论氢化物的形成及其在分析测试领域的应用

论述了氢化物形成的普遍性、氢化物的物理化学性质、元素周期系各类元素的氢化物类型。认为一些金属离子、非金属离子在酸性介质中与硼氢化钾（钠）作用及金属锌等强还原剂作用生成氢化物。综述了氢化物的形成在分析测试领域的应用：试样分解、分离富集、容量分析、光度分析、原子光谱分析、质谱分析。     

化学地层学研究中的若干注意事项

化学地层学因其交叉学科特点和研究对象的复杂性使得研究过程中任何一个环节的不足都将造成测试出现偏差,成果的可信度也将出现问题。高昂的成本也要求研究者把有限的资源集中到正确的目标上。近20年研究历程却恰恰将此类性质的问题陆续暴露了出来。如采样阶段获取原生性状考虑不充分或依据不足、测试阶段缺乏校验、数据分析阶段挖潜和综合利用有待完善以及化学岩、碎屑岩和生物岩各自的基础性和针对性研究有待提高等。有些问题带有相当程度的普遍性,有些甚至是严重的核心技术问题。笔者结合最新相关研究成果对上述问题进行了逐一分析和系统修正。     

Carbon and oxygen isotopic composition of car- bonate cements of different phases in terrigenous siliciclastic reservoirs and significance for their origin： A case study from sandstones of the Triassic Yanchang Formation, southwestern Ordos Basin, China

Early carbonate cements in the Yanchang Formation sandstones are composed mainly of calcite with relatively heavier carbon isotope （their δ^18O values range from -0.3‰- -0.1‰） and lighter oxygen isotope （their δ^18O values range from -22.1‰- -19.5‰）. Generally, they are closely related to the direct precipitation of oversaturated calcium carbonate from alkaline lake water. This kind of cementation plays an important role in enhancing the anti-compaction ability of sandstones, preserving intragranular volume and providing the mass basis for later disso- lution caused by acidic fluid flow to produce secondary porosity. Ferriferous calcites are characterized by relatively light carbon isotope with δ^13C values ranging from -8.02‰ to -3.23‰, and lighter oxygen isotope with δ^18O values ranging from -22.9‰ to -19.7‰, which is obviously related to the decarboxylation of organic matter during the late period of early diagenesis to the early period of late diagenesis. As the mid-late diagenetic products, ferriferous cal- cites in the study area are considered as the characteristic authigenic minerals for indicating large-scaled hydrocarbon influx and migration within the clastic reservoir. The late ankerite is relatively heavy in carbon isotope with δ^13C values ranging from -1.92‰ to -0.84‰, and shows a wide range of variations in oxygen isotopic composition, with δ^18O values ranging from -20.5‰ to -12.6‰. They are believed to have nothing to do with decarboxylation, but the previously formed marine carbonate rock fragments may serve as the chief carbon source for their precipitation, and the alkaline diagenetic environment at the mid-late stage would promote this process.     

Helium-argon isotopic tracing for the Pb-Zn-Ag polymetallic ore deposits in the central-south segment of the Da Hinggan Ling Range

In recent years big strides have been made in the exploration of ores in the central-south segment of the Da Hinggan Ling Range, though some debates still exist on the metallogenesis and sources of ore-forming materials. Pyrite and other sulfides in direct relation to the Pb-Zn-Ag ore deposits were chosen for the He and Ar isotopic analysis of ore-forming fluids, and the first He and Ar isotope data have been obtained from the study region. ^3He/^4He ratios in 14 samples collected from 7 mining districts are 2.17×10^-6-12.52×10^-6, averaging 6.86×10^-6 and their R/Ra ratios are 1.56-9.01 Ra, averaging 4.37 Ra. By projecting the data points onto the ^3He-^4He concentrations diagram, all the points fall near the mantle helium area. The calculated mantle-source helium ratios are within the range of 19.58%-76.96%, with an average of 49.52%. Argon isotopic characteristics are close to those of mantle source, indicating that the ore-forming material was transport upwards via the multi-stage evolution of mantle plume and concentrated as ores in the favorable loci of mantle branch structures.     

Geochemical Eccentricity of Ground Water Allied to Weathering of Basalts from the Deccan Volcanic Province,India: Insinuation on CO<Subscript>2</Subscript> Consumption

Analyses of 72 samples from Upper Panjhara basin in the northern part of Deccan Plateau, India, indicate that geochemical incongruity of groundwater is largely a function of mineral composition of the basaltic lithology. Higher proportion of alkaline earth elements to total cations and HCO₃>Cl + SO₄ reflect weathering of primary silicates as chief source of ions. Inputs of Cl, SO₄, and NO₃ are related to rainfall and localized anthropogenic factors. Groundwater from recharge area representing Ca + Mg–HCO₃ type progressively evolves to Ca + Na–HCO₃ and Na–Ca–HCO₃ class along flow direction replicates the role of cation exchange and precipitation processes. While the post-monsoon chemistry is controlled by silicate mineral dissolution + cation exchange reactions, pre-monsoon variability is attributable chiefly to precipitation reactions + anthropogenic factors. Positive correlations between Mg vs HCO₃ and Ca + Mg vs HCO₃ supports selective dissolution of olivine and pyroxene as dominant process in post-monsoon followed by dissolution of plagioclase feldspar and secondary carbonates. The pre-monsoon data however, points toward the dissolution of plagioclase and precipitation of CaCO₃ supported by improved correlation coefficients between Na + Ca vs HCO₃ and negative correlation of Ca vs HCO₃, respectively. It is proposed that the eccentricity in the composition of groundwater from the Panjhara basin is a function of selective dissolution of olivine > pyroxene followed by plagioclase feldspar. The data suggest siallitization (L < R and R _k) as dominant mechanism of chemical weathering of basalts, stimulating monosiallitic (kaolinite) and bisiallitic (montmorillonite) products. The chemical denudation rates for Panjhara basin worked out separately for the ground and surface water component range from 6.98 to 36.65 tons/km²/yr, respectively. The values of the CO₂ consumption rates range between 0.18 × 10⁶ mol//km²/yr (groundwater) and 0.9 × 10⁶ mol/km²/yr (surface water), which indicates that the groundwater forms a considerable fraction of CO₂ consumption, an inference, that is, not taken into contemplation in most of the studies.     

甘肃庆城庄19井区上三叠统延长组长82亚油层组 低渗透储层的地质特征

长82亚油层组是甘肃庆城地区庄19井区上三叠统延长组中储集砂岩相对富集的层位,但砂岩低渗透性的特点显著,成为影响该区石油储产量增长的主要地质因素.结合前人的相关工作,通过钻井岩心观察、测井曲线分析、储层岩石实验测试等工作,详细地分析了庄19井区长82亚油层组低渗透储层的地质特征,认为沉积微相和压实作用、胶结作用是控制低渗透性储集砂岩发育和分布的主要地质因素,寻找以水下分流河道微相为代表的有利储集相带砂岩体是油气勘探的重要方向.     

山东玲珑金矿床成矿流体地球化学特征

玲珑金矿床第一成矿阶段与含金黄铁矿共生的石英中主要发育4种类型的原生流体包裹体:Ⅰ气液两相,Ⅱ含CO2三相,ⅢCO2,Ⅳ单液相包裹体。流体包裹体成分激光拉曼光谱分析及测温结果显示:①Ⅰa型包体,气液比10%~15%,均一温度为162.7~235.6℃,w(NaCl)(盐度)为4.65%~7.59%,气相平均摩尔分数为:H2O 96.48%,CO22.4%;②Ⅰb型包体,气液比30%~45%,均一温度266.9~349.2℃,w(NaCl)为10.8%~13.4%,气相平均摩尔分数为H2O 69.75%,CO224.74%;③Ⅱ型含CO2包体,CO2相所占比例为20%~90%,其均一温度为193.5~321.6℃,w(NaCl)2.9%~5.3%,CO2相中,H2O的摩尔分数为27.72%,CO2为70.6%。包裹体成分分析及测温结果综合研究认为,玲珑金矿成矿过程中存在大气降水热液与地幔来源流体的混合作用,前者与从流体中分离出的富CO2流体混合,以不同比例被捕获形成Ⅱ型包体;而与分异出CO2后的CO2不饱和地幔流体混合,被捕获形成Ⅰb型包体。两种流体混合导致的含矿热液物化条件变化对金的沉淀成矿具有重要意义。     

氧化锰矿物的生物成因及其性质的研究进展

土壤中的氧化锰矿物是原生矿物风化和成土过程的产物,是最具反应活性的一类矿物,决定着环境中许多物质的形态、迁移和转化,在元素生物地球化学循环中起着重要的作用,其形成机制和环境效应备受关注。已有的研究表明,环境中氧化锰的形成与微生物作用紧密相关,微生物作用可使自然环境中的Mn(Ⅱ)氧化速率提高105倍。参与Mn(Ⅱ)氧化的微生物在环境中广泛存在,已知的典型锰氧化细菌分布在变形菌门、放线菌门或厚壁菌门,它们均通过胞外聚合物中的多铜氧化酶来催化氧化Mn(Ⅱ)。细菌氧化Mn(II)成Mn(Ⅳ)是酶催化的两个连续的快速单电子传递过程,Mn(Ⅲ)在溶液中以与酶结合的瞬时中间态出现。生物形成氧化锰的最初形态为层状锰矿物,与δ-MnO2或酸性水钠锰矿很类似,且结晶弱,粒径小,锰氧化度高,结构中的八面体空穴多,因而比化学形成的氧化锰具有更强的吸附、氧化等表面活性。环境中Mn(Ⅱ)微生物氧化及形成的Mn(Ⅲ)中间体与碳、氮、硫等生命元素的地球化学循环的关系令人关注。     

(ϖμ/ϖT) P of the lower mantle

We estimate (/T) _P of the lower mantle at seismic frequencies using two distinct approaches by combining ambient laboratory measurements on lower mantle minerals with seismic data. In the first approach, an upper bound is estimated for |(/T) _P | by comparing the shear modulus () profile of PREM with laboratory room-temperature data of extrapolated to high pressures. The second approach employs a seismic tomography constraint ( lnV _S / lnV _P ) _P =1.8–2, which directly relates (/T) _P with (K _S /T) _P . An average (K _S /T) _P can be obtained by comparing the well-established room-temperature compression data for lower mantle minerals with theK _S profile of PREM along several possible adiabats. Both (K _S /T) and (/T) depend on silicon content [or (Mg+Fe)/Sil of the model. For various compositions, the two approaches predict rather distinct (/T) _P vs. (K _S /T) _P curves, which intersect at a composition similar to pyrolite with (/T) _P =–0.02 to –0.035 and (K _S /T) _P =–0.015 to –0.020 GPa/K. The pure perovskite model, on the other hand, yields grossly inconsistent results using the two approaches. We conclude that both vertical and lateral variations in seismic velocities are consistent with variation due to pressure, temperature, and phase transformations of a uniform composition. Additional physical properties of a pyrolite lower mantle are further predicted. Lateral temperature variations are predicted to be about 100–250 K, and the ratio of ( lnp/ lnV _S ) _P around 0.13 and 0.26. All of these parameters increase slightly with depth if the ratio of ( lnV _S / lnV _P ) _P remains constant throughout the lower mantle. These predicted values are in excellent agreement with geodynamic analyses, in which the ratios ( ln / lnV _S ) _P and ( / lnV _S ) _P are free parameters arbitrarily adjusted to fit the tomography and geoid data.     

Laboratory study of the rates and products of the phototransformations of naphthalene adsorbed on samples of titanium dioxide,ferric oxide,muscovite, and fly ash

The photodegradation of naphthalene (NPH), chosen as a model of polynuclear aromatic pollutants, has been studied in the presence of a layer of four water-insoluble inorganic solids which can be found in the troposphere (TiO₂, Fe₂O₃, muscovite, and a fly ash sample). Direct photolysis of NPH is negligible at >340 nm. Dark adsorption of NPH on TiO₂ (mainly anatase, nonporous, 50 m² g^–1) at 293 K corresponds to a surface coverage ofca. 50% at equilibrium. Under these conditions (saturated surface), the stationary-state photocatalytic degradation reaches 0.4 molecule nm^–2 h^–1 (>340 nm, radiant fluxca. 22 mW cm^–2). Dioxygen is required and its partial pressure in air is such that the degradation is zero order in O₂. Water vapor markedly increases the rate. The other particulates have also an effect, less important than that of TiO₂, however quite noticeable with respect to surface area unit for the fly ash sample which contains 3.2% Fe₂O₃. Apart from 1,4-naphthoquinone, which is the main intermediate product in all cases, 2-naphthol, phthalide, phthaldialdehyde, phthalic acid, acetophenone, benzaldehyde, benzoic acid are also formed on dry TiO₂. Depending on their volatility, these compounds are transferred to the gas phase or remain principally adsorbed on the solid particles where they are further transformed. For instance, phthalic acid (or anhydride) and benzoic acid are generated from 1,4-naphthoquinone. Degradation mechanisms are briefly discussed.