Accumulation of copper in the Permian Kupferschiefer: A result of post-depositional redox reactions

Within the Central European Zechstein Basin the Permian Kupferschiefer has been deposited under anoxic conditions. In most parts of the basin, the metal content does not exceed values commonly observed in black shales. However, in areas near to the Zechstein sea-shore which are simultaneously related to rift zones a significant base metal enrichment is observed. Organic geochemical analyses of the copper-mineralized sections in the Kupferschiefer from Southwest Poland show that significant changes in the composition of organic matter are associated with the metal enrichment processes. Porphyrins, commonly abundant constituents of the shale, have been decomposed by oxidizing fluids. Additionally, aliphatic hydrocarbons have been largely removed from the bitumen and alkylated aromatic systems were affected by side-chain degradation. This particular type of alteration is explained by ascending oxidizing solutions which transported high amounts of base metals from Lower Permian red beds into the Kupferschiefer horizon acting as a geochemical trap. The metal precipitation is suggested to be a result of thermochemical sulphide production with organic matter acting as hydrogen source. In areas such as the Lower Rhine Basin in the bottom section of the Kupferschiefer the base metals lead and zinc as well as barium have been accumulated from basinal Carboniferous formation waters. Copper enrichment is not observed because potential source rocks are missing in this area. However, the observed compositional changes of the organic matter do not point towards thermochemical redox processes.     

氧化还原障在热液铀矿成矿中的作用

铀是变价元素,氧化还原条件控制铀的迁移和沉淀。铀在氧化环境中呈U~(6+)形式存在,在还原条件下则以U~(4+)形式存在。氧化态六价铀主要以可溶的碳酸铀酰/氟化铀酰络合物形式在水溶液中迁移,还原态四价铀主要以沥青铀矿和铀石等形式富集沉淀成矿。热液铀矿的形成需要一对空间上密切共生的氧化障/氧化剂和还原障/还原剂,二者缺一不可。首先,氧化障中氧化剂将富铀岩石中的铀大量氧化形成U~(6+),溶解进入水溶液迁移;第二,高氧化性富铀溶液遇到还原障,U~(6+)还原成U~(4+)沉淀下来,富集形成铀矿。前人虽然对铀的地球化学性质及氧化还原反应在铀成矿中作用已比较了解,但如何在实际铀矿成矿系统中准确识别氧化还原障,有效利用氧化还原障的控矿机理指导找矿,还存在一些模糊认识,制约了铀成矿理论的发展和找矿方法的提升。本文以我国最重要的砂岩型铀矿、火山岩型铀矿、花岗岩型铀矿和变质型铀矿为例,总结了与铀矿化有关的氧化还原障的主要类型,探讨了红层等蒸发盐地层(氧化障),有机质、煌斑岩等中基性岩脉(还原障)与铀矿之间的关系及控矿机制,揭示了成矿盆地中铀-煤、铀-气(油)共生的机制,阐明了翁泉沟硼、铁、铀矿共生原因,建立了不同类型铀矿成矿模型。     

Gas chromatographic determination of lignin in sediment

After the oxidation of river and marine sediments with CuO under alkaline conditions, the phenolic compounds in the oxidation products are determined gas chromatographically and compared to that of lignin oxidation products. The method of CuO oxidation is compared to that of nitrobenzen. The quantitative determination of produced phenolic compounds by capillary gas chromatography is examined and the blank and repetibility of the method are tested.     

控制砂岩型铀矿床中铀迁移转化的主要水文地球化学作用实验

采集中国北方某砂岩型铀矿床中的含铀矿石样品,共进行7组土柱模拟实验,分别探究氧化-还原条件、HCO-3浓度、有机质和微生物对铀迁移转化的影响。结果表明:氧化-还原条件改变对铀迁移转化会产生重要影响,含氧入渗水带来的氧化环境使含水介质中沉淀态铀大量氧化溶解;HCO-3的促解吸作用及铀酰络合物的强迁移能力对地下水中铀迁移转化影响较大;有机质会参与含水介质中矿物吸附点位竞争,从而造成铀的解吸;微生物作为氧化-还原反应的催化剂,在氧化剂氧化沉淀态铀的反应中起重要作用;氧化作用、解吸作用和溶解作用对地下水中铀迁移转化的贡献比例分别为65.28%、23.91%和10.81%。     

内蒙古克鲁伦凹陷伊敏组下段砂岩铀成矿条件、特征及成因

为查明内蒙古克鲁伦凹陷伊敏组下段砂岩铀成矿规律和成因,系统总结了内外部铀源、构造环境、岩性-岩相特征、后生氧化作用等关键控矿条件以及铀成矿特征,较精准厘定了目的层时代及其铀成矿年龄,进而构建了砂岩铀成矿模式。结果表明:克鲁伦凹陷的主攻找矿目的层为伊敏组下段,侏罗纪中酸性火山岩、海西期花岗岩、下白垩统伊敏组和地下水的U含量高,指示了内外部铀源十分丰富;目的层形成于断-坳转换期,发育扇三角洲相—滨浅湖相沉积体系,(水下)分流河道微相灰色砂体发育,岩性以含砾粗砂岩、砂砾岩为主,结构疏松,透水性好;原生砂体中富含碳屑及植物茎干,自身还原容量较高,是一套良好的含矿建造;该砂体普遍发育强烈的褐黄色面状古潜水(局部古潜水-层间)后生氧化作用,进而控制了矿体的形成和形态;矿体埋深一般小于150 m,每平方米U质量为0.46~1.00 kg,主要呈透镜状和似层状;铀矿化砂岩全岩U-Pb定年获得了(67.1±5.9)Ma和(63.7±5.2)Ma的等时线成矿年龄;结合凹陷构造演化史,建立了伊敏组下段4个阶段的古潜水-层间氧化铀成矿模式,即早白垩世早期成矿前富铀建造准备阶段、早白垩世中晚期含矿目的层形成阶段、古近纪主成矿阶段和新近纪成矿停滞保存阶段,并指出区内深部(500 m以浅)仍具有较好的古潜水-层间氧化带型铀矿成矿潜力。     

The crucial role of deep-sourced methane in maintaining the subseafloor sulfate budget

Methane (CH₄) is a powerful greenhouse gas and its largest reservoir on Earth is held in marine sediments. CH₄ in marine sediments is mainly stored in gas-hydrate reservoirs and deep sedimentary strata along continental margins, where large amounts of deep-sourced CH₄ ascend to different degrees toward the seafloor. However, the amount of deep-sourced CH₄ and its role in subseafloor carbon and sulfur cycling remains poorly constrained. We analyzed sulfate (SO₄^2?) profiles of 157 sites along with previous published 85 sites to determine the regional distribution and amount of SO₄^2? reduction for an area of 1.23 × 10⁵ km² of the northern South China Sea. Then we compared these obtained results with estimates based on sedimentation rates from the same area. Significantly higher regional SO₄^2? flux estimates based on SO₄^2? profiles (4.26 × 10^?3 Tmol a^?1), compared to lower estimates based on sedimentation rates (1.23 × 10^?3 Tmol a^?1), reflect abundant ascending deep-sourced CH₄. The difference of the regional SO₄^2? flux estimates (3.03 × 10^?3 Tmol a^?1) represents the amount of SO₄^2? reduced by CH₄ through the anaerobic oxidation of CH₄ (AOM). Deep-sourced CH₄ contributes 71% to total SO₄^2? consumption in the study area, largely exceeding SO₄^2? consumption by organoclastic sulfate reduction. Our findings substantiate that deep-sourced CH₄ governs subseafloor carbon and sulfur cycling to a previously underrated extent, fueling extensive chemosynthesis-based ecosystems along continental slope and rise.     

鄂尔多斯盆地北部砂岩铀矿床粘土矿物与氧化带成因关系研究

对鄂尔多斯盆地北部铀成矿带产铀层位中侏罗统直罗组砂岩进行系统采样和分析,以探讨砂岩中粘土矿物特征与氧化带成因之间的关系。采用X?射线粉晶衍射、电子探针分析等现代分析手段,测定粘土矿物相对含量、微观形貌特征。结果表明:研究区古层间氧化的演变序列为砂体原始灰色→古氧化作用(红色或黄色)→碳酸盐化(残留了部分红色)→后期还原作用(绿色),对应的岩石蚀变期次为早期氧化酸性蚀变→氧化期后弱碱性蚀变→晚期还原弱碱性蚀变;早期氧化砂岩在还原性气体作用下,Fe³⁺还原转化为Fe²⁺,高岭石在有Fe2+存在的条件下会向绿泥石转化,这一反应在碎屑颗粒表面,形成许多极细小的针叶状绿泥石,从而使古层间氧化亚带呈现特征的绿色。     

高盐强酸性地下水中复合苯系污染物原位芬顿氧化实验研究

在原位氧化过程中,实际场地地下水和含水介质的物化特征是影响氧化效果的重要因素,而目前对此影响的研究较少。以某场地实际高盐强酸性复合苯系污染地下水为研究对象,以地下水中2-硝基-4-甲氧基苯胺(2-nitro-4-methoxyaniline,2-N)和3-硝基-4-甲氧基苯胺(3-nitro-4-methoxyaniline,3-N)为特征污染物,探究芬顿(Fenton)试剂原位氧化特征,并研究液相环境因素(初始H2O2浓度、初始Fe2+浓度、初始pH值、初始醋酸(Acetic acid,HAc)浓度、初始SO4^2-浓度)以及含水层介质对Fenton法去除2-N和3-N的影响。结果显示:(1)Fenton法去除2-N和3-N效果显著,且在初始液相条件为c(H2O2)=7 mmol/L、c(Fe²⁺)=4 mmol/L、pH=4、c(HAc)=0 mg/L和c(SO4^2-)=0 mmol/L时去除效果最佳;(2)各因素对Fenton法氧化2-N和3-N的影响不同,加入H₂O₂和Fe²⁺使2-N和3-N去除率上升,增大HAc浓度使2-N和3-N去除率下降;(3)含水层介质对2-N和3-N具有一定吸附性,且对3-N的吸附性强于2-N,二者在本实验中最大吸附态占比分别为29%和42%,而吸附态的存在会抑制Fenton法对2-N和3-N的去除;(4)矿物分析结果显示介质含有少量黄铁矿,在硫酸环境下,介质腐蚀溶解释放Fe²⁺,在达到一定浓度后,无需额外添加Fe²⁺即可完成Fenton反应进而去除2-N和3-N。     

~(35)SO_4~(2-)示踪法测定九龙江河口沉积中硫酸盐还原速率

在2011年7月利用35SO2-4培养示踪法测定九龙江河口两个站位(A站位位于咸淡混合区,盐度3~5;B站位位于海相区,盐度20~25)沉积柱中硫酸盐还原速率的垂直分布。结果显示A站位沉积柱中硫酸盐还原速率变化范围为54~2 345nmol/(cm3·d),从表层到底部先增大后减小,最大值出现在20cm深度附近;B站位硫酸盐还原速率在24~987nmol/(cm3·d)之间,分别在10cm和78cm深度附近出现两个峰值,分别为876nmol/(cm3·d)和987nmol/(cm3·d)。综合分析两个站位孔隙水中SO2-4、甲烷浓度和沉积物中总有机碳、温度和氧化还原电位的垂直变化趋势与其硫酸盐还原速率的分布规律,表明A站位沉积物中硫酸盐还原以有机矿化为主;B站位受到有机质矿化和甲烷厌氧氧化的共同作用;两个站位硫酸盐还原速率及垂直分布趋势受孔隙水中SO2-4浓度、有机质活性和温度的共同影响;根据各个层位硫酸盐还原速率估算两个站位硫酸盐还原通量(以硫计)分别为527.9mmol/(m2·d)和357.1mmol/(m2·d),表明硫酸盐还原是九龙江河口有机质厌氧矿化的重要路径。