六氟化硫法测量33S/32S、34S/32S和36S/32S的方法研究

六氟化硫法是测量硫同位素组成的新方法。与传统的二氧化硫法相比，六氯化硫法有灵敏度高，准确度高，能同时测定扩δ³³S、δ³⁴S和δ³⁶S的优越性。本文介绍了国内第一台同位素分析用的六氟化硫制样装置，并报导了对硫化银、黄铁矿、黄铜矿、陨硫铁、方铅矿和闪锌矿等天然硫化物用六氟化硫法进行硫同位素测定的结果。结果表明，我们的装置和方法达到了国际上现有的水平，并在操作的方便性、可靠性及样品适用范围方面有所改进。     

异构比φiC4 /φnC4 和φiC5 /φnC5 的石油地质意义

同分子量的正构烷烃和异构烷烃存在着物理化学性质差异,在运移过程中受围岩的物理化学性质及其它外部因素的影响必然产生分异效应,从而使二者在空间分布上具有一定的特征和规律,异构比指标可以在一定程度上反映出这种特征和规律性。用异构比φ_iC4 /φ_nC4 和φ_iC5 /φ_nC5 指标可以判断有机质的成熟度,研究轻烃运移的途径、方向、生成环境及轻烃的生物降解。     

磁异常矢量倾角法及Za/Ta2、Ha/Ta2比值法

本文提出一种利用磁异常失量倾角这个参量对二度磁异常作定量解释的方法。矢量倾角是T_a(由Z_a、H_a所合成)与测线所夹的角度,其特征可以由其正切即Z_a/H_a值所反映。     

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TiO2/电气石复合物的光催化性能

采用溶胶-凝胶法制备TiO2/电气石复合光催化剂,通过光降解甲基橙实验考察复合光催化剂的活性,发现复合物中2%电气石的制备比例就可以显著提升TiO2降解有机物活性,降解率(0.5h)达99.87%,明显优于纯TiO2(0.5h)83.64%,提高了约20%。经XRD、BET、SEM等手段对样品进行分析得知:经800℃以下长时间热处理,电气石的结晶构造不变;900℃热处理使电气石结构破坏。SEM分析显示复合物中TiO2颗粒呈球簇状,均匀包覆在电气石表面形成颗粒膜层。     

南京直立人的U/Th和U/Pa年代

中国直立人化石的准确定年对于研究人类演化有着极为重要的意义。1993～1994年在南京汤山葫芦洞发现的两个直立人头盖骨化石和一枚牙化石被称为“南京直立人”。其中1号头盖骨化石之上的方解石钙板的U/Th年龄为53.3_(-1.2)~(+1.5)万年;但考虑到定年的准确性,则为53.3_(-3.0)~(+3.5)万年。其~(231)Pa/~(235)U活度比值为0.998±0.006。这表明“南京直立人”的年代应该大于50万年。与”南京直立人”伴生的动物牙化石U/Th年代为18.5～29.0万年;U/Pa年代为13.7～17.2万年。此外,对于同一颗牙化石,牙釉的年龄小于牙本质的年龄。同一样品的U/Pa年龄也显著小于其U/Th年龄。因此,牙化石的U摄取过程并不符合U早期摄取模式。多数牙化石分析点在~(234)U/~(238)U-~(230)Th/~(238)U图上落在位于U早期摄取和线性摄取模式曲线之间,指示牙化石的U摄取过程很可能介于上述两种模式之间。如果这一假设成立,那么牙化石的U/Th和U/Pa线性摄取模式年龄则为其年代的上限。因为不受U摄取过程~(234)U/~(238)U变化的影响,U/Pa线性摄取模式年龄比U/Th较为可靠。最小的U/Pa线性摄取模式年龄为1Ma,这是”南京直立人”上限年龄的估计。从定年结果看,”南京直立人”可能生活在海洋同位素(MIS)16阶段,但这不是最终结论。     

CaMnSi2O6-CaAlSiAlO6系统的实验研究

冶金炉渣是在迅速冷却的条件下结晶的,铸石是在熔体的固相线以下恒温结晶的,这两种情况皆属不平衡状态。过去的硅酸盐体系的实验研究几乎仅局限于平衡状态,对非平衡状态研究甚少,只是近来才开始这方面的研究。在硅锰渣铸石和硅锰渣微晶铸石中,主要矿物为锰铸普通辉石--钙锰辉石与钙契尔马克分子（CaAlSiAlO₆）以及少量的Mg₂Si₂O₆的固溶体,其次是钙蔷薇辉石和钙长石,另外还有极少量的方锰石、硫化锰等。     

P–V–T equation of state of Ca3Al2Si3O12 grossular garnet

The thermoelastic parameters of synthetic Ca₃Al₂Si₃O₁₂ grossular garnet were examined in situ at high-pressure and high-temperature by energy dispersive X-ray diffraction, using a Kawai-type multi-anvil press apparatus coupled with synchrotron radiation. Measurements have been conducted at pressures up to 20 GPa and temperatures up to 1,650 K: this P, T range covered the entire high-P, T stability field of grossular garnet. The analysis of room temperature data yielded V _0,300 = 1,664 ± 2 ?³ and K ₀ = 166 ± 3 GPa for K^￠₀ K^{\prime}_{0} fixed to 4.0. Fitting of our P–V–T data by means of the high-temperature third order Birch–Murnaghan or the Mie–Grüneisen–Debye thermal equations of state, gives the thermoelastic parameters: (∂K _0,T /∂T) _P  = −0.019 ± 0.001 GPa K⁻¹ and α _0,T  = 2.62 ± 0.23 × 10⁻⁵ K⁻¹, or γ ₀ = 1.21 for fixed values q ₀ = 1.0 and θ ₀ = 823 (Isaak et al. Phys Chem Min19:106–120, 1992). From the comparison of fits from two different approaches, we propose to constrain the bulk modulus of grossular garnet and its pressure derivative to K _T0 = 166 GPa and K^￠_T0 K^{\prime}_{T0}  = 4.03–4.35. Present results are compared with previously determined thermoelastic properties of grossular-rich garnets.     

氟对磷酸盐矿物形成影响的试验研究——Ca2+-HPO42--HCO31--F1--H2O体系

我們在前一篇文章里曾討論了Ca²⁺-HPO₄^2--F^1--H₂O体系中氟对磷酸盐矿物形成影响的若干方面。为了使該項模拟試驗工作更符合于表生作用条件,我們在叶連俊教授的指导下,在上述实驗体系中增加了一个組分--HCO₃^1-,进行了Ca²⁺-HPO₄^2--HCO₃^1-F^1--H₂O体系的試驗研究。其目的为进一步探索在合有HCO₃^1-組分的体系中氟对磷酸盐矿物形成的影响,以及CO₃^2-能否进入磷灰石晶格和磷酸盐矿物与碳酸盐矿物的沉积分异順序等問題。     

室温常压下 Ca2+-Mg2+-HCO31--H2O 体系的试验研究

世界上很多海域中的现代碳酸盐沉积正在形成,如巴哈马滩、美国的佛罗里达湾、古巴的巴塔诺湾、中东的波斯湾等地,以及丹麦的某些近海地区。产于这些海域中的现代碳酸盐沉积物,其矿物组成主要是文石,其次为镁方解石,纯方解石较少,现代白云石沉积更为少见。我国的现代碳酸盐沉积见于南海诸岛及海南岛的沿海地带。作者曾利用粉晶照相鉴定了采自我国南海二十余种珊瑚、瓣鳃类、腹足类、有孔虫等现代海相生物壳体的物相,发现除有孔虫和海胆壳是由镁方解石构成外,其余生物壳体皆由文石构成。     

H2O2在α-Fe2O3表面非均相氧化SO2机理的模拟研究

通过密度泛函理论模拟了H_2O_2和SO_2气体在矿物氧化物(α-Fe_2O_3)表面上的非均相反应,研究了H_2O_2和SO_2在α-Fe_2O_3(001)表面的吸附机制和氧化机制。研究结果表明,SO_2、H_2O_2均在α-Fe_2O_3(001)表面通过Fe原子进行吸附,H_2O_2相比于SO_2优先吸附在α-Fe_2O_3(001)表面,且H_2O_2在表面的赋存形式趋向于两个·OH形式吸附。通过二者共吸附的局域态密度、差分电荷密度、Mulliken电荷布局分析结果发现,SO_2和H_2O_2的共吸附形式是通过H_2O_2产生的·OH吸附在α-Fe_2O_3(001)表面,同时SO_2被H_2O_2产生的·OH氧化[S(SO_2)-电荷布局:0. 79 e→1. 32 e; O(H_2O_2)-电荷布局:-0. 77 e→-1. 11 e]形成·OH+SO_2团簇。模拟结果表明大气微量气体H_2O_2能够在矿物氧化物表面介导SO_2吸附并促进SO_2的转化,为理解H_2O_2在大气中非均相氧化SO_2的反应过程提供了理论依据。     

Hydrous olivine (Mg1? y? Fe2+y)2? x ?v x ? SiO4H2 x – a new DHMS phase of variable composition observed as nanometer-sized precipitations in mantle olivine

 An olivine grain from a peridotite nodule 9206 (Udachnaya kimberlite, Siberia) was investigated by TEM methods including AEM, HRTEM, SAED and EELS techniques. A previous study of the 9206 olivine sample revealed OH absorption bands in the IR spectrum and abundant nanometer-sized OH-bearing inclusions, of hexagonal-like or lamellar shape. Inclusions, which are several hundred nm in size, consist of 10 ? phase, talc and serpentine (chrysotile and lizardite). The lamellar (LI) and hexagon-like small inclusions of several ten nm in size (SI) are the topic of the present paper. AEM investigations of the inclusions reveal Mg, Fe and Si as cations only. The Mg/Si and Fe/Si atomic ratios are lower in the inclusions than in the host olivine. The Si concentration in the olivine host and both lamellar inclusions and small inclusions is the same. A pre-peak at 528eV was observed in EEL spectra of LI and SI, which is attributed to OH⁻ or Fe³⁺. From these data it is concluded that there is a OH⁻- or Fe³⁺-bearing cation-deficient olivine-like phase present. HRTEM lattice fringe images of LI and SI exhibit modulated band-like contrasts, which are superimposed onto the olivine lattice. Diffraction patterns (Fourier-transforms) of the HREM images as well as SAED patterns show that the band-like contrasts in HRTEM images of the inclusions are caused by periodic modulations of the olivine lattice. Three kinds of superperiodicity in the olivine structure such as 2a, 3a and 3c, were observed in SAED patterns. The corresponding olivine supercells labelled here as Hy-2a, Hy-3a and Hy-3c were derived. The M1-vacancies located in the (100) and (001) octahedral layers of the olivine lattice are suggested to form ordered arrays of planar defects (PD), which cause the band-like contrasts in HRTEM patterns as well as the superperiodicity in the SAED patterns. The vacancy concentrations as well as the chemical composition of Hy-2a, Hy-3a and Hy-3c olivine supercells were calculated using crystal chemical approaches, assuming either {(OH)^< _O−V^" _Me−(OH)^< _O}^↔, or {F e ^< _Fe −H _Me ^′}^↔ or {2F e ^< _Fe −V _Me ^"}^↔ point defect associates. The calculated theoretical compositions Mg_1.615Fe⁺² _0.135v_0.25SiO₄H_0.5 (Hy-2a) and Mg_1.54Fe²⁺ _0.12v_0.33SiO₄H_0.66 (Hy-3a and Hy-3c) are in a good agreement with the AEM data on inclusions. Hy-2a, Hy-3a and Hy-3c are considered to be a hydrous olivine with the extended chemical formula (Mg_1-yFe²⁺ _y)_2−xv_xSiO₄H_2x. The crystal structure of hydrous olivine is proposed to be a modular olivine structure with Mg-vacant modules. The crystal chemical formula of hydrous olivines in terms of a modular structure can be written as [MgSiO₄H₂] · 3[Mg_1.82Fe_0.18SiO₄] for Hy-2a, [MgSiO₄H₂] · 2[Mg_1.82Fe_0.18SiO₄] for Hy-3a and Hy-3c. Hydrous olivine is suggested to be exsolved from the olivine 9206, which has been initially saturated by OH-bearing point defects. The olivine 9206 hydration as well as the following exsolution of hydrous olivine inclusions is suggested to occur at high pressure-high temperature conditions of the upper mantle. Received: 15 January 2001 / Accepted: 2 July 2001     

岩爆岩石弹射性能综合指数 Krb判据

本文以正在施工的南盘江天生桥大型水电站引水隧洞中产生岩爆的石灰岩为试件,在电液闭路伺服控制刚性试验机上进行了大量的岩石弹射试验。依据荷载-位移全过程曲线,分析了有效弹射能 W_eff 与岩爆岩石脆性指数 K_u、应力下降指数 K_σ以及弹性应变能指数 K_w 之间的关系,提出了岩爆岩石弹射性能综合指数 K_rb判据。     

莱河矿(Fe0.52+Fe1.03+SiO4)的超结构

莱河矿于1976年在中国辽宁省的磁铁矿床中首次被发现,许多人对它进行过研究。该矿物为黑色、不透明,化学式为Fe_0.58²⁺Fe_1.0³⁺Mg_0.03Si_0.96O₄,虽然它的晶体结构近似于橄榄石,但已确定为单斜晶系,空间群为P2₁/b。本文作者利用X射线、电子探针、高分解能透过电子显微镜对该矿物进行了系统的研究,发现它具有假双晶、超结构和显微条纹结构。     

Thermal expansion along the NaAlSi2O6–NaFe3+Si2O6 and NaAlSi2O6–CaFe2+Si2O6 solid solutions

The high temperature volume and axial parameters for six C2/c clinopyroxenes along the NaAlSi₂O₆–NaFe³⁺Si₂O₆ and NaAlSi₂O₆–CaFe²⁺Si₂O₆ joins were determined from room T up to 800°C, using integrated diffraction profiles from in situ high temperature single crystal data collections. The thermal expansion coefficient was determined by fitting the experimental data according to the relation: ln(V/V ₀) = α(T − T ₀). The thermal expansion coefficient increases by about 15% along the jadeite–hedenbergite join, whereas it is almost constant between jadeite and aegirine. The increase is related to the Ca for Na substitution into the M2 site; the same behaviour was observed along the jadeite–diopside solid solution, which presents the same substitution at the M2 site. Strain tensor analysis shows that the major deformation with temperature occurs in all samples along the b axis; on the (010) plane the higher deformation occurs in jadeite and aegirine at a direction almost normal to the tetrahedral–octahedral planes, and in hedenbergite along the projection of the longer M2–O bonds. The orientation of the strain ellipsoid with temperature in hedenbergite is close to that observed with pressure in pyroxenes. Along the jadeite–aegirine join instead the high-temperature and high-pressure strain are differently oriented.     

Cl-/SO42-铁盐对含可溶性胞外多聚物Acidithiobacillus ferrooxidans溶液中铁矿物形成的影响

铁细菌胞外多聚物作用下聚集的铁可通过氧化或者沉淀作用使铁稳定或沉积,从而形成铁矿物。本文基于铁细菌胞外多聚物(extracellular polymeric substances,EPS)对铁矿物形成的调控作用,介绍了Cl-/SO_4~(2-)的Fe(Ⅲ)或Fe(Ⅱ)盐作用下,含可溶性EPS的氧化亚铁硫杆菌(Acidithiobacillus ferrooxidans)溶液中铁矿物的形成,观察了溶液pH值变化及形成铁矿物的矿相与结构,并采用XRD、FTIR和FESEM对其进行表征。结果发现反应溶液中OH-离子可与Fe3+形成微米级"针垫"聚集球状或纳米级小球形施威特曼石和微米级"菱形"块状黄钾铁矾铁矿物沉淀。反应溶液中的可溶性EPS可调控和促进铁矿物的形成,但对Fe2+的氧化未产生影响;外源Fe盐可促进施威特曼石向黄钾铁矾转化。随着Cl-/SO_4~(2-)摩尔比例的增加(即Cl-含量的不断增加),两矿相间的转化明显受到抑制,且铁矿物颗粒之间的集聚作用明显减弱;反之,SO_4~(2-)含量升高时,有利于铁矿物间的转化和聚集球状颗粒形貌结构的形成。     

玄武岩的 MnO-TiO2-P2O5判别图的修改与补充

近些年来,人们广泛地利用火山岩的主元素或微量元素的特征对火山岩进行地球化学、成因岩石学和构造岩石学的研究。Mullen(1983)利用玄武岩的 MnO、TiO₂和P₂O₅建立大洋型玄武岩的 MnO×10-TiO₂-P₂O₅×10的构造背景判别图(以下简称MTP图)和圈出了大陆拉斑玄武岩在 MTP 图中的分布范围。他选择了能反映玄武岩形成过程中的重要地球化学特征和成因机制的元素组作为该图的端元组分。     

用84Sr作稀释剂时样品中87Sr/86Sr比值的计算

用Rb-Sr法测定地质年龄,对地质样品中的锶往往要进行两种同位素分析:非稀释分析以测定⁸⁷Sr/⁸⁶Sr比值;稀释分析以测定样品中⁸⁶Sr的含量。随着稀释剂⁸⁴Sr丰度的提高,Wasserburg et al.(1964),Van schmus(1965),Wetherill与Bickford(1965)采用了以一代二的办法——用稀释分析既测定含量又测⁸⁷Sr/⁸⁶Sr比值。由于稀释剂中⁸⁴Sr高度富集,⁸⁷Sr/⁸⁶Sr受到的影响小,在当时的技术条件下,这些作者没有对一些数据处理进行讨论。但随着计算技术的应用,大大提高了测量精度,稀释剂对⁸⁷Sr/⁸⁷Sr的影响则必须加以考虑。