Geochemistry of organic matter and elements of black shale during weathering in Northern Guizhou,Southwestern China: Their mobilization and inter-connection

Different from previous studies on effect of weathering upon geochemical variation along a single weathered profile, this paper provides a new methodology validated by comparing a weathered outcrop samples and their stratigraphic counterpart un-weathered core samples in a nearby shallow borehole. This outcrop and borehole penetrated the Ordovician-Silurian Wufeng–Longmaxi shales, located in the same anticline structure in the northern part of Guizhou Province, Southern China. The mineral composition, major, trace and rare earth elements (REEs) composition and Rock-Eval parameters of outcrop and core samples were analyzed and compared. Organic matter (OM) was observed in the microscope and extracted for elements analysis. The results show that short-term weathering still has significant influence on OM, mineral and elemental composition of black shales. The elements composition shows the outcrop profile was moderately weathered. The REEs compositions do not alter much during weathering process and the REEs composition and their relative ratios still are valid for rock origin determination. The OM, mainly composed by graptolite and bitumen, even entering the highly-over thermal maturity, is still sensitive to the weathering with a systematic loss 30–50% of TOC along the outcrop profile, which suggests that the OM consumption is predominantly controlled by weathering duration and the distance from the weathering surface. In turn, OM has significant influence on the trace elements transportation behavior during weathering. Some trace elements associated with the OM such as V, Cr, Th, U, Ni and Co, change significantly in their absolute concentration during weathering, but their relative ratios do not necessarily change too much and might be still reliable proxies for paleo-environmental determination. The mobility of shale minerals during weathering is in the following order: plagioclase?>?potassium feldspar and dolomite >pyrite and OM. Short-term weathering can also result in considerable transportation of elements and significant variation of minerals content in black shale, which may pose potentially high environmental and engineering risk in the regions rich in black shale.     

Early Cretaceous K-rich rhyolites from the Duolong Cu–Au deposit,southern Qiangtang,China: evidence for crustal growth

We report new zircon U–Pb age, Hf isotopic, and major and trace element data for rhyolites from the Duolong Ore Concentration Area of the Southern Qiangtang Terrane. Building on previous studies, we constrain the tectonic setting and propose a model to explain the geodynamics and crustal growth during regional magmatism in the Early Cretaceous. The analysed rhyolites yield laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) zircon U–Pb ages of 115 and 118 Ma. The rocks are K-rich (K₂O = 6.66–9.93 wt.%; K₂O/Na₂O = 8.2–19.7 wt.%), alkaline and peraluminous (A/CNK = 1.02–1.46), and are characterized by high SiO₂ contents (72.8–78.8 wt.%) similar to highly fractionated I-type granites. Fractionation of Fe–Ti oxides, plagioclase, hornblende, Ti-bearing phases, apatite, monazite, allanite and zircon contributed to the variations in major and trace element chemistry. High K₂O contents are likely due to partial melting of the continental crust. The samples have positive zircon εHf(t) values ranging from +7.1 to +11.2. These features, together with young zircon Hf crustal model ages of 489–721 Ma, indicate that the K-rich rhyolites were derived from juvenile lower crust with an input of a mantle-derived component. We suggest that the Early Cretaceous K-rich rhyolites formed in a continental arc setting during northward subduction of Bangong Co–Nujiang oceanic lithosphere. Basaltic magma underplating was responsible for vertical crustal growth, triggered by slab roll-back in the Duolong Ore Concentration Area in the Early Cretaceous.     

熔融制样-X射线荧光光谱法测定电气石中12种主次量元素

电气石是一类含硼的铝硅酸盐矿物,化学成分复杂、化学稳定性强,不易湿法分解,B_2O_3含量较高,导致其主次量元素的同时测定存在一定困难。本文采用熔融法制样,建立了X射线荧光光谱法测定电气石Na_2O、MgO、Al_2O_3、SiO_2、P_2O_5、K_2O、CaO、TiO_2、V_2O_5、Cr_2O_3、MnO、TFe_2O_3等主次量元素的分析方法。样品与四硼酸锂-偏硼酸锂-氟化锂(质量比为4.5∶1∶0.4)混合熔剂的稀释比例为1∶10,消除了粒度效应和矿物效应;在缺少电气石标准物质的情况下,选择土壤、水系沉积物及多种类型的地质标准物质绘制校准曲线,利用含量与电气石类似的标准物质验证准确度,测定结果的相对标准偏差小于4.2%。采用所建方法测定四种不同类型电气石实际样品,测定值与经典化学法基本吻合。本方法解决了电气石不易湿法分解和硼的干扰问题,测定结果准确可靠,与其他方法相比操作简便,分析周期短。     

北淮阳东段卢镇关群和佛子岭群地层含矿性地球化学评价

卢镇关群和佛子岭群广泛分布于北淮阳成矿带内,但是对其含矿性研究一直较为薄弱。文章通过对卢镇关群和佛子岭群成矿元素的地球化学特征研究,评价地层含矿性。成矿元素富集系数(K)分析表明卢镇关群和佛子岭群各组中Mo元素均富集,W、Pb、Ag、Cu元素也存在不同程度的富集,存在潜在成矿可能;成矿元素后期叠加强度(D)分析表明本区的Mo、Ag、Cu等元素存在不同程度的后期叠加作用;成矿元素变异系数(CV)分析表明本区成矿元素具有一定的成矿潜力。对卢镇关群和佛子岭群成矿能力评序得出最优势矿种为Mo元素,并且卢镇关群和佛子岭群是北淮阳钼矿的理想矿源层,为区内钼矿提供了成矿物质。成矿元素与主微量元素的相关性分析表明Cu、W、Ag、Pb、Zn等元素受碎屑岩特征和氧化还原环境控制。     

赣南狮吼山硫铁-钨多金属矿床H-O-S同位素组成特征

狮吼山硫铁-钨多金属矿床位于银坑-青塘整装勘查区北部,是赣南地区唯一大型硫铁矿床。磁黄铁矿-黄铁矿(-黄铜矿-白钨矿)矿体赋存于石炭系梓山组上段地层中含铁、含钙层位,主要形成于石英-硫化物阶段。本文通过分析原生矿石矿物中H-O-S同位素组成特征,结合Pb同位素和成矿年代测试结果,探讨成矿流体来源及成矿演化过程。矿石硫化物中δ~(34)S组成特征(-5. 50‰～-0. 20‰,集中于-3. 0‰～0. 0‰)显示,硫源以岩浆硫为主,较宽的变化范围预示成矿流体遭受了叠加和改造作用。δD-δ~(18)O同位素组成主要集中于岩浆水与变质水重叠区域(δD=-74. 4‰～-48. 0‰,δ~(18)O_(H_2O)=3. 76‰～10. 86‰),说明成矿流体以岩浆水和变质水为主,后期有少量的天水混入。综合分析认为,该矿床成矿流体主要来自深部岩浆水,岩浆热液与含钙地层的接触交代作用形成大规模变质流体,再加上少量的天水混入,流体间的不混溶作用使成矿物质在岩体与含钙层位接触部位富集沉淀,形成热液充填交代型矿床。     

西南印度洋脊龙旂热液区富铝蚀变黏土矿物类型和地球化学特征研究

产出于不同地质背景下的热液成因黏土矿物组成、晶体结构及化学成分等信息,可指示与海底热液作用有关的水-岩反应过程和流体的物理化学条件变化。但目前对于以西南印度洋脊为代表的超慢速扩张脊热液区的黏土矿物研究程度较低,尚未了解其经历的热液蚀变作用及形成过程。本文综合应用SEM-EDS、XRD、FT-IR、EPMA和LA-ICP-MS等多种分析测试手段对采自龙旂热液区矿化蚀变角砾的形貌结构、矿物组成及其化学成分进行系统表征。研究表明:该蚀变角砾中的共生矿物相主要由具二八面体结构、富Al端元的蒙皂石族矿物贝得石与蛋白石组成,角砾中可见呈细粒浸染状的TiO_2。蚀变黏土矿物的化学成分较为单一,具有富Al、贫Mg和贫Fe的特征;其稀土元素总量普遍不高(2. 43～43. 45μg/g),配分模式呈负Eu异常(0. 31～0. 53)而未显示Ce异常(1. 09～1. 16)。推断产出于硫化物堆积丘体边部的矿化角砾长期受酸性、相对还原的、低温热液流体持续叠加和淋滤改造,除Al和Ti以外大部分元素被活化迁移,形成矿物组成简单的富铝黏土矿物相。本研究查明了龙旂热液区新的蚀变黏土矿物类型及其元素地球化学特征,反映该区广泛发育低温热液蚀变作用,为进一步探讨西南印度洋超慢速扩张脊热液成矿系统的水-岩反应过程提供了一定依据。     

不同颜色青海软玉微观形貌和矿物组成特征

青海软玉颜色丰富,近年来对青海软玉矿物学的研究不少,但针对不同颜色青海软玉矿物学特征的研究还存在欠缺。本文利用偏光显微镜、扫描电子显微镜、电子探针及粉晶X射线衍射仪器,从透闪石微形貌特征、微观结构、矿物组成及结晶度四个方面,研究了青海软玉颜色与矿物学特征的对应关系。结果表明:白玉、烟青玉、糖玉中透闪石主要为纤维状,显微纤维变晶结构,结晶度为96. 12%～96. 88%;青白玉和翠青玉中透闪石主要为叶片状,显微叶片变晶结构,结晶度为97. 35%,97. 32%;青玉和碧玉中透闪石主要为叶片状,显微叶片-隐晶质变晶结构,结晶度为95. 48%,95. 29%;黄玉中透闪石主要为柱状,显微柱状变晶结构,结晶度为97. 84%。青海软玉主要组成矿物均为透闪石,含量在95%以上,部分次要矿物如翠青玉中的榍石、黄玉中的钙长石、青玉中的菱镁矿、碧玉中的铬铁矿、糖玉中的斜黝帘石只出现在特定颜色的青海软玉样品中。研究认为不同颜色青海软玉矿物学特征确实存在差异,这些特征为研究不同颜色青海软玉成矿环境及成矿条件提供了科学依据。     

碘化氨除锡后封闭酸溶-电感耦合等离子体质谱测定锡矿石中的共生和伴生元素

锡矿石是难分解的矿物,主要存在形式是锡石(SnO_2),且共生和伴生元素多,常用的酸溶方法几乎不能溶解SnO_2,从而给锡矿石中的共生与伴生元素的准确测定带来困难。本文基于碘化氨在较低温度下熔融可产生无水状态的碘化氢,利用碘化氢的酸性和氨的还原性分解SnO_2,使Sn呈SnI_4升华分离的原理处理锡矿石。实验中以高纯铂丝作催化剂,加入碘化铵在450℃的马弗炉中分解锡矿石30 min,使得Sn以SnI_4形式挥发,除锡率达到98%以上,再用2 mL氢氟酸和1 mL硝酸封闭溶解残渣,电感耦合等离子体质谱测定钴镍铜铌钽钍铀等24个共生和伴生元素。元素检出限在0. 001～2. 9μg/g之间,90%以上元素的相对标准偏差(RSD)小于5%,相对误差小于10%。本方法解决了锡矿石难分解的问题,可测定共存金属元素,也适合测定Sn含量在1. 27%～62. 49%之间的锡矿石中的微量和痕量元素及锡精矿中的微量元素。     

川北地区寒武系筇竹寺组钙质结核裂缝充填物特征及指示意义

川北地区寒武系筇竹寺组钙质结核泥页岩中早成岩期钙质结核较发育,结核裂缝中见多期次矿物充填。为揭示钙质结核裂缝形成机理,本次结合岩石学特征及地球化学特征等开展系统研究。川北筇竹寺组钙质结核裂缝中见三~四期矿物充填。第一期微晶方解石表面较脏,阴极发光暗淡,δ13C_(PDB)、δ18O_(PDB)平均值分别为-4.26‰及-7.69‰;第二期为细—中晶粒状方解石充填,阴极发光为橘黄色,流体包裹体均一温度为平均值为86.4℃,δ13C_(PDB)、δ18O_(PDB)平均值分别为-3.15‰及-7.41‰;第三期为粗晶方解石充填阴极发光暗淡,流体包裹体均一温度平均值为96.6℃,δ~(13)C_(_(PDB))、δ~(18)O_(_(PDB))平均值分别为-1.73‰及-10.28‰;第四期为重晶石充填。结合区域构造史—热演化史分析表明,钙质结核裂缝中四期充填物分别指示早期脱水、烃源岩早成熟期生烃、加里东构造运动抬升释压及深埋藏期硫酸盐热还原作用事件。     

甘肃北山地区上石炭统—下二叠统干泉组的时代、分布及其构造意义

甘肃北山地区位于中亚造山带最南端,上古生界的沉积层序对探讨该区构造与盆地演化有重要意义。上石炭统—下二叠统干泉组的时代和分布尚不明确,限制了沉积层序和构造演化的研究。本研究通过对北山南部独山地区和柳园地区的地层学研究,获得干泉组上段火山岩LA-ICP-MS锆石U-Pb年龄293.8±4.8 Ma和"石炭系未分"火山岩年龄293.9±2.7 Ma和291.7±2.3 Ma。同位素年龄和古生物数据证明干泉组时限为晚石炭世卡西莫夫期(Kasimovian)—早二叠世萨克马尔期(Sakmarian),在研究区广泛出露。北山南部下石炭统维宪阶—中二叠统卡匹敦阶为基本连续的沉积层序,代表了研究区由小型断陷海盆发育为大型裂谷盆地的演化过程:早石炭世维宪期—早二叠世阿瑟尔期,白山组、石板山组和干泉组下段为一系列分散的断陷海盆中的滨浅海相沉积物;早二叠世萨克马尔期(约294~292 Ma),干泉组上段的火山岩表明盆地演化进入火山活动强烈的裂陷期;早二叠世亚丁斯克期—中二叠世卡匹敦期(约286~265 Ma),双堡塘组和菊石滩组组成裂谷盆地沉降期的海侵充填序列。