砂岩型铀矿床层间氧化带前锋区稀有元素富集机制

在深入研究砂岩型铀矿床层间氧化带各地球化学分带中铀及其伴生元素的分布规律时,发现一些单价态(不变价)元素也常常富集在层间氧化带前锋区,其典型代表是钪(Sc)、钇(Y)和稀土元素(REE)等。作者在综合分析前苏联众多砂岩型铀矿床各地球化学分带中各种元素大量测试数据的基础上,论述了层间氧化带前锋区Eh值和pH值的变化规律以及它们所导致的变价元素(U、Se、Mo和V)和不变价元素(Sc、Y和REE)的分布规律和富集机制。实际上,层间氧化带前锋区既是氧化-还原电位(Eh值)又是酸碱度(pH值)的急剧变化区,两者大致同步消长。层间氧化带前锋区有两类地球化学障:单纯的还原障和还原-碱性综合障。两种地球化学障的发育与强度取决于原始未氧化岩石中硫化物、有机质和碳酸盐的含量。     

东胜铀矿床孙家梁和沙沙圪台地段控矿因素对比

根据铀成矿作用及铀矿体的产出特点分析,认为东胜铀矿床孙家梁和沙沙圪台地段铀成矿过程明显受铀储层的古层间氧化作用、后期改造及还原保矿作用的控制。研究表明,由于不同地段的控制因素存在差异,造成铀矿化特点不一致。因此,掌握不同地段的控矿因素,有助于判断古层间氧化带前锋线的产出位置,对扩大东胜铀矿床规模、预测富铀矿体产出部位以及区域找矿具有指导意义。     

Oxidation Experiment of Natural Megacrystal Ch'nopyroxene: Implications for Assignment of Mossbauer Spectra

The Mossbauer spectra of natural megacrystal clinopyroxene are usually fitted by 4 sets of symmetric doublets, A-A', B-B', C-C' and D-D', respectively, in terms of increasing Qs value in literature. But the assignments of those doublets are quite different, except the D-D' doublet assigned to Fe3+ at the lattice site Ml in previous papers. Particularly, the assignment and interpretation of the C-C' doublet are diverse.The oxidation experiments of natural megacrystal clinopyroxene collected from the Hannuoba basalt, North China, were performed under controlled conditions of temperature at 1000℃ and oxygen fugacity of FMQ buffer in 1, 2, 3 and 5 days respectively. The oxidized samples were then measured by X-ray diffraction spectrometry and Mossbauer spectrometry. The oxidation of clinopyroxene is characterized by Fe2+→ Fe3+ at Ml under the subsolidus conditions, which is consistent with the increase of the area of the D-D' doublet when the heating time increases. Accordingly, the area of the A-A' and B     

新矿物——铊明矾

铊明矾 (lanmuchangite ,TlAl[SO4]2 ·12H2 O)是在贵州滥木厂铊 (汞 )矿床富铊矿体氧化带中发现的一种铊的硫酸盐新矿物。该矿物为产于氧化带的次生矿物 ,其共生矿物为水绿矾、镁铝矾、钾明矾、黄钾铁矾、石膏、自然硫、砷华及某些未知矿物。其矿物集合体大小一般为 2～ 10mm ,集合体多为致密块状 ,单晶呈他形粒状 ,4 0～ 90 μm ,偶见平行柱状集合体 ,半自形至自形柱状晶体 ,直径 15～ 65 μm。白色至淡黄色 ,玻璃光泽 ,透明 ,易溶于水。偏光显微镜下无色 ,均质体 ,实测折光率为 1.4 95。维氏硬度为 94～ 12 4kg/mm2 ,摩氏硬度为 3 .1～ 3 .4 ,实测密度 2 .2 2 g/cm3。平均化学成分 :Tl2 O =3 3 .2 5 % ,Al2 O3=8.0 7% ,SO3=2 5 .19% ,SiO2=0 .10 % ,K2 O =0 .3 5 % ,CaO =0 .0 8% ,MgO =0 .0 6% ,FeO =0 .0 4 % ,H2 O =3 3 .4 6% ,总和 10 0 .60 % ,除结晶水由热重分析 (TG)求得 ( 3件样品平均 )外 ,其余成分均由电子探针分析 ( 6点平均 )求得。化学式为(Tl1.0 0 K0 .0 5) 1.0 5(Al1.0 1Si0 .0 2 Ca0 .0 1Mg0 .0 1Fe0 .0 1) 1.0 6 [SO4]2 .0 2 ·11.86H2 O ,理论式为TlAl[SO4]2 ·12H2 O。X射线粉末衍射主要强线 [d(I,hkl) ]为 :0 .4 3 14 ( 10 0 ,2 2 0 ) ,0 .2 80 1( 70 ,3 3 1) ,0 .70 3 ( 5 4 ,1     

Modelling of the nighttime nitrogen and sulfur chemistry in size resolved droplets of an orographic cloud

A chemistry module has been incorporated into a Lagrangian type model that computes the dynamics and microphysics of an orographical cloud formed in moist air flowing over the summit of Great Dun Fell (GDF) in England. The cloud droplets grow on a maritime aerosol which is assumed to be an external mixture of sea-salt particles and ammonium-sulfate particles. The dry particle radii are in the range 10 nm<r<1 µm. The gas-phase chemical reaction scheme considers reactions of nitrogen compounds that are important at night. The treatment of scavenging of gases into the aqueous phase in the model takes into account the different solubilities and accommodation coefficients. The chemistry in the aqueous phase focusses on the oxidation of S(IV) via different pathways.Sensitivity analyses have been performed to investigate deviations from gas-liquid equilibria according to Henry's law and also to study the influence of iron and of nitrogen compounds on the aqueous-phase oxidation of dissolved SO₂. When addressing these questions, special attention has been given to the dependence on the droplet size distribution and on the chemical composition of the cloud condensation nuclei on which the droplets have formed. It was found that the oxidation of S(IV) via a chain reaction of sulfur radicals can be important under conditions where H₂O₂ is low. However, major uncertainties remain with respect to the interaction of iron with the radical chain. It was shown that mixing of individual cloud droplets, which are not in equilibrium according to Henry's law, can result in a bulk sample in equilibrium with the ambient air. The dependence of the aqueous-phase concentrations on the size of the cloud droplets is discussed for iron, chloride and NO₃.     

512可地浸砂岩型铀矿床地质特征和远景评价

本文介绍了５１２矿床区域地质背景、矿床基本特征、近期勘探成果、地浸效果和矿区远景评价。该矿床的成矿条件有利，属层间氧化带砂岩型，有可能发展成可地浸的、低品位的万吨级矿床，其矿田远景将更为可观。     

甲烷被黑云母氧化形成二氧化碳的实验研究与意义

CH4和CO2是岩浆热液系统中的重要挥发组分，两者之间的转换机制是一个重要的科学问题，在碳循环和流体作用等诸多方面都具有重要意义。例如在成矿过程中，CH4和CO2的加入会改变成矿流体性质，CO2还能缓冲流体pH，对成矿元素的迁移和沉淀富集有重要影响。前人通过研究瑞士阿尔卑斯山中部石炭纪、二叠纪、三叠纪地层裂隙石英中的流体包裹体发现，在较高温度条件下，黑云母的绿泥石化能将CH4氧化生成CO2，然而缺少相关的实验地球化学证据。因此，本项研究选择黑云母作为氧化剂开展了CH4的氧化实验研究。通过对黑云母- 甲烷- 水体系、黑云母- 碳化铝- 水体系以及甲烷- 水体系的实验研究发现，证实了黑云母能够将CH4氧化为CO2，起始反应温度约150℃，远低于地质研究结果。对于黑云母- 甲烷- 水体系和甲烷- 水体系实验，采用熔融毛细硅管作为反应腔，而对于黑云母- 碳化铝- 水体系实验，则采用粗石英管作为反应腔。对反应后黑云母残片的能谱分析表明，变价元素Fe含量大量降低，表明黑云母中三价Fe作为氧化剂参与了反应。这一结果为地质系统中黑云母等铁锰暗色矿物在中低温条件下氧化CH4形成CO2提供了实验和理论支撑。而CH4向CO2的转变过程，将改变热液流体的性质，有利于富CO2成矿流体的形成，对金属矿床形成具有重要意义。     

硫化矿氧化率测定问题的研究：Ⅲ.硫化锌矿中氧化锌的分离测定

研究了络合剂乙二胺作为分离流化锌矿中锌矿物的选择性溶剂的优越性及其具体应用条件。１０％乙二胺－１０％（ＮＨ４）２ＳＯ４溶液于室温下电磁搅拌浸取，氧化锌矿物的浸取率＞９７％，而闪锌矿等在该溶剂体系中溶解率≤０．２％，具有比较高的选择性。方法已用于实际样品分析。     

Degradation of Isoprene in the Presence of Sulphoxy Radical Anions

Autoxidation of S(IV) initiated by manganese sulphate or potassium peroxydisulphate in alkaline aqueous solutions was significantly slowed down by dissolved isoprene, which decayed in the process. The laboratory experiments were carried out in a batch, perfectly mixed reactor, which had no gas space. The concentration–time profiles of oxygen were measured with a Clark-type electrode. The profiles of sulphite species and of isoprene were evaluated from the UV spectra of solutions. The kinetic analysis indicated that isoprene reacted directly with sulphate radical anions produced during the S(IV) autoxidation. A relative second-order rate constant of (2.12 ± 0.37) × 10⁹ M^–1 s^–1 was determined for this reaction at 25 °C, pH (8.0–8.5) and ionic strength of (1.7–4.9) × 10^–3 M (the reference rate constant of the reaction of sulphate radical anions with sulphite ions equalled 3.4 × 10⁸ M^–1 s^–1). A tentative mechanism of isoprene oxidation during S(IV) autoxidation, which included formation of isoprene – SO^– ₄ adduct, was based on the analogy to the gas-phase reactions of isoprene and to the liquid-phase reactions of sulphate radical anions with other compounds. Atmospheric significance of the aqueous-phase reaction of isoprene with sulphate radicals was discussed. Approximate analysis showed the reaction is a potential sink for isoprene in the aqueous phase and in the gas–liquid systems of high liquid water content (LWC > 10^–5 m³ m^–3). The aqueous-phase oxidation of isoprene can produce secondary pollutants, and influence transformation and the long-range transport of SO₂ in the atmosphere.     

Inhibition of the S(IV) Autoxidation in the Atmosphere by Secondary Terpenic Compounds

To better understand the role of terpenic compounds in atmospheric chemistry the influence of sobrerol, a water-soluble product of photochemical autoxidation or ozonolysis of -pinene, on the rate of S(IV) autoxidation was studied. Laboratory experiments were performed under heterogeneous conditions, at constant supply with S(IV) by dissolution of CaSO₃.1/2 H₂O fine particles and with air oxygen by diffusion through a planar gas-liquid interface. The progress of S(IV) autoxidation, uncatalysed or catalysed by Fe₂(SO₄)₃ or CoSO₄, was followed conductometrically. The inhibiting effect of sobrerol was discussed in terms of the chain reaction terminated in a step linear with respect to sulphoxy radicals. A method was proposed for quantification of the inhibiting effect and the rate constant (2.0–3.8)10⁸ M^–1s^–1 was given for the step eliminating sulphate radicals. Further consequences of the inhibition: shifting the reaction locus from the gas-liquid (droplet) interface to the liquid (droplet) bulk and strong oscillations in the rate of S(IV) autoxidation resulting of the activity of sobrerol-derived radicals were also shown.