-6）最高的小型独立硒矿床，其赋矿岩石主要为硅质岩，且发育程度较高。早二叠世晚期的黑色碳质硅质岩系，是区内的赋矿层位，它局限于特定的沉积相位，即碳酸盐合地海盆浅部沼泽（藻沼）环境沉积的黑色碳质硅质岩相带，硒矿化层和这套碳质硅质岩相带密切相关，其矿化相带呈NW向展布。硅质岩的SiO2含量变化较大（64.2%-94.85％），平均为75.9%;Fe2O3、Fe2O3、FeO、MnO、TiO2、Al2O3和MgO等含量相对，与其它热水成因硅质岩相近；硅质岩富含As、Sb、Fe和Ag，而贫Cu、Co和Ni；在Al-Fe-(Cu+Co+Ni)三角图、U-Th相关图和P2O3-Y相关图上的投影特征，也同样显示出硅质岩的热水成因特征。另本区硅质岩中的Cr含量较大，且（Fe+Mn）/Ti的比值为6.34，这表明硅质岩在成因上还可能和二叠纪峨眉山玄武岩喷发的火山作用有一定的联系。

Mo稳定同位素研究进展

随着表面热离子质谱（TIMS）和多接收器电感耦合等离子体质谱（MC-ICP-MS）的广泛应用以及同位素分析方法的改进,近10年来非传统稳定同位素（Cu、Zn、Fe、Se、Mo、Cr、Hg等）的研究得到迅速发展。其中,由于Mo同位素的分馏明显受氧化还原条件的控制,使其在指示古环境及古气候的变化方面有独特的地球化学指示意义。同时,Mo同位素在指示成矿物质来源和海洋Mo循环等方面也取得较大成果。因此,Mo同位素地球化学研究已成为国际地学领域的一个前沿和热点。本文综合前人的研究成果,结合近期自己的工作,论述了Mo同位素地球化学研究领域的一些重要进展,详细介绍了Mo同位素的化学分离、提纯和质谱分析技术,并对其应用前景进行了展望.

新疆霍什布拉克铅锌矿床地质、地球化学特征研究

新疆霍什布拉克铅锌矿床的矿体和含矿地层的产状一致,主矿体的矿石具有条带状、纹层状构造,矿石中大量发育霉球状、管状和环带状生物结构,显示出层控、热水沉积成因的特点。含矿地层和矿石样品的主量元素PER图解显示含矿碳酸盐岩以含石膏的灰岩为主,围岩的白云岩化微弱,矿化与硅化关系密切。矿石、含矿碳酸盐岩和页岩、粉砂质灰岩和泥质粉砂岩等碎屑岩具有各自鲜明的微量元素分布特征,上层矿体矿石中较强的富集过渡族元素Ti、V、Cr、Mn、Co、Ni、非活动性元素Zr、Hf及大离子亲石元素Sr和Pb,亏损活动性元素Na、K、Rb、Ba和非活动性元素Nb、Th。其围岩重结晶泥晶灰岩富集Ti、Mn、Ni、Sr和Pb,亏损Na、K、V、Fe、Rb、Ba、Zr、Hf、Nb和Th。下层矿体的围岩页岩和泥质、粉砂质灰岩样品的微量元素分布在平均上地壳线附近,部分样品较明显的富集Ti、V、Cr、Mn、Co、Ni、Rb、Y、Zr和Hf,亏损Na、Fe、Sr、Nb。上层矿体矿石和下层矿体围岩中的部分碎屑岩富集强亲岩浆元素Cr、Co、Ni,且上层矿体矿石的稀土元素分布模式具有强的正Eu异常,部分下层矿体围岩具有较明显的正Eu异常。地质和地球化学特征显示该矿床属于热水沉积矿床中的SEDEX型矿床.

湘黔地区早寒武世黑色岩系沉积学及地球化学研究

中国南方古生代广泛分布富有机质的黑色页岩，分布层位较多(如下寒武统牛蹄塘组底部的黑色页岩、奥陶系五峰组页岩、志留系龙马溪组黑色页岩、泥盆系深水台间盆地的黑色碳质、硅质页岩，以及二叠系的黑色页岩、硅质岩等），并伴有Mo、Ni、PGE、V、Au、Ag等贵重金属元素富集层，尤其是湘黔地区下寒武统牛蹄塘组底部的黑色页岩，作为瞬时灾变沉积物，可与全球大洋缺氧事件对比。贵州省遵义地区黄家湾和湖南张家界地区柑子坪剖面为该地区较典型的剖面，前人已进行了大量的岩石地层、生物地层、元素地球化学研究工作，但沉积学方面尚缺乏系统性与较深入研究，特别是关于以黄家湾剖面为代表的浅水沉积体系与柑子坪剖面为代表的深水相黑色页岩沉积体系之间的时空关系缺乏统一的认识，且有机地球化学研究涉及甚少。因此，本文从沉积学和地球化学两方面，特别是有机地球化学方面，探讨了湘黔地区下寒武统底部牛蹄塘组黑色岩系的成因以及相应的灾变事件－大洋缺氧事件，取得如下认识： (1)本文对研究区下寒武统地层进行了较全面的清理，重新厘定了研究区下寒武统地层系统。下寒武统自下而上划分为牛蹄塘组、明心寺组、金顶山组和清虚洞组，其时代经历了梅树村阶、筇竹寺阶、沧浪铺阶和龙王庙阶，与西伯利亚地区同期沉积相比，分别对应晚Tommotian、Atdabanian、Botonian和Toyonian期。 (2)确定了研究区下寒武统岩石类型有碳酸盐岩、泥质岩和碎屑岩三大类。下寒武统下、中部泥质岩、粉砂岩及砂岩发育，且以泥质岩为主，少有碳酸盐岩发育，而上部清虚洞组灰岩(白云岩)发育。下寒武统牛蹄塘组黑色岩系主要由黑色页岩、石煤、硅质页岩、硅岩、粉砂岩、磷块岩、重晶石岩等组成，主要矿物组合为石英、伊利石和黄铁矿以及少量重晶石、磷灰石和方解石。从生物地层、岩石地层、年代地层来看，牛蹄塘组底部黑色页岩与南亚、西亚、欧洲、北美等地Tommotian期广泛分布的黑色页岩有很好的可对比性。 (3)基于对地层清理、古生物以及岩石学特征的详细研究，研究区下寒武统可划分为碎屑岩海相和碳酸盐岩海相两个沉积体系组。碎屑岩海相又分为滨岸、内陆棚、外陆棚、斜坡亚相；碳酸盐岩海相主要为开阔台地亚相。从时空上看，地层由老到新，粒度逐渐变粗，水体逐渐变浅，从外陆棚-斜坡、内陆棚到滨海，最后为开阔台地相；从西向东，由浅水相区的滨岸到内陆棚，最后到深水相区的外陆棚到斜坡。 (4)晚震旦世灯影组灰白色粉晶白云岩样品的SiO2含量比较低，MgO、CaO、CO2含量较高。牛蹄塘组黑色碳质泥岩、碳质页岩以SiO2含量为主，其次为Al2O3和Fe2O3。微量元素含量具有如下特征：地层由老到新，从灯影组白云岩→牛蹄塘组磷块岩/硅质岩→多金属富集层，呈现出增加趋势，此后至黑色页岩又有回落。特征微量元素(如Mo、Ni、V、U等)及其比值(如V/(V+Ni)、V/Cr、Ni/Co、U/Th、δU等)显示这套富含有机质黑色页岩为热水沉积，其沉积环境为含氧量逐渐减少的贫氧-缺氧的还原环境。 (5)稀土元素总量(∑REE)从6.67ppm变化到481ppm，平均含量为123ppm，轻稀土相对比较富集。经PAAS标准化的稀土配分模式曲线具有近于水平或略显右倾特征。灯影组Ce异常值均小于-0.10，代表当时海水处于氧化阶段。而牛蹄塘组底部和上部Ce异常值大于-0.10，接近0，代表弱的缺氧沉积环境。对于牛蹄塘组中部，其值小于-0.10，说明缺氧环境持续了一段时间后，海洋出现了一个短暂的充氧期。根据Ce异常和参考海平面，研究区晚震旦世-早寒武世可识别出3个主要海平面升降旋回。而Eu异常为0.002-1.16，大多数样品显示负Eu异常，表明其沉积环境为缺氧的还原环境。 (6)所有样品均含丰富的正构烷烃、类异戊二烯烃、萜类化合物以及甾类化合物，尤其是具有重要价值的甲基三环萜烷系列、25-降藿烷系列以及甲基甾烷。在GC谱图上，正构烷烃显示明显的单峰型分布特征，碳数分布范围为nC14-nC31，主峰碳为nC18、nC19或nC20，无明显的奇偶碳数优势分布。类异戊二烯烃、萜类化合物以及甾类化合物等的特点也表明，早寒武世黑色岩系不同层位中有机质的先质均来源于菌藻类生物，有机质类型属于腐泥型，沉积环境为强还原到弱还原环境。有机质成熟度指标显示了研究区有机质热演化程度高，一般已经达到生油门限或高成熟阶段，其中以黑色页岩的演变程度最高，但仍未达到演变的最终阶段。 (7)在地层剖面上，有机碳含量为0.05-12.31％，平均为4.97%；有机碳同位素组成(δ13Corg)从-29.49－-34.41‰（PDB），发生负偏移，偏移量达到4.3‰，而δ13Ｃcarb值从晚震旦世的-4.6‰下降至早寒武世的-10.6‰，具有6.0‰的负偏移，δ18Ocarb值在-13.7－-2.3‰(PDB)之间。δ13Corg与δ13Ｃcarb变化具有一致性，表明其偏移与有机质组分无关。在Tommotian晚期，海平面持续上升，海洋循环引起海洋的含氧量减少，可能是引起δ13Ｃ负偏移的一个原因。另外，加上海洋条件急剧恶化，底层水缺氧更严重。因此可确定研究区Tommotian期缺氧事件的存在。 上述研究表明，湘黔地区早寒武世黑色岩系的形成和Tommotian期缺氧事件的发生既与区域背景有关，又与有机质遭受细菌降解、生物爆发致使生物生产率的提高有关，还与海平面升降有关。扬子地台在晚震旦世-早寒武世处于全球海平面上升阶段，底层洋流活跃，大量营养物质被上升流周期性地带到表层水中使生物大量繁殖，生物生产率增加，底层水含氧量减少。在这种背景下，氧化作用缓慢，海进期间歇性的上升洋流把富有机质的缺氧水带到相对深水区，导致黑色页岩广泛分布。由于表层浮游生物大量死亡，腐烂分解吸收大量溶解氧，再加上上升洋流也分解有机质，因此底层水迅速变成“无氧状态”，导致沉积物中海洋生物死亡，有机质突然急增而大量保存下来，加强了缺氧环境。

内蒙古乌兰图嘎超大型锗矿床含锗煤的地球化学

乌兰图嘎锗矿是我国近年来发现的产在煤层中的超大型锗矿床，锗金属储量达1600吨，其成矿地质条件与成矿模式不同于临沧锗矿和俄罗斯远东地区的锗矿。本文以乌兰图嘎含锗煤的地球化学特征为重点，利用X射线衍射、扫描电镜、电子探针、ICP-MS和数理统计等多种分析方法，系统研究了乌兰图嘎含锗煤的矿物学、微量元素和稀土元素地球化学特征，结合与其他地区含锗煤地球化学特征的对比，初步探讨了乌兰图嘎锗矿的成因。论文获得以下几点主要认识： 1. 乌兰图嘎含锗煤中的主要矿物包括石英、蒙脱石；次要矿物包括长石、高岭石、伊利石；另含少量三水铝石、角闪石、叶蜡石、石膏、绿泥石、锐钛矿、黄铁矿、方解石、白云石和草酸钙石。扫描电镜和电子探针分析表明，乌兰图嘎含锗煤中还存在锆石、闪锌矿、白钨矿、重晶石、黄铜矿、卤化物、磷酸盐以及含Pb、Bi、Cr、As和Sb矿物。未发现含锗矿物。首次在乌兰图嘎含锗煤和红旗煤矿的无矿煤中发现含Ag矿物。 2. 与上地壳平均组成相比，乌兰图嘎锗矿褐煤明显富集Be、Ge、Sb、W和U，亏损Rb、Nb、Sn和Ta。乌兰图嘎锗矿褐煤中Be、Ge、Sb、W和U的平均含量明显高于乌兰图嘎砂岩和红旗煤矿褐煤，以及美国煤和世界煤的平均组成。乌兰图嘎锗矿含矿煤的稀土元素平均含量略高于美国煤或世界煤的平均组成、乌兰图嘎砂岩以及同时代的红旗煤矿无锗煤中的稀土元素含量。稀土元素与锗含量无明显的相关性。 3. 按元素组合不同，煤中微量元素可划分为4个组：Ge-Mo，Tl-Ga-Zn-Co，Rb-Cs和W-U-Cd-Y-Pb-Cu-Hf-Zr-Th-Sn-Nb-Ta-Ti-Sb-Ba-Sr-Mn-Be组合。第一组合包括与灰分呈负相关的元素，它们主要表现出有机亲合性。 剩下三组包括与灰分呈负-较高相关的元素，其主要与硫化物或铝硅酸盐矿物结合。大多数含锗煤的稀土元素含量与灰分呈高度正相关，表明含锗煤中的稀土元素主要来自陆源碎屑并主要与同沉积矿物相结合。稀土元素在少数高锗煤中的富集与存在独居石有关。 4. Ge和Mo富集在不同剖面的不同部位，其余微量元素和稀土元素或多或少地跟随灰分的分布。TiO2标准化的元素剖面揭示乌兰图嘎褐煤样品中的Be/TiO2、Ge/TiO2、W/TiO2、U/TiO2、Mo/TiO2、Sb/TiO2、Tl/TiO2和Sr/TiO2比值较乌兰图嘎砂岩和红旗煤矿褐煤中的参考值高出许多。这些元素（Be、Ge、W、U、Mo、Sb、Tl和Sr）的大部分(>90%) 可能由溶液带入煤层。稀土元素与TiO2的比值总体接近矿区砂岩以及红旗煤矿无矿煤中的对应比值。 5. 乌兰图嘎含锗煤具有与矿区砂岩和红旗煤矿无矿煤类似的、页岩式的球粒陨石或北美页岩标准化稀土元素分配模式；与上覆砂岩的稀土元素组成相比，少量含锗煤表现出轻微但明显的中-重稀土富集，表明少量的中-重稀土在后生作用中被叠加或保留在乌兰图嘎含锗煤中。乌兰图嘎锗矿的含锗煤以较高的LREE/HREE和Eu/Eu*比值以及平坦的北美页岩标准化稀土元素分配模式为特征，明显区别于临沧锗矿和俄罗斯远东地区锗矿中的含矿煤。 6. 乌兰图嘎锗矿含锗煤中大多数的微量元素和稀土元素可能来源于花岗岩源区，Be、Ge、Sb、W和U的富集可能与后生的、侧向迁移的含锗溶液有关。含锗溶液自花岗岩源区淋滤出这些元素并将其搬运至褐煤中，煤中有机质将溶液中的锗固定而聚集成矿。

中国南方含硒建造中硒稳定同位素与化学形态的地质意义

氧化还原敏感元素硒的地球化学循环非常复杂, 它的循环主要受氧化还原势、酸碱度、温度、压力等条件的控制。长期以来，关于硒的主要研究集中在环境生物地球化学领域。对于硒的地质地球化学行为的研究，学者们认为硒不可能独立形成矿床,它主要以伴生元素的形式赋存于一些热液矿床（如，拉尔玛硒-金热液矿床等）。 二十世纪末, 我国学者开始关注硒的矿床地球化学行为, 发现了目前唯一的渔塘坝沉积型的独立硒矿床。另外，下寒武统底部黑色岩系（如，遵义牛蹄塘组）处于地球发展演化的关键时期且富集了众多的有用金属元素, 因此它引起了全世界广大地质学家的普遍关注和重视。这些黑色岩系的共同特点是含有大量的有机质和丰富的金属元素(PGE，Cu，Ni，Mo，Au，U，V，Mn，Fe，Co，Bi，Cr，Se等)。但遵义牛蹄塘组中Ni-Mo多金属层的成因一直争论不休。 本文以拉尔玛硒-金热液矿床、渔塘坝独立硒矿床、遵义黄家湾含Ni-Mo-Se多金属层剖面为研究对象，主要通过硒稳定同位素的测试和不同化学形态的分析结合其他的地球化学参数（如，C-S-Fe体系，氧化还原敏感元素），示踪富硒地层的沉积环境，研究不同地质体系中硒稳定同位素的组成，进而完善硒同位素的理论体系，探讨硒富集过程中的形态迁移途径，并为矿床的形成提供更完善的地球化学证据。通过一系列的研究工作，我们取得了以下几点认识： (1) 通过不同的消解方法准确测定了低硒,高硒样品的总硒含量,相对标准偏差小于10%，而且不同的消解方法测得同样的结果, 满足了地质样品中微量元素的测试要求。由于不同消解方式存在自身的优缺点,我们建议根据不同的样品类型,不同的研究目的选取合适的消解方法。 (2) 通过巯基棉吸附装置达到了纯化富集样品硒的目的, 硒的回收率一般大于90%, 满足同位素测试的需要。应用自制的氢化物发生器与Nu-MC-ICP-MS联用,实现了在线气体进样测试硒稳定同位素的目的。 采用标准样品匹配测试方法校正仪器测试过程中的质量分馏。 硒稳定同位素的测试精度为2δ=0.30‰, 标准NIST SRM 3149采用与样品同样的处理方法,没有发现前处理过程的同位素分馏。 (3) 传统地球化学参数对沉积环境的指示意义。通过氧化还原敏感微量元素及其与TOC的关系和C-S-Fe体系的分析，对渔塘坝独立硒矿床的多元素富集及沉积环境, 遵义黑色岩系沉积环境进行了详细的解释。TS-TFe的关系表明样品中有过量的硫存在，可能为有机硫或为其他亲硫元素提供有利的沉淀条件。C-S-Fe体系及微量元素指数V/(V + Ni) 说明渔塘坝矿区的硅质岩和页岩的沉积环境为缺氧到静海环境， Ni/Co、V/Cr几乎不能作为该区缺氧环境的指示参数, 后者可能由于Cr的外源输入（碎屑、热液等）所致。 C-S-Fe体系及微量元素指数V/(V + Ni)体系指示遵义黑色岩系的沉积环境为微含氧到缺氧的条件, 但对于Ni-Mo矿而言, V/(V + Ni)体系指示其为含氧条件沉积，这可能与Ni-Mo多金属层的成因有关。但铁的硫化度可以指示Ni-Mo多金属层极端的缺氧还原环境。 (4) 硒的形态对古氧化还原条件和矿物质来源的示踪意义。黑色岩系的硒形态分布不同于海洋沉积物，体现了成岩作用对硒形态分布的改变。黑色岩系中硒的主要形态为有机结合态和硫化物/硒化物结合态。硫化物/硒化物结合态比例与铁的硫化程度（DOS）之间明显的相关关系说明在海洋环境中硒主要通过氧化还原反应富集在富有机质的沉积物与沉积岩中。这种相关关系与岩石类型没有关系，这使得将硫化物、硒化物结合的Se（-II）比例作为一个氧化还原条件示踪剂更加可行。DOS与硫化物/硒化物结合态硒的关系，及Se（IV）与Se（-II）的关系均说明遵义牛蹄塘组的K-斑脱岩形成于碱性的氧化环境，Ni-Mo多金属层沉积于微酸性的极端还原环境，而渔塘坝矿床形成于微碱性的还原缺氧环境。生物的同化作用与异化作用之间本身存在互补关系，但这种互补关系却存在不同的转化趋势。不同的转化趋势可能主要受氧化还原反应和酸碱度的控制，其他的地质作用也可能起着重要作用（如，硅酸盐、Fe（II）的含量，硫化物、有机质含量，风化程度等）。同时我们发现相同的氧化还原条件下可能存在不同的富集途径。Ni-Mo多金属层中极少的有机结合态硒暗示海洋同生沉积主要被生物异化还原控制，而沉积物从海洋富集硒的途径主要为直接由Se（VI）和Se（IV）到Se（-II）的还原途径，从高价态到元素态的还原途径可能偶有发生但强度很小。 (5) 硒稳定同位素对矿床成因及物质来源的示踪意义。热液或表生环境中,硒的再次活化迁移对硒同位素的大范围分馏是很重要的。较少的硫化物结合态硒和较大范围的硒同位素组成说明渔塘坝矿床形成时经历了多次氧化还原过程。干酪根硒同位素组成与全岩相似, 而且样品富集轻同位素暗示该矿床硒来的富集主要通过海洋硒的生物吸收同化异化还原与多次无机氧化还原实现。对于拉尔玛金硒矿床而言，未蚀变岩体的硫化物结合态硒富集轻同位素，而后期低温流体的蚀变作用导致蚀变岩体中硫化物结合态硒富集重同位素。干酪根的硒同位素组成暗示热液输入的硒为该矿床硒的主要来源，硒从热液直接进入干酪根的机制是一致的。随着硫含量的增加岩石和矿体中的硒逐渐富集重同位素, 说明海水对矿床富集的贡献是很有限的。遵义黑色岩系中硒同位素组成与Se（-II）之间的关系, 单质硒的缺乏，硒的富集与同位素的关系说明，热液为主要的硒来源，而早寒武世海水中的硒主要通过Se（VI）和Se（IV）到Se（-II）的直接生物还原实现。三个区域的S/Se比值综合说明硫与硒的共同沉降过程中不存在硒的同位素分馏。不同化学形态的分布与不同形态中硒稳定同位素的结合可能会更好的解释硒的全球地球化学循环。 (6) 根据目前硒的同位素分馏体系及所测得的数据,我们初步建立了不同时代、不同成因黑色岩系中硒稳定同位素的分馏模式。

地幔柱与岩浆成矿-峨嵋山大火成岩省地震波速层物相解释及典型PGE矿床成岩成矿机制研究

地幔柱概念在19世纪60至70年代就被提出，但是由于板块构造理论在解释地球上岩浆活动的分布规律时取得了空前的成功，在当时这一理论是被排斥的。板块边界概念可以解释地球上绝大部分的岩浆产出，但在解释板内岩浆的成因时往往显得力不从心，尽管这些岩浆的体积只占地球岩浆总量的2％。地幔柱理论模型发展到现在得到不同学科的支持。地质学、地球化学、地球物理学、古生物学、比较行星学、实验岩石学等等都提供了直接或间接的证据，证明地幔柱几乎存在整个地：质历史时期。当前地幔柱理论中在地球化学领域有两大研究热点：高钦低钦玄武岩的起源以及地幔柱中是否存在循环俯冲洋壳物质。完全解决这些问题才可能深入系统地建立地慢柱成矿作用模型。现在已经建立了一些矿床类型与地慢柱作用的联系：如现在认为赋存在金伯利岩中的金刚石矿床的形成与地慢柱作用密不可分，一些岩浆硫化物矿床和岩浆氧化物矿床很显然是地慢柱岩浆作用形成的，如西伯利亚火成岩省的Noril'sk-Talnakh铜镍铂族元素矿床以及KeweenawaJI大陆裂谷体系的Dultlth杂岩体的Cu-Ni矿床。另外还有赋存在大型基性一超基性层状岩体中的PGE、Ni和cu矿床，如Great Dyke和布什维尔德杂岩体。一些超大型热液矿床也与地慢柱有可能的联系（Pirajno，2000）：如270oMa形成的超大型Kidd Creek火山成因块状硫化物矿床（Bleeker et al.，1 999；Wynan et al.，1999）和南澳大利亚1600Ma形成的超大型olymPicD翻矿床。本文的研究工作包含两方面内容：通过热力学计算峨眉山玄武岩在深部的结晶分异，对峨眉山大火成岩省的岩浆量分布和岩浆氧化物矿床（华Ti磁铁矿矿床）的分布以及下地壳高波速层的物相进行理论解释；对峨眉山大火成岩省金宝山PGE典型矿床进行成岩成矿的地球化学研究，预测整个大火成岩省的岩浆硫化物矿床产出位置。大多数峨眉山玄武岩的 MgO＜7％，Ni为4-232ppm，它们是原始岩浆结晶分异后的产物。峨眉山玄武岩省下地壳和上地幔之间存在厚度为：8-25km1，P彼速为7.1-7.8km／s的附加层（高地震波速层）。滇西地区出露的洲套第三纪富碱斑岩，地球化学和同位素研究表明斑岩的岩浆源是来自“壳一慢混合层”，源区的形成时代为220-25Ma，与峨眉山玄武岩的形成时代一致。所以有理由认为该附加层是由峨眉山玄武岩在此结晶分异形成的。与地慢柱有关的洋岛Hawaii、Marquesas Islands；海底高原Oniong Java、大陆火山岩省ColumbiaRiver Plateaus地震彼研究都表明在上地慢顶部有一高速附加层，Farnetani etal.（1996）的研歼表明高速附加层是由来自地幔柱的岩浆在此结晶分异形成的。玄武岩是一种混合的部分熔融产物，是不同成分的地幔橄榄岩在不同的压力下熔出的。这种降压熔融高温高压实验是做不到的。熔出的熔体成分是温度、压力及橄榄岩成分（源区）的函数，形成的岩浆是一个多压熔融的集合体。热力学计算能够较为精确地计算出生成的岩浆成分和约束岩浆产生的过程。岩浆的结晶分异也是同样的情形，尤其是分离结晶过程，实验岩石学是很精确难模拟其过程的。热力学计算使用的MELTS程序，MELTS适用范围很广，适用于模拟岩石熔融生成岩浆和岩浆的冷却结晶。现今峨眉山大火成岩省的地壳厚度为40恤，这被认为是后期褶皱加厚的缘故。根据峨眉山玄武岩中辉石斑晶成分和玄武岩本身成分计算出分异结晶的压力为6kb，那么当时的地壳厚度约为20km：选择氧逸度为QFM，这一氧逸度范围认为是大多数大陆溢流玄武岩结晶分异时的氧化还原环境。热力学计算结果通过峨眉山玄武岩成分进行约束和验证。Al2O3、NaZO＋K 20、CaO与MgO计算的演化趋势线与实际观察的演化符合较好，橄榄石和斜方辉石的结晶使得CaO随着MgO的降低而增高；当单斜辉石成为液相线矿物时，cao也随着Mgo的降低而降低了。单斜辉石在岩浆演化到MgO＝10．3％时成为液相线矿物。整个计算过程中斜长石未成为液相线矿物，这与大多数玄武岩不具有Eu异常是一致的，并月＿Al2O3随着MgO的减小单调增加也说明了这点。不过大多数峨眉山玄武岩常含有斜长石斑晶，这是低压下结晶分异的结果。由于斜长石密度小，所有很难与高铁玄武岩分离。整个计算的难点也是创新点是波速计算。通过分离的堆晶矿物组合中各种矿物的成分和质量分数计算的附加层波速比观察值高，不过堆积岩体常常会有残留岩浆存在矿物晶粒间，这样会降低岩石的压缩波速。大型基性一超基性岩体常常会残留有或者捕获5-30％的岩浆。假定两个高波速附加层分别捕获7叭，和巧％的残留岩浆，计算的结果就大体等于观察值。热力学和质量平衡计算研究表明：高地震波速层为橄榄辉石岩一辉石岩的巨型侵入岩体；峨眉山中岩区的岩浆量最大也符合含V-Ti磁铁矿矿床只产在中岩区，如太和、白马、攀枝花、红格等岩体；西岩区的岩浆量最小表明几乎没有可能在西岩区形成有规模的V-Ti磁铁矿矿床，实际观察仅仅只见到数量少而小的岩体；东岩区下地壳厚达20灿1的高波速层暗示东岩区上地壳的侵入岩体积也应该具有相当规模，应该是V－Ti磁铁矿矿床成矿区。目前在东岩区很少发现与峨眉山玄武岩有关的岩浆矿床的主要原因是：东岩区的剥蚀深度不够，没有可观的侵入岩体出露，而中岩区侵入岩都侵入在元古代地层中。按照质量平衡的计算方法，最保守的估算整个峨眉地慢柱岩浆事件产生的岩浆量为8.9*106km3，上地壳峨眉山玄武岩和侵入岩体积为3.9*106km3。如果按照初始覆盖面积5x106km2计算（与西伯利亚暗色岩初始覆盖面积相当），喷发高峰期为2Ma，计算的喷发速率为3.9km3／year。这并不亚于西伯利亚暗色岩的喷发速率4km3／year。这对于研究峨眉山大火成岩浆事件与二叠·三叠交界或end-QuadaluPian生物灭绝之间的可能联系具有重要意义。本文另一方面的研究工作是：首先系统地介绍了岩浆硫化物矿床的基本原理，然后通过金宝山PGE矿床实例研究，提出金宝山岩体成岩模式，并且对整个峨眉山大火成岩省的岩浆硫化物矿床产出位置进行理论预测。详细地球化学研究表明金宝山镁铁一超镁铁岩是峨眉山大火成岩省古老火山岩浆房的残留物。岩体主要由底部超镁铁岩和上部镁铁岩组成，两种岩石的质量大致相同。根据超镁铁岩的矿物组合计算的成岩时的氧逸度较高，热力学方法计算的成岩压力为2kb左右。超镁铁岩的包嵌结构和铁铁岩的微晶一细晶结构说明超镁铁岩为镁铁岩结晶的矿物堆积形成的。镁铁一超镁铁岩的蚀变程度不同以及Sc、Sr、Eu等元素在两类岩石中的不同特征指示了整个成岩过程。金宝山岩体的原始岩浆 MgO=8％说明高镁玄武岩并不是形成PGE矿床的必要条件。金宝山的成岩模式是：在火山喷发前，岩浆侵位时橄榄石和少量铬尖晶石先结晶，沉淀在岩浆房底部；随后结晶的是斜方辉石和斜长石，斜方辉石也沉淀在岩浆房底部，斜长石由于密度较小集中中岩浆房上部，岩浆房的中部是：少量的斜长石小斑晶。由于斜方辉石和斜长石的结晶，这样岩浆中的Sc、Sr和Eu就会亏损，也是岩浆房底部堆积岩的原始捕获岩浆。火山喷发后，由于压力的突然降低，岩浆房底部的堆晶会发生再熔融，几乎消耗掉所有的斜方辉石，橄榄石也呈熔蚀状浑圆形态，重新熔融的斜方辉石导致超镁铁岩中残留岩浆比原始捕获岩浆更加富Sc，这种岩浆由于富MgO和在快速冷却的环境下同时结晶，最终形成光性方位一致的单刹辉石。喷发后岩浆房空间的剩余导致围岩-灰岩进入，造成岩浆房中剩余岩浆强烈的碳酸盐化。峨眉山玄武岩Cr-Mg#的相关关系定义一条正常玄武岩演化线。大多数这些玄武岩的Ni也保持了这种演化关系，其中低钦玄武岩和过渡型高钦玄武岩Ni-Mg＃相关关系远离了正常演化线，这些玄武岩的Cu-Mg#相关关系也有类似的情形。峨眉山低钦和过渡类型高钦玄武岩Ni和 Cu的非正常亏损，表明它们在地表下经历了硫饱和事件。金宝山岩浆硫化物矿床成岩模型的建立，为在整个大火成岩省寻找岩浆硫化物矿床提供了一种新认识。低钦和过渡型高钦玄武岩的古老火山口下部是岩浆硫化物矿床的所在地。