Ag_2S-Cu_2S-PbS和Ag_2S-Cu_2S-Bi_2S_3体系相关系及相关矿物共生组合研究

本文用抽空石英管法对三元硫化物体系Ag_2S-Cu_2S-PbS和Ag_2S-Cu_2S-Bi_2S_3在500℃的相图进行了研究。 Ag_2S-Cu_2S-PbS体系500℃相关系,受方铅矿和固溶体f.c.c.(Ag_xCu_(2-x)S)、b.c.c.(Cu_xAg_(2-x)S)所控制。在接近PbS-Cu_2S连线处有一液相区。随温度下降,方铅矿可与Cu_2-Ag_2S二元系上所有各相平衡共存。 Ag_2S-Cu_2S-Bi_2S_3体系在500℃时则包含六个固溶体,即块硫铋银矿、铜银铅铋矿、杂硫铋银矿、硫铋铜矿、CuBi_3S_5、Cu_3Bi_5S_9和新合成“C”(Ag_(1.1)Cu_(4.8)Bi_(5.8)S_(12))。最令人感兴趣的是无铜、无铅的铜银铅铋矿(Ag_2Bi_4S_7)合成成功。 以上二个三元系中矿物稳定性及共生关系也根据相图研究结果进行了讨论。     

离子色谱法测定水样中S2-、SO2-3、SO2-4、S2O2-3

该种方法利用离子色谱仪的电导检测器与电化学检测器串联,十几分钟即可连续完成水中S2-、SO2-3、SO2-4、S2O2-3的测定,方法具有快速、高效、方便、灵敏、选择性好等特点.方法的检出限分别为S2-12.5μg/L;SO2-3 22.4μg/L;SO2-4 5.0μg/L;S2O2-3 5.0μg/L.相对标准偏差在1.5%～6.9%之间,能够满足水中S2-、SO2-3、SO2-4、S2O2-3四种阴离子分析测试的需要.     

Effects of Pb^2＋, Cd^2＋ and Cu^2＋ on the Aqueous Zn^2＋ Sorption by Hydroxyapatite

In this paper, the behaviors of aqueous zinc sorption by hydroxyapatite in the co-existence of Pb^2＋, Cd^2＋ and Cu^2＋ are investigated, the effects of Pb^2＋, Cd^2＋ and Cu^2＋ on the sorption of Zn^2＋ are discussed, and the hydroxyapatite sorption capabilities for Pb^2＋, Cd^2＋, Cu^2＋ and Zn^2＋ are compared. The experimental results show that the Zn^2＋ removal efficiency decreases gradually with the increase of the Cd^2＋ concentration of the solution, and there is no sorption preference between Cd^2＋ and Zn^2＋. On the other hand, the Zn^2＋ removal efficiency rapidly decreases rapidly with the increase of the Cu^2＋ concentration of the solution, and there is a clear sorption preference between Cu^2＋ and Zn^2＋. It is noticed that the Zn^2＋ removal efficiency is hardly changed with the variance of Pb^2＋ concentration because the removal mechanisms for these two ions are totally different. It is concluded that the adsorption affinities of the heavy metals for the hydroxyapatite follows this sequence： pb^2＋〉 Cu^2＋〉 Cd^2＋〉 Zn^2＋.     

K_2O-Al_2O_3-SiO_2-H_2O体系的相平衡研究

K_2O-Al_2O_3-SiO_2-H_2O体系形成一些主要造岩矿物,如长石、石英和云母等,因此受到有关学者的广泛重视。为了探讨岩石的形成机制,国外许多学者曾研究过该体系矿物的稳定范围。近年来,伊万诺夫、J.W.谢德(Shade)、R.P.温特施(Wintsch)、D.M.伯特(Burt)、H.W.戴(Day)和J.J赫姆利(Hemley)等也先后用热力学方法研究过该体系的相平衡关系。但至今,该体系中某些矿物的相平衡关系仍然有争议,例如,     

H_2O_2增效TiO_2/凹凸棒石光催化体系降解亚甲基蓝

以钛酸四丁酯为前驱体,天然凹凸棒石为载体,采用溶胶凝胶法制备了TiO_2/凹凸棒石复合光催化剂,并用XRD、TEM对其进行表征.以亚甲基蓝染料为模拟污染物,采用300 W汞灯为紫外光源,以光催化实验来评价该催化剂的活性,并研究了H_2O_2的引入对光催化活性的影响.实验结果表明,H_2O_2能显著提高染料的脱色效率:亚甲基蓝的初始浓度为50 mg/L,催化体系为2 mmol/L H_2O_2+0.5 g/L TiO_2/凹凸棒石+UV(紫外线),光催化10 min后其脱色率为95%,相对于单独的0.5 g/L TiO_2/凹凸棒石+UV催化体系,其脱色率提高了约50%.全波段扫描显示,加入H_2O_2后,亚甲基蓝在290 nm对应的苯环吸收蜂急剧下降,665 nm对应的最大吸收峰则近乎消失,且没有新的吸收峰产生.     

Cu_2S-PbS-Bi_2S_3和Ag_2S-PbS-Bi_2S_3体系相关系及相关矿物共生组合研究

本文用抽空石英管法对三元硫化物体系Ag_2S-PbS-Bi_2S_3和Cu_2S-PbS-Bi_2S_2的500℃相关系进行了研究。Cu_2S-PbS-Bi_2S_3体系的相图特征是Bi_2S_3-CuPbBiS_3。之间完全固溶关系,以及它与二元系Cu_2S-Bi_2S_3和PbS-Bi_2S_3各相之间双变关系。Ag_2S-PbS-Bi_2S_3体系相图被PbS-AgBi_S_2之间的完全固溶关系分成两部分:富铋与富银。富银部分仅有辉银矿与PbS-AgBiS_2固溶体之间简单双变关系,而富铋部分却包含丰富的银、铅铋硫盐。在抽空石英管法500℃下合成成功的有块硫铋银矿固溶体、铜银铅铋矿、硫铋铅矿固溶体、富硫铋铅矿和辉铅铋矿。 以上两个体系中矿物之间共生长关系及稳定范围也作了简短讨论。     

同安郭山高岭土中 SiO_2与 Al_2O_3、Fe_2O_3与 TiO_2的相关关系的初步探讨

众所周知,在高岭土中 SiO_2与 Al_2O_3之间的比值是确定高岭石矿物含量的一个重要参数,而 Fe_2O_3与 TiO_2的含量则是评价高岭土质量的重要参数。所以 SiO_2、Al_2O_3、Fe_2O_3、TiO_2是高岭土进行化学成分分析的重要分析项目。大量的分析结果表明,高岭土中的 SiO_2含量增高,Al_2O_3含量则相应降低;而 Fe_2O_3     

四元体系K_2SO_4-K_2B_4O_7-K_2CO_3-H_2O 273K时介稳相平衡研究

采用等温蒸发法研究K2SO4-K2B4O7-K2CO3-H2O四元体系在低温273K时的介稳固液相平衡关系,测定了介稳平衡液相的溶解度和密度。研究发现,该四元体系273K时的介稳平衡相图有3个固相结晶相区分别为K2SO4,K2B4O7.4H2O和K2CO3.3/2H2O;3条单变量曲线E1E,E2E和E3E;一个共饱点E,在共饱点E处的液相中各盐的溶解度分别为K2CO3(43.46%),K2SO4(2.52%)和K2B4O7(3.10%);研究结果表明K2CO3对K2B4O7和K2SO4有强烈的盐析作用。实验证明在富含硼钾的扎布耶盐湖卤水中,低温平衡条件下硫酸钾和硼酸钾极易从溶液中结晶析出,而碳酸钾则由于溶解度大,介稳性强,即使在低温条件下也难以从溶液中析出。     

离子色谱法测定水样中S^2－、SO3^2－、SO4^2－、S2O3^2－

该种方法利用离子色谱仪的电导检测器与电化学检测器串联，十几分钟即可连续完成水中S^2-、SO3^2-、SO4^2-、S2O3^2-的测定，方法具有快速，高效，方便，灵敏，选择性好等特点。方法的检出限分别为：S^2-12.5μg/L；SO3^2-22.4μg/L;SO4^2-5.0μg/L；S2O3^2-5.0μg/L。相对标准偏差在1.5%-6.9%之间，能够不中S^2-、SO3^2-、SO4^2-、S2O3^2-四种阴离子分析测试的需要。     

溶液中Pb~(2+),Cd~(2+)和Cu~(2+)离子对羟基磷灰石吸附Zn~(2+)行为的影响

本文研究了在Pb~(2+),Cd~(2+)和Cu~(2+)等离子共存的条件下,羟基磷灰石对溶液中Zn~(2+)离子的吸附行为,讨论了Pb~(2+),Cd~(2+)和Cu~(2+)离子对Zn~(2+)吸附行为的影响;比较了羟基磷灰石对上述离子的吸附能力。实验结果表明:随着Cd~(2+)离子浓度增大,对Zn~(2+)的去除率逐渐增高,羟基磷灰石对Cd~(2+)和Zn~(2+)离子无吸附选择性。而随着Cu~(2+)离子浓度增大,对Zn~(2+)的去除率急剧下降,表现出明显的吸附选择性。另一方面,对Zn~(2+)的去除率几乎不随Pb~(2+)离子浓度的变化而改变,这是由于羟基磷灰石对这两种离子的吸附行为与机理不同。上…     

新疆坡北矿区ZK2-6孔钻探施工技术

新疆坡北矿区ZK2-6孔施工中遇到多层蚀变带,最长连续强蚀变带达30 m,在以往施工过程中,因卤水配制的泥浆性能难以保证,不利于孔壁的稳定,导致在钻进过程中,孔壁剥落超径、断钻杆事故频发。钻杆断开后,由于孔壁坍塌,找不到事故头,从而导致钻孔报废。针对蚀变、破碎地层钻进易发生的孔壁坍塌、超径、掉块及卤水泥浆性能难以保证等问题,开展相关研究,提出相应的技术措施,圆满完成了坡北工区ZK2-6孔的钻探施工。     

Thermodynamics of multicomponent pyroxenes: III. Calibration of Fe2+(Mg)-1, TiAl2(MgSi2)-1, TiFe 2 3+ (MgSi2)-1, AlFe3+(MgSi)-1, NaAl(CaMg)-1, Al2(MgSi)-1 and Ca(Mg)-1 exchange reactions between pyroxenes and silicate melts

A thermodynamic model for the Gibbs free energy of igneous pyroxenes with the general formula [Na, Ca, Fe²⁺, Mg]^M2[Fe²⁺, Mg, Ti, Al, Fe³⁺]^M1[Al, Fe³⁺, Si]^TetSiO₆ is calibrated from experimentally determined compositions of coexisting pyroxene and silicate melt. The model is based upon the general formulation, and relies upon the calibration of the “quadrilateral” subsystem, previously published by the present authors. The calibration database of pyroxene-liquid equilibria spans a broad spectrum of temperature, pressure and oxygen fugacity conditions, ranging from 1000°–1600°C, 0.001–30 kbar and iron-wüstite to air. Chemical potentials of endmember pyroxene components as well as exchange potentials between pyroxenes and coexisting liquids are defined utilizing the present authors' thermodynamic melt model. Model parameters are extracted from these relations by regression analysis. The resulting model and derivative endmember properties are internally consistent with an existing standard state thermodynamic database. The success of the model and its applicability to igneous petrogenesis are demonstrated by comparing calculated and experimentally determined liquidus compositions, temperatures and symmetry states for pyroxenes crystallizing from a variety of silicate melts, ranging in composition from tholeiites and angrites through rhyolites to potash ankaratrites.     

Raman spectroscopic study of clinopyroxenes in the system CaScAlSiO6 - CaAl2SiO6

Seven clinopyroxenes in the system CaScAlSiO₆- CaAl₂SiO₆ synthesized at 1 atm and under high pressure have been studied by Raman spectroscopy. The T-O-T stretching band of CaScAlSiO₆ pyroxene can be deconvoluted into three bands corresponding to Al-O-Al, Al-O-Si, and Si-O-Si stretching vibrations, although that of CaAl₂SiO₆ can be deconvoluted into the two bands (Al-O-Al+Al-O-Si) and Si-O-Si. The Al-O-Si Raman shifts of CaScAlSiO₆ and CaAl₂SiO₆ pyroxenes are found to fall on the linear plot of the relationship between T-T distance and Raman shifts in ABSi₂O₆-type pyroxenes, suggesting that the Al-O-Si chains are relatively long. Variation of areal fractions of the Raman bands demonstrates that the partial disordering of Al/Si depends on the ionic radius and electronegativity of the octahedral ion.     

鄂尔多斯盆地西南缘镇泾油田6-2沉积相研究

延长组长6-2是鄂尔多斯盆地西南缘镇泾油田的一个重要勘探层位．通过岩心观察、测井资料、薄片研究、粒度分析，对镇泾油田长6-2沉积微相进行了深入研究．认为该区长6-2由一个完整的中期基准面旋回组成，水下分流河道主要发育在中期基准面缓慢上升初期和快速下降阶段，由于水下分流河道的强烈侵蚀作用，河口坝砂体不发育．中期基准面缓慢上升初期的河道具有深而窄的特点，砂体横向变化快，勘探难度大，而与之相对的是中期基准面快速下降阶段，水下分流河道具有厚而广的特点，为本区最为有利的勘探目的层．通过对不同可容空间下水下分流河道砂体厚度与河道宽度的研究，发现其具有很好的相关性，得出该区的砂体厚度与河道宽度的经验公式，为下一步勘探开发提供了强有力的理论依据。     

鄂尔多斯盆地西南缘镇泾油田长6-2沉积相研究

延长组长6-2是鄂尔多斯盆地西南缘镇泾油田的一个重要勘探层位.通过岩心观察、测井资料、薄片研究、粒度分析,对镇泾油田长6-2沉积微相进行了深入研究.认为该区长6-2由一个完整的中期基准面旋回组成,水下分流河道主要发育在中期基准面缓慢上升初期和快速下降阶段,由于水下分流河道的强烈侵蚀作用,河口坝砂体不发育.中期基准面缓慢上升初期的河道具有深而窄的特点,砂体横向变化快,勘探难度大,而与之相对的是中期基准面快速下降阶段,水下分流河道具有厚而广的特点,为本区最为有利的勘探目的层.通过对不同可容空间下水下分流河道砂体厚度与河道宽度的研究,发现其具有很好的相关性,得出该区的砂体厚度与河道宽度的经验公式,为下一步勘探开发提供了强有力的理论依据.     

4-(5-硝基-2-吡啶偶氮)-1,3-二氨基苯光度法同时测定钴和钯

基于Co(Ⅱ)、Pd(Ⅱ)与4-(5-硝基-2-吡啶偶氮)-1,3-二氨基苯(5-NO2-PADAB)在不同酸度介质中显色的差异,建立了差减法同时测定钴和钯的方法。在室温下,Co(Ⅱ)与5-NO2-PADAB仅能在pH 6.2~8.0定量反应,钴配合物形成后即非常稳定,加酸酸化后,其最大吸收波长由518 nm红移至580 nm,且灵敏度显著提高;而在强酸性介质中仅Pd(Ⅱ)与5-NO2-PADAB能发生显色反应,其最大吸收波长位于586 nm。在586 nm处,钴、钯配合物吸光度具有良好的加和性,其表观摩尔吸光系数分别为1.28×105L.mol-1.cm-1和1.04×105L.mol-1.cm-1。钴、钯的浓度分别在0~0.48 mg/L和0~1.2 mg/L符合比尔定律。所拟方法已用于矿样中钴、钯的同时测定,结果与原子吸收法相符,相对标准偏差(RSD,n=6)分别为1.6%和1.0%。     

Experimental Study of Cement - Sandstone/Shale - Brine - CO2 Interactions

Background

Reactive-transport simulation is a tool that is being used to estimate long-term trapping of CO₂, and wellbore and cap rock integrity for geologic CO₂ storage. We reacted end member components of a heterolithic sandstone and shale unit that forms the upper section of the In Salah Gas Project carbon storage reservoir in Krechba, Algeria with supercritical CO₂, brine, and with/without cement at reservoir conditions to develop experimentally constrained geochemical models for use in reactive transport simulations.

Results

We observe marked changes in solution composition when CO₂ reacted with cement, sandstone, and shale components at reservoir conditions. The geochemical model for the reaction of sandstone and shale with CO₂ and brine is a simple one in which albite, chlorite, illite and carbonate minerals partially dissolve and boehmite, smectite, and amorphous silica precipitate. The geochemical model for the wellbore environment is also fairly simple, in which alkaline cements and rock react with CO₂-rich brines to form an Fe containing calcite, amorphous silica, smectite and boehmite or amorphous Al(OH)₃.

Conclusions

Our research shows that relatively simple geochemical models can describe the dominant reactions that are likely to occur when CO₂ is stored in deep saline aquifers sealed with overlying shale cap rocks, as well as the dominant reactions for cement carbonation at the wellbore interface.     

Chemistry of some Pb-(Cu,Fe)-(Sb,Bi sulfosalts from France and Portugal. Implications for the crystal chemistry of lead sulfosalts in the Cu-poor part of the Pb2S2-Cu2S-Sb2S3-Bi2-Bi2S3 system

Electron microprobe analysis of Pb-Cu(Fe)-Sb-Bi sulfosalts from Bazoges and Les Chalanches (France), and Pedra Luz (Portugal), give new data about (Bi, Sb) solid-solution and incorporation of the minor elements Cu, Fe or Ag in jaskolskiite, and in izoklakeite-giessenite and kobellite-tintinaite series. Jaskolskiite from Pedra Luz has high Sb contents (from 17.9 to 20.7 wt.%), leading to the extended general formula: Cu _x Pb_2+x (Sb_1–y Bi _y )_2–x S₅, with 0.10 x 0.22 and 0.19 y 0.41. Fe-free, Bi-rich izoklakeite from Bazoges has high Ag contents (up to 2.2 wt. %), leading to the simplified formula Cu₂Pb₂₂Ag₂(Bi, Sb)₂₂S₅₇; in Les Chalanches it contains less Ag content (1.2 wt.%), but has an excess of Cu that gives the formula: Cu_2.00 (Cu_0.49Ag_1.18)_=1.67Pb_22.70(Bi_12.63Sb_8.99)_=21.62S_57.27.In tintinaite from Pedra Luz, the variation of the Fe/Cu ratio can be explained by the substitution: Cu + (Bi, Sb) Fe + Pb; Fe-free kobellite from Les Chalanches has a Cu-excess, corresponding to the formula Cu_2.81Ag_0.54Pb_9.88(Bi_10.37Sb_5.21)_=15.38S_35.09. Eclarite from the type locality, structurally related to kobellite, shows a Cu excess too. In natural samples of the kobellite homologous series, Fe is positively correlated with Pb, and its contents never exceed that of Cu. Ag substitutes for Pb, together with (Bi, Sb). Taking into account the possibility of Cu excess, but excluding formal Cu²⁺ and Fe³⁺, general formulae can be written:     

The liquidus surface of the system forsterite - kalsilite - quartz at 28 kb under dry conditions,in presence of H2O,and of CO2

Summary The system forsterite-kalsilite-quartz (Fo-Ks-Qz) has been studied at 28 kb and variable temperatures in the presence of CO₂ or H₂O and in the absence of volatiles to clarify the role of potassium in mantle phase equilibria. Under dry conditions, the forsterite--enstatite (En)-sanidine (San) peritectic (En + liquid Fo + San) occurs at 1460°C ± 20 °C at Fo₅Ks₆₂Qz₃₃ and the Fo-San-Ks eutectic at 1440 ± 10 °C at (Fo ₆Ks ₆₉Qz ₂₅). Dry melting of forsterite-enstatite-sanidine produces liquids at 1460°C which lie well to the Ks side of the Fo-San join. Under water-saturated-conditions, there is a large liquidus of phlogopite (Ph). The extrapolation of the Fo Ph join to intersect the Fo-Ph reaction boundary defines a thermal divide for liquids trending either towards the Ks-San-Ph or Qz-San-Ph eutectics. Under CO₂-saturated conditions, the olivine-enstatite cotectic moves to much lower SiO₂ compositions, such that the Fo-En-San eutectic occurs < 1260 ± 20 °C at compositions well within Fo--San-Ks field. The experimental study of the system establishes mechanisms through variation of CO₂ H₂O (C-H-0) by which a simplified phlogopite-bearing harzburgite may yield potassic liquids ranging from hypersthenenormative (and fractionating on a path to SiO₂ oversaturation) to strongly leucite (or kalsilite)-normative. The fractionation of hydrous silica-undersaturated liquids may trend either towards SO₂-oversaturated minimum or towards SiO₂-undersaturated minimum depending upon the role of phlogopite.

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Die Liquidusfläche des Systems forsterit-kalsilite-quarz bei 28 kbar unter trockenen bedingungen, sowie bei anwesenheit von H₂O und CO₂

Zusammenfassung Das System Forsterit-Kalsilit-Quarz (Fo-Ks-Qz) wurde bei 28 kbar und variablen Temperaturen in Anwesenheit von CO₂ and H₂O sowie bei Abwesenheit von Volatilen untersucht, um die Rolle des Kaliums in den Phasengleichgewichten des Erdmantels aufzuklären. Unter trockenen Bedingungen liegt das Forsterit-Enstatit(En)-Sani din(San)-Peritektikum (En + liquid -> Fo + San) bei 1460±:E 20°C undFo ₅Ks ₆₂Qz ₃₃ und das Fo-San-Ks Eutektikum bei 1440± 10 °C und Fo₆Ks ₆₉Qz ₂₅. Trockenes Schmelzen von Forsterit-Enstatit-Sanidin erzeugt Schmelzen bei 1460°C, die deutlich auf der Ks-Seite der Linie Fo-San liegen. Unter wassergesättigten Bedingungen besteht ein großer Liquidus für Phlogopit (Ph). Die Extrapolation der Fo-Ph-Linie bis zum Schnitt mit der Grenze der Fo-Ph-Reaktion definiert eine thermische Scheidelinie für Schmelzen, gegen die Eutektika von Ks-San-Ph oderQz-San-Ph zu tendieren. Unter CO₂-Sättigung verschiebt sich das Olivin-Enstatit-Kotektikum zu viel niedrigeren SiO₂-Gehalten, so daß das Fo-En--San-Eutektikum bei 1260°C und Zusammensetzungen klar innerhalb des Fo-San-Ks-Feldes auftritt. Das experimentelle Studium des Systems setzt die Mechanismen durch Variation von CO₂-H₂O (C-H-O) fest, durch welche ein vereinfachter Phlogopit-führender Harzburgit kalibetonte Schmelzen liefern kann, die von Hypersthen-normativ (und auf einem Fraktionierungsweg zu SiO₂-Übersättigung führend) bis zu stark Leuzit-(oder Kalsilit-)normativ variieren. Die Fraktionierung von wäßrigen SiO₂-untersättigten Schmelzen kann je nach der Rolle des Phlogopits entweder gegen ein SiO₂-übersättigtes Minimum oder gegen ein SiO₂-untersättigtes Minimum tendieren.

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混合气体在水溶液中的溶解度计算模型

该文将段振豪及合作者建立的单气体溶解度模型推广到混合气体系,建立了能够计算CO2-CH4-N2-C2H6-H2S混合气 体在电解质水溶液中溶解度的热力学模型。本模型将DMW92方程扩展到上述多组分混合气体系并使用其计算气体组分的 逸度系数,采用Pitzer活度系数模型描述液相并沿用段振豪及合作者以前确定的纯CO2、CH4、C2H6和H2S的溶解度模型参 数,而纯N2的溶解度模型参数由本研究确定。由于本模型不包含依赖混合气体溶解度实验数据确定的参数,因此对混合气 体溶解度的计算是预测性的。通过与实验数据的对比,证实了本模型能够在宽广的温度、压力范围内准确预测 CO2-CH4-N2-C2H6-H2S混合气体在水溶液中的溶解度（对于CO2和CH4的摩尔百分数超过90%的混合气体,本模型适用于 273~523 K和0~2000×105 Pa的温压范围）。本模型的计算表明,相对于纯CO2气相,少量CH4、N2或H2S的加入会降低CO2的溶解度。对于CO2-H2O-NaCl型流体包裹体,少量CH4的加入会增大流体包裹体的均一压力。相关的计算程序可从通讯作者 处获得。