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.

中国东海陆架盆地构造-热演化研究

East China Sea Shelf Basin (ECSSB), as a basin with prospect of oil & gas resource and due to its special geological location on the west margin of the west Pacific, attracts a lot of attention from many geologists in the world.Based on systematic temperature measurements, bottom hole temperature (BHT) and the oil temperature data, the geothermal gradients in the ECS SB are calculated and vary from 25 to 43°C/km, with a mean of 32.7°C/km. The geothermal gradient in Fuzhou Sag has the higher value(40.6°C/km) in Taibei Depression than that in others. The lower value (27.2 °C/km) occurs in in Xihu Depression. The middle values occurs in Jiaojiang and Lishui sags in Taibei Depression with a mean value of 34.8 °C/km. Incorporated with the measured thermal conductivity, heat flow values show that the ECSSB is characterized by present-day heat flow around 70.6mW/m2, varying between 55 and 88 mW/m2. No significant difference in heat flow is observed between the Xihu and the Taibei Depressions. These heat flow data suggest that the ECSSB is geothermally not a modem back-arc basin.Applying the paleogeothermal gradient based method, thermal history is reconstructed using vitrinite reflectance (VR) and apatite fission track (AFT) data. The results suggest that the thermal history was different in the Taibei and the Xihu depressions. Paleo-heat flow values when the pre-Tertiary formations experienced their maximum temperature at the end of the Paleocene reached a mean of 81 mW/m2 in the Taibei Depression, much higher than the present-day value. The lower Tertiary sediments in the Xihu Depression experienced maximum temperatures at the end of Oligocene and reached a mean paleo-heat flow value of 83.4 mW/m2. The time, when the paleo-heat flow reached the maximum value, suggests that the ECSSB rifted eastward.Tectonic subsidence analysis shows that the timing of the major rifting episode was different across the ECSSB. The rifting occurred from the Late Cretaceous to the early Eocene in the Taibei Depression, followed by thermal subsidence from the late Eocene to the end of Miocene. In contrast, in the Xihu Depression the initial subsidence lasted until the early Miocene and thermal subsidence to the end of Miocene. From Pliocene to the present, an accelerated subsidence took place all along the West Pacific margin of the east Asia.The thermal lithosphere thickness is determined by temperature profile in the lithosphere, the mantle adiabat or the dry basalt solidus. It indicates that the thermal lithosphere reached the thinnest thickness at the end of Eocene in the Taibei Depression and the end of Oligocene in the Xihu Depression, respectively, corresponding with a value of 57-66km and 56-64km. In Taibei Depression, the lithosphere thickness decreased 16-22km from the end of Mesozoic to Paleocene. After Paleocene, the thickness increased 13-16km and reached 71-79 km at present-day. In Xihu Depression, From the end of Oligocene to present-day, the thickness increased 10-13km and reached 69-76km at present-day. The evolution of the lithosphere thickness is associated closely with the lithosphere stretching.Combining the reconstructed thermal history and the burial history, the maturation of the Jurassic oil-source rock shows that the main hydrocarbon generation phase was in the mid-Jurassic and a secondary hydrocarbon generation occurred at the end of Paleocene. The secondary generation was controlled mainly by the tectono-thermal background during the Paleocene.

层控夕卡岩型矿床成矿系统的元素活动性及质量迁移——以铜陵冬瓜山铜矿床为例

应用改善了的质量平衡方程研究冬瓜山层控夕卡岩型铜矿床成矿系统的元素活动性及质量迁移,结果表明:系统中Zr ,Hf ,Y和Nb 为不活动元素,其余均为活动元素。主量元素中仅CaO 为迁出组分,其质量迁移量为84 % ,其余均为带入组分,带入量最大的SiO2 的质量迁移量高达2384 %;稀土元素均为带入组分,其中,中稀土较轻稀土和重稀土的活动性更强;其它微量元素中,带入序列由强到弱为:Cr →Ta →Sn →Th ,迁出序列由强至弱依次为:U →Sb →Ni →Sr →Ba →Rb →Co →W;成矿元素Cu 和Ag 为带入组分,其中Cu 的带入量最大,质量迁移量高达1200 %。本文还得出两点具普适性认识: ①稀土元素较其它微量元素对体系条件的变化更为敏感,且往往表现出明显的规律性变化,能更好地示踪地质地球化学过程。②不同元素在不同体系中的行为特征差异极大,仅凭经验判定某一元素为不活动元素往往不可靠。因此,在开展质量平衡研究时,首先采用适当方法确认体系的不活动元素是一项不可或缺的前提工作。

锑的表生地球化学行为与环境危害效应

锑(Sb) 是一种典型的有毒有害重金属元素。由于自然过程和人为活动的影响,锑及其化合物广泛分布于大气、土壤、水体等表生环境中,锑的环境污染日益严重。Sb 不是植物必需元素,但能够被植物体及农作物吸收。Sb 对人体和动物体产生慢性毒性及潜在致癌性。本文主要通过分析Sb 的主要矿物、锑及其化合物在表生环境中的分布与迁移特性,来阐述人体可能的锑暴露途径及由此产生的环境危害效应。

贵州老万场金矿床红土化作用及对金赋存状态的制约

红土的矿物成分、硅酸盐成分和化学蚀变指数(CIA)特征表明，贵州老万场红土化过程经历了粘土化、铝土矿化、铁化三种化学风化作用；地球化学上属早期红土化作用阶段。风化过程中K2O、Na2O、CaO相对于Al2O3的淋失量很高，显示较强的化学蚀变作用。红土剖面中成矿元素Au、As、Sb含量变化很大。Au通常为40～4551ng／g；Sb普遍小于0．1％；As通常为0．n％，最高1．8％。它们普遍高于大厂层硅质岩中相应成矿元素的含量。红土化过程中，Au、As的富集与Fe的富集作用有明显的关系，并与红土剖面中相对还原的部位有关，而sb则在相对氧化的环境中聚集。红土剖面中稀土元素含量普遍较高，轻重稀土元素之比通常小于10，稀土元素分布模式非常相似，与大厂层稀土元素特征有明显差别。微量元素图解显示红土剖面中的大离子亲石元素、不相容元素与大厂层也有明显的不同。成矿元素问的差异性也很明显，表明大厂层岩石可能并不为老万场红土层的发育提供直接的物质来源，红土层的发育似乎与后期第四系的冲积物、洪积物有关。成矿物质也可能不与大厂层直接有关。带能谱的透射电镜(TEM-EDX)观察表明金的存在形式多样，虽然金主要以浑圆状的自然金颗粒产出，但也可以被针铁矿(含砷针铁矿)、石英硅质吸附，或被伊利石等吸附。显示红土化过程中铁还原作用对金富集的重要性。

贵州老万场金矿成矿物质来源的研究

硅酸盐成分研究表明老万场红土化过程经历了粘土化、铝土矿化、铁化三种化学风化作用;风化中化学蚀变较强,K2O、Na2O、CaO 相对于Al2O3 的淋失量很高。在红土剖面上成矿元素的含量变化很大。相关性分析表明,红土化过程中,Au、As 的富集与脱硅富铝化程度关系不大,而与铁的富集有明显的关系;Au、As 的富集与相对还原的环境有关,而Sb 则在相对氧化的环境中易于聚集。可能反映了红土剖面中潜水面下部附近相对还原的环境Au、As 易于富集。大厂层样品和老万场红土剖面样品在成矿元素(Au、As、Sb) 含量、稀土元素含量、轻重稀土比值、配分曲线上以及微量元素特征包括大离子亲石元素、不相容元素上的较大差异,显示了红土层的发育与大厂层岩石有较大的差别,暗示它们物质来源上的一定差异性。

扬子地块西南缘大面积低温成矿时代

中国西南地区(川、滇、黔、桂、湘)发育有世界上很典型的低温成矿域，其面积之大(约90万km2)、包含的矿种之多(Au、Hg、Sb、As、P、Pb-Zn、U、Ni-Mo-PGE、重晶石、冰州石和分散元素等)、矿床组成和组合之复杂，在全球十分鲜见。扬子地块西南缘是中国西南大面积低温成矿域的重要组成部分。近年来，作者采用Rb-Sr、Sm-Nd、Ar-Ar等多种同位素定年方法，对扬子地块西南缘产出的磷矿、金矿、锑矿等低温矿床的成矿时代进行了较系统的研究。文章总结了这些研究成果，并结合前人的资料，初步拟定出该区存在三期大规模低温成矿作用，它们分别相当于晚元古代一早古生代(晚震旦世—早寒武世)、晚加里东期(晚志留世—早泥盆地)和燕山期(晚侏罗世一中自垩世)。该区的磷矿、重晶石矿和黑色页岩中的镍钼铂矿主要形成于晚元古代一早古生代，同位素年龄主要为585～540 Ma；赋存于前寒武纪浅变质碎屑岩中的金一锑．钨矿床主要形成于晚加里东期，同位素年龄主要为435-380 Ma；产于寒武系以后地层中的锑矿床主要是在中燕山期成矿，同位素年龄主要为160～140 Ma；而该区的卡林型金矿和汞矿主要在燕山中晚期大规模成矿，同位素年龄主要为170-80 Ma。

中国早古生代若干高硒黑色岩系中层状硅质岩的地球化学特征及其成因意义

在中国早古生代若干高硒黑色岩系中发育有数层的厚度不等的层状硅质岩，si02含量一般在90％ 以上，岩石富Fe，相对贫Mn、A1、Ti。亲石元素大量亏损，但富典型的热水沉积指示元素Ba、As、Sb，也有一定的铂族元素(PGE)的异常，稀土元素的配分模式呈左倾，有明显的Ce的负异常和轻微的Eu的正异常。63o si值变化范围为一0．7‰ ～1．2‰ ， O值变化范围为17．6％-29．0‰ 。硅质岩的地球化学表明其为热水沉积作用的产物。文章最后讨论了热水成因硅质岩的形成与硒富集的关系，认为形成硅质岩的构造环境可能是地壳深部se得以上升到浅部聚集的前提，而含硅热液则可能是硒的良好的”溶剂”。

银和锰之间可能存在的联系

一般认为Ag与Pb、Zn、Cu共生，少数与Au、Sn、Sb、W、As等共生，很少有学者注意到Ag和Nn共生。关于Ag和Nn之间的研究多集中在银锰矿石选矿方面。也有部分学者通过研究渐新世含银矿床中还原锰的离析和生物化学作用。推测前寒武纪的一些生物地球化学作用。从已有的资料看。大多数锰矿床都缺乏银分析数据，过去只认为在表生风化作用下形成的铁-锰帽可能会造成银的富集。并把它划归成铁锰帽型银矿。

陆相热水沉积成因硅质岩与超大型锗矿床的成因—— 以临沧锗矿床为例

临沧锗矿床的硅质岩中存在大量的热水沉积构造和植物化石, 该硅质岩富SiO2 , 低TiO 2和Al2O3, Al/(Al+Fe+Mn)比值平均为0.010, 明显富集Ge, Sb, As, W; 其次Cs, U, Mo和Tl有不同程度的富集, 稀土总量一般小于1 μg/g, 最大2.324 μg/g , 相对富集LREE; δ Eu为0.452 ~ 5.141, δ Ce为 0.997 ~ 1.174; 稀土元素北美页岩标准化模式呈平坦状或向左倾斜; 氧同位素组成与热泉硅华类似. 上述特征表明本区硅质岩属陆相热水沉积成因. 硅质岩作为中寨锗矿体的顶板或夹层, 在空间上与锗矿体紧密接触. 硅质岩中含锗5.6 ~ 360 μg/g, 平均78 μg/g. 靠近硅质岩的煤中锗含量明显升高. 随着煤中锗含量的不断升高, 含矿煤的特征微量元素比值及稀土元素的球粒陨石标准化分配模式与硅质岩越来越相似. 临沧锗矿床煤中锗可能主要由与煤层形成近同时的、以热水成因硅质岩为标志的热水活动带入.

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。

云南墨江金矿床硅质岩的地质地球化学特征及其意义

墨江金矿床厂组中下段硅质岩具有典型的沉积构造，岩石富集∑Fe和As 、Sb、Bi、Ga等微量元素（相对于地壳克拉克值），而相对贫AI2O3；稀土元素以总量（∑REE）低，负铈异常为特征，与热水沉积的硅质岩特征相似。在判别硅质岩形成与作用的一系列主量和微量元素图解上，本区的硅质岩位于热水沉积作用范围，但四十八两山段硅质岩有趋近于正常化学沉积作用。利用硅质岩的氧同位素计算出它的形成温度为128－146℃。地质、地球化学特征表明本区硅质岩的形成与热水沉积作用有关，但四十八两山段硅质岩受到正常化学沉积作用的影响。

云南墨江金矿热水喷流沉积成岩成矿的地质地球化学证据

在墨江金矿区发现了两个热水喷流沉积旋回，赋矿地层烂山段出露的硅质岩和（黄铁矿）硫化物岩具有低TiO2,Al2O3和富含As,Sb,Au,Ag,Hg含量特征，稀土元素具有总量低，轻稀土总量高于重稀土特征，其球粒陨石标准化模式为向右倾曲线，大多数样品具有负Eu异常；而其北美页岩标准化曲线向左倾，在SiO2-Al2O3,Al-Fe-Mn和Al2O3-TFeO-CaO等地球化学图解上，大多数样品位于热水沉积区，当样品中含有火山角砾成分时偏离热水沉积区，研究表明硅质岩和（黄铁矿）硫化物岩主要由热水喷流沉积形成的，再结合矿床地质特征，认为墨江金矿存在早期热水喷流沉积成岩成矿作用，形成了矿化或低品位矿石，并可能与下伏火山喷发有关，这为墨江金矿的成因研究和进一步找矿开辟新的思路。

八方山大型多金属矿床热水沉积岩相特征与矿化剂组分关系

陕西八方山大型(金)多金属矿床赋存在于中泥盆统吉维特晚期的热水沉积岩相中。富SiO2酸酐型热水同生—交代沉积作用形成热水同生沉积微相(层状硅质岩)、热水同生交代微相(微晶石英岩及硅化灰岩)；富Fe^2+ - Mg^2+碳酸盐型热水同生沉积作用形成层状含铜硅质铁白云岩；在同生断裂附近，因热水液压致裂-隐爆作用形达含铜黄铁矿硅质铁白云石角砾岩；富Na^+铝硅酸盐型／富Fe^2+、Mg^2+碳酸盐型热流体在同生断裂中形成热水充填微相(穿层脉状钠长石碳酸岩)；低温热卤水(富F、Ba、B、As、Sb)形成热卤水同生沉积微相。矿质大规模沉淀的地球化学动力学因素为：在热水沉积成矿盆地中，在单一成分热水体系的温度、压力改变而发生快速化学沉淀；不同成分、性态的热水混合后，强烈的酸—碱作用及Eh-pH剧变等，触发热水体系失稳，引起矿质大规模沉积。[SiO2]和F可能是重要的矿化剂。

贵州织金磷矿岩元素地球化学特征

采用电感耦合等离子体．质谱仪（ICP-MS）对贵州织金戈仲伍剖面戈仲伍组磷矿岩样品的微量、稀土元素含量进行了测定。戈仲伍组磷矿岩主要为生物碎屑白云岩、硅质磷块岩，普遍形成生物碎屑结构，以小壳类动物化石及藻类化石为主。分析结果表明，磷矿岩中As、Sb等微量元素富集，Co／Ni的比值为0．14，明显小于1；U／Th比值介于1．27-7．39之间。平均值为3．40；在lgw（U）．lgw（Th）关系图、Cr-Zr的关系图中样品点几乎都落在热水沉积区。表现出热水沉积成因的地球化学特征。磷矿岩中普遍富集稀土元素，含稀土总量∑REE较高。尤其富集Y重稀土元素；磷矿岩具Ce负异常，指示环境处于氧化程度相对较高状态；稀土元素北美页岩标准化模式曲线为帽状形态，指示在磷矿岩形成过程中有生物或有机质参与作用；磷矿岩普遍具Eu正异常、稀土总量较高、∑IREE／∑HREE比值较高的特征，暗示戈仲伍组磷矿岩具有正常海相沉积伴有海相热水沉积混合成因的特征.