Determination of Ge, As, Se and Te in Silicate Samples Using Isotope Dilution-Internal Standardisation Octopole Reaction Cell ICP-QMS by Normal Sample Nebulisation

A method for the determination of Ge, As, Se and Te in silicate samples using isotope dilution-internal standardisation (ID-IS) octopole reaction cell (ORC) ICP-QMS by normal sample nebulisation was developed. The method does not involve either hydride generation or ion exchange. Germanium, Se and Te were determined by isotope dilution (ID), and As was determined by ID-IS. A silicate sample with an added Ge-Se-Te spike was digested with an HF-HNO₃-HBr mixture, dried, re-dissolved with HF and the supernatant liquid was directly aspirated into an ORC-ICP-QMS instrument with He or H₂ gas. No matrix effects were observed down to a dilution factor (DF) of ∼ 70 for Ge, Se and Te and DF of ∼ 1000 for As, which resulted in 3s detection limits in silicates of 2, 1, 0.1 and 4 ng g⁻¹, respectively. Advantages of the method are the simple sample introduction as well as a capability of determining S, Ti, Zr, Nb, Mo, Sn, Sb, Hf and Ta by ID-IS-ICP-QMS/SFMS from the same solution. Furthermore, the total sample solution consumption was only 0.253 ml with DF = 2000. Therefore, only a 0.13 mg test portion was required. To demonstrate the applicability of this technique, Ge, As, Se and Te in eight silicate reference materials were determined, as well as S, Ti, Zr, Nb, Mo, Sn, Sb, Hf and Ta in four carbonaceous chondrites.     

地洼盆地砂岩铜矿床成矿作用的化学动力学和热力学研究

对我国南方中新生代地洼盆地中的砂岩铜矿床进行了化学动力学与热力学的理论与实验研究。矿源岩中以辉铜矿和黄铜矿最有利于溶解和迁移，ＮａＣｌ对Ｃｕ的溶解和含矿流体的形成起了催化作用。溶液中Ｃｕ以络合物的形式迁移，其中以一价铜氯络合物为主；温度的降低和溶液中性化导致了络合物的失稳、分解和铜矿物的沉淀。铜矿物的化学动力学和热力学制约了砂岩铜矿中以辉铜矿为主及矿床分带的形成。     

元素分析仪-同位素比值质谱测量碳氮同位素比值最佳反应温度和进样量的确定

沉积有机质的碳氮稳定同位素值是进行古气候、古环境及生态系统研究不可或缺的主要研究手段,目前碳氮同位素主要利用元素分析仪-同位素比值质谱(EA-IRMS)系统来测定。EA-IRMS测定过程中的反应温度及样品进样量直接影响反应物在测试中的燃烧程度,从而影响测试数据的精度。本文利用EA-IRMS技术,以标准样品为参考,在不同转化温度下测试碳氮同位素值,研究保证测试精度的最佳反应温度条件;同时,通过分析不同含氮量样品的检测限,明确了样品含氮量与最低检测限之间的关系,确定了精确测定氮同位素值的最低进样量。结果表明:反应温度对测试精度有显著影响,在碳同位素测定时,将反应温度设定为900℃或以上时测试精度均能达到±0.2‰;氮同位素测定时,反应温度须设定为950℃时测试精度才能达到±0.3‰。实验得出样品含氮量与检测限之间的线性相关性为R2=0.873,开展氮同位素测定时可根据此关系来判断和控制进样量。     

佳木斯地块西缘金矿带构造效应与壳幔作用--以鹤岗隆起为例

佳木斯地块西缘金矿带的形成受左行走滑断裂带和深部流体控制，壳-幔作用和地球动力体制转换是成矿物质活化→运移→聚集→成矿的基本动力学保障，构造应力场转换是其重要表现形式。深切地幔牡丹江岩石圈断裂的活动发生了深熔作用，使成矿物质得以活化、运移的重要驱动力，是成岩成矿作用发生的根本原因之一。地幔流体通过壳-幔相互作用形成了含矿流体，为流体成矿作用提供了矿源，并沿深断裂运移到更高的层位，在物理化学条件发生改变时沉积成矿。佳木斯地块西缘金矿带是受深断裂控制的，矿床之间是相互联系的，是在一个构造应力体制下完成它们的成矿作用的。北北东向和伴生的北西西向断裂，并有中生代浅成-超浅成岩体或脉岩侵位是今后找矿的方向。     

Numerical study of the oxidation process of dimethylsulfide in the marine atmosphere

A box model, involving simple heterogeneous reaction processes associated with the production of non-sea-salt sulfate (nss-SO ₄ ^2– ) particles, is used to investigate the oxidation processes of dimethylsulfide (DMS or CH₃SCH₃) in the marine atmosphere. The model is applied to chemical reactions in the atmospheric surface mixing layer, at intervals of 15 degrees latitude between 60° N and 60° S. Given that the addition reaction of the hydroxyl radical (OH) to the sulfur atom in the DMS molecule is faster at lower temperature than at higher temperature and that it is the predominant pathway for the production of methanesulfonic acid (MSA or CH₃SO₃H), the results can well explain both the increasing tendency of the molar ratio of MSA to nss-SO ₄ ^2– toward higher latitudes and the uniform distribution with latitude of sulfur dioxide (SO₂). The predicted production rate of MSA increases with increasing latitude due to the elevated rate constant of the addition reaction at lower temperature. Since latitudinal distributions of OH concentration and DMS reaction rate with OH are opposite, a uniform production rate of SO₂ is realized over the globe. The primary sink of DMS in unpolluted air is caused by the reaction with OH. Reaction of DMS with the nitrate radical (NO₃) also reduces DMS concentration but it is less important compared with that of OH. Concentrations of SO₂, MSA, and nss-SO ₄ ^2– are almost independent of NO _x concentration and radiation field. If dimethylsulfoxide (DMSO or CH₃S(O)CH₃) is produced by the addition reaction and further converted to sulfuric acid (H₂SO₄) in an aqueous solution of cloud droplets, the oxidation process of DMSO might be important for the production of aerosol particles containing nss-SO ₄ ^2– at high latitudes.     

湿斜压大气中暴雨中尺度系统发展的一种可能机制

根据暴雨中尺度系统发生时的大气运动特征,在绝热、无摩擦条件下,从湿斜压原始方程出发,考虑大气运动的涡度及散度演化不仅受动力场的制约,而且还受到热力场的约束,采用不同于传统研究涡度及散度方程的分析方法,导出了新形式的涡度及散度方程。在此基础上,分析了湿斜压大气中对流层中低层气流旋转与辐合持续增长的动力特征,初步揭示了湿斜压大气中暴雨中尺度系统发展的动力机制。     

Hercynian subduction-related processes within the metamorphic continental crust in Calabria (southern Italy)

Linking the deformation history of mylonitized continental rocks to the progress of devolatilization reactions that trigger reaction softening is critical for the understanding of crustal scale processes. We have analysed the field geometries and microstructures of deformed rocks within the southern Hercynian belt in Calabria, as well as modelled the pressure–temperature–deformation (P–T–d) trajectory of a main ductile shear zone that tectonically coupled the deeper crustal Mammola Paragneiss Unit with the upper crustal Stilo–Pazzano Phyllite Unit. P–T modelling of the mylonitic Mammola Paragneiss Unit was performed through calculation of phase equilibrium diagrams with the software thermocalc in the MnNCKFMASHTO model system. The prograde P–T–d trajectory is based on the zoning profiles of garnet porphyroblasts and their mineral inclusions, primarily barroisite and epidote. P–T modelling shows that peak metamorphic conditions of ~0.9 GPa and 585°C were reached during a D_n-1 under-thrusting event. The following exhumation during the D_n mylonitic event, and contact metamorphism during D_n+1 and D_n+2 folding events, have also been modelled because they are essential to restore the previous tectono-metamorphic history. The exhumation trajectory was modelled down to 0.3 GPa with temperatures of 440–460°C, under fluid-deficient conditions, as well as the final late Carboniferous contact metamorphism up to T_max of 680–720°C. The prograde path shows clear evidence for thermal buffering during garnet growth at the expense of chlorite, with a heating-dominated stage after chlorite breakdown. Subsequently, a rheological change associated with epidote breakdown (i.e. reaction softening) occurred, highlighted by a net steepening of the P/T trajectory towards the pressure peak. On the basis of the barroisite inclusions within garnet porphyroblasts as well as the ‘hairpin’ shape of the reconstructed P–T–d path (before contact metamorphism), we infer that the unusual low T/P gradient for the Hercynian crust exposed in the Mammola Paragneiss Unit records its involvement in the Palaeotethys–Gondwana subduction beneath Laurussia during D_n-1 under-thrusting. We present a new palaeotectonic interpretation along the southern Hercynian belt in Calabria during the Upper Mississippian–Lower Pennsylvanian, that is consistent with previous geochronology studies.     

乙烯底油HK~200℃馏分的催化聚合生产汽油工艺条件研究

介绍了以乙烯底油的HK-200℃馏分油为原料,用一种新配方的三氯化铝催化剂进行催化聚合,制取优质汽油的方法；对催化聚合反应的工艺条件进行了大量的实验研究,探索出生产中各种最佳的工艺参数,为中小型石油化工企业提供了一条经济效益显著的乙烯底油的综合利用途径。     

电感耦合等离子体质谱法测定高纯铟中铁

建立了基于碰撞/反应池（CCT）技术的电感耦合等离子体质谱法（ICP-MS）测定高纯铟中铁元素的方法。在CCT模式下,有效地消除了如⁴⁰Ar¹⁶O等多原子离子对待测元素的干扰,不分离基体就可直接测定铁。方法检出限为0.06ng/mL,精密度（RSD,n=11）<8%,回收率为94.0%～102.1%。方法与现行的国家标准分析方法相比,操作简便、高效。