江达-维西火山岩浆弧中段德钦岩体年代学、地球化学及岩石成因   总被引：6，自引：5，他引：1  

张万平  王立全  王保弟  王冬兵  戴婕  刘伟 《岩石学报》2011,27(9):2577-2590

本文对江达-维西火山岩浆弧德钦岩体的寄主岩石——花岗闪长岩及其镁铁质微粒包体(MME)——闪长岩进行了详细研究。二者LA-ICPMS锆石U-Pb年龄分别为254.6±1.8Ma和253.5±1.6Ma,二者形成时代一致。地球化学研究结果表明,花岗闪长岩富K₂O和Na₂O,且K₂O>Na₂O,富Al₂O₃,A/CNK平均为0.96;闪长岩富K₂O和Na₂O,但K₂O2O,富Al₂O₃和MgO,A/CNK平均为0.72;花岗闪长岩的稀土总量低于闪长岩,二者轻重稀土分馏明显,配分曲线为右倾的轻稀土富集型;二者均富集大离子亲石元素而亏损高场强元素Nb、Ta等;二者均具有相对较高的Mg^#(58.8~65.8),并具有相对较高的相容元素Cr、Ni含量(花岗闪长岩平均值分别为115×10^-6和31.6×10^-6,闪长岩平均值分别为398×10^-6和98.2×10^-6;花岗闪长岩和闪长岩¹⁷⁶Hf/¹⁷⁷Hf的平均值分别为0.282383和0.282287,二者ε_Hf(t)平均值分别为-8.3和-11.8,反映了二者属于I型花岗岩,可能为岩浆混合作用的产物。地球化学特征及Hf同位素组成一致显示岩浆来源于地壳的部分熔融,伴有不同比例的地幔物质加入,形成于弧陆碰撞-后碰撞的构造背景,暗示金沙江结合带在~255Ma已经进入了弧陆碰撞-后碰撞的地质时期。  相似文献   

川南玄武岩气孔中硅铁灰石杏仁体的特征与研究     

张良钜  刘靖娜  曾伟来  李东升  黎琪  曾南石  阮青锋 《岩石矿物学杂志》2014,33(5):917-923

川南普格杏仁状玄武岩气孔中产出硅铁灰石、绿泥石、石英、方解石、沥青等5种不同成分类型的杏仁体。硅铁灰石杏仁体呈圆形或椭圆形,其直径多为5～8 mm,由杏仁体壁至中心,依次分别产出石英→铁镁绿泥石→硅铁灰石。硅铁灰石晶体呈铁黑色、薄板状,由5个平行双面单形组成。微区X射线衍射分析结果显示,硅铁灰石属三斜晶系,空间群为P1 。化学成分分析表明,硅铁灰石氧化物含量(ω_B/%)为SiO₂ 53.55%、CaO 18.84%、Fe₂O₃ 13.65%、FeO 9.68%、MgO 1.44%、H₂O⁺1.74%,FeO/Fe₂O₃=0.71;铁镁绿泥石氧化物含量(ω_B/%)为SiO₂ 33.17%、Al₂O₃ 13.03%、Fe₂O₃ 8.45%、FeO 13.06%、MgO 18.82%、H₂O⁺12.12%、CaO 0.87%,FeO/Fe₂O₃=1.55。硅铁灰石杏仁体的矿物组合变化表明,玄武岩晚期的成矿热液由富Mg、Fe向富Si、Ca演化,硅铁灰石是由偏酸性、弱还原环境向偏碱性、弱氧化环境转化时所形成的过渡性产物。  相似文献   

磁异常矢量倾角法及Z_a/T_a²、H_a/T_a²比值法     

管志宁 《物探与化探》1979,3(6):8-16,39

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。  相似文献   

北秦岭太白山晚中生代正长花岗岩成因及其地质意义   总被引：1，自引：1，他引：0  

张志华  赖绍聪  秦江锋 《岩石学报》2014,30(11):3242-3254

本文对北秦岭中段太白岩体北部正长花岗岩进行了系统研究.结果表明,岩石为高钾钙碱性I型花岗岩,SiO₂=68.49%~72.84%,富Al₂O₃(14.13%~16.48%),相对富K₂O,K₂O/Na₂O=0.45~1.57(多数样品大于1),A/CNK=0.97~1.05,属于准铝质-铝质系列.岩石富集大离子亲石元素(LILE),亏损高场强元素(HFSE),具弱负Eu 异常(δEu=0.58~0.89),高Sr、低Yb/Y.正长花岗岩锶同位素初始比值I_Sr=0.7053~0.7112,ε_Nd(t)=-18.6~-0.1(平均为-9.2),二阶段模式年龄t_2DM值为0.83~2.11Ga,变化较大,显示其源区主要为古老的壳源物质.铅同位素比值²⁰⁶Pb/²⁰⁴Pb=17.492~17.524,²⁰⁷Pb/²⁰⁴Pb=15.470~15.485,²⁰⁸Pb/²⁰⁴Pb=37.750~38.097,与南秦岭基底相近.锆石U-Pb年龄为153.17±0.89Ma和151.0±1.4Ma,形成于晚中生代.太白正长花岗岩源于古老地壳物质的部分熔融,并有年轻幔源组分的参与,形成于挤压向伸展转换的深部动力学背景.  相似文献   

藏南洛扎地区淡色花岗岩锆石U-Pb年龄、Hf同位素、地球化学与岩石成因   总被引：3，自引：1，他引：2  

黄春梅  赵志丹  朱弟成  刘栋  黄玉  董铭淳  胡兆初  郑建平 《岩石学报》2013,29(11):3689-3702

洛扎岩体位于高喜马拉雅淡色花岗岩带的东部,锆石U-Pb测年显示其形成年龄为17.7Ma。洛扎岩体的岩性主要为电气石二云母花岗岩和电气石白云母花岗岩,岩石富硅(SiO₂为73%~75%)、富钾(K₂O为3.9%~4.9%),强过铝(Al₂O₃为14.5%~15.5%,A/CNK大于1.1),属于高钾钙碱性系列的强过铝淡色花岗岩。岩石具有明显的轻重稀土分异和Eu负异常(Eu/Eu^*=0.57),强烈富集大离子亲石元素,相对亏损高场强元素。岩石具有高Rb/Sr(>4)、低CaO/Na₂O (0.19~0.26)的特征,指示了其源岩为泥质岩石。(⁸⁷Sr/⁸⁶Sr)_t和ε_Nd(t)值的变化范围分别为0.725802~0.727276和-13.4~-12.9; 锆石的ε_Hf(t)变化范围为-13.9~-7.5,其较大的变化范围暗示了洛扎淡色花岗岩源区具有不均一性。洛扎岩体可能的构造-岩石成因是,藏南拆离系的启动使深部减压,致使变泥质岩中的白云母发生脱水熔融而形成淡色花岗岩岩浆。岩浆通过STDS所形成的构造薄弱带上侵,沿STDS主拆离断层分布。所以洛扎淡色花岗岩形成于STDS启动所引起的地壳伸展、快速隆起背景下,构造减压所导致的变质岩中白云母的脱水熔融。  相似文献   

河北省青龙满族自治县四拨子-六拨子钼铜矿床成矿流体及成矿机制探讨     

李强  孟祥元  武峰  王立生  张志欣  杨富全  刘锋 《岩石学报》2012,28(1):302-318

河北省青龙满族自治县四拨子-六拨子钼铜矿位于燕辽成矿带东部,是近年来发现的中型钼铜矿床。辉钼矿呈细脉状、网脉状、浸染状、薄膜状赋存于长城系石英砂岩及白云岩中的矽卡岩带,钼矿化与硅化关系密切。矿体呈似层状、脉状和透镜状。矿床的形成经历了矽卡岩期和石英-硫化物期,铜和钼矿化主要形成于石英-硫化物期。研究表明,矽卡岩期矿物以发育液体包裹体为特征,石英-硫化物期石英中主要发育液体包裹体、含CO₂两相和三相包裹体。矽卡岩期成矿流体为高-中温(192~497℃)、中-低盐度(5.41%~16.53% NaCleqv)、中-低密度(0.59~0.92g/cm³)的NaCl-H₂O体系。石英-硫化物期成矿流体为中-低温(主要变化于160~330℃)、低盐度(2.07%~15.17% NaCleqv)和中低密度(0.69~1.01g/cm³)的NaCl-H₂O-CO₂ (±CH₄/N₂)型流体。石英的δD_SMOW为-128‰~-80‰,δ¹⁸O_SMOW值为9.6‰~14‰,δ¹⁸O_H2O值为-3.61%~5.30‰,表明成矿流体具有岩浆水混合大气降水的特征。硫化物的δ³⁴S变化于-0.9‰~5.7‰,平均值为2.9‰,表明成矿物质中硫来自深部岩浆。成矿时代为早侏罗世早期,成矿作用与花岗斑岩岩浆期后热液活动有关。  相似文献   

西藏拉萨地块南缘晚白垩世镁铁质岩浆作用的年代学、地球化学及意义   总被引：8，自引：6，他引：2  

管琪  朱弟成  赵志丹  董国臣  莫宣学  刘勇胜  胡兆初  袁洪林 《岩石学报》2011,27(7):2083-2094

镁铁质岩石所反映出的壳幔作用信息可以为地壳增生发生的时间和方式提供可靠的证据。本文报道了南部拉萨地块东段朗县至米林之间晚白垩世镁铁质岩石的岩石学、锆石U-Pb年代学、全岩地球化学以及锆石Hf同位素数据。锆石U-Pb定年结果表明,角闪辉长岩侵位于98~88Ma,高Al₂O₃(17.25%~19.46%),低MgO含量(3.89%~5.07%)及Mg^#(44~50),与高铝玄武岩特征相似,属于中钾钙碱性岩石,富集大离子亲石元素(LILE)、亏损高场强元素(HFSE),铕异常不明显(δEu=0.82~1.06),(⁸⁷Sr/⁸⁶Sr)_i值为0.70427,ε_Nd(t)值为3.0,具有高且正的锆石ε_Hf(t)值(+11.8~+17.2)。这些晚白垩世镁铁质岩石可能是来自俯冲板片的沉积物熔体交代地幔楔物质发生部分熔融并经历一定程度镁铁质矿物分离结晶作用产物。  相似文献   

Thermochemistry of yavapaiite KFe(SO₄)₂: Formation and decomposition     

Ferenc Lázár Forray  Alexandra Navrotsky 《Geochimica et cosmochimica acta》2005,69(8):2133-2140

Yavapaiite, KFe(SO₄)₂, is a rare mineral in nature, but its structure is considered as a reference for many synthetic compounds in the alum supergroup. Several authors mention the formation of yavapaiite by heating potassium jarosite above ca. 400°C. To understand the thermal decomposition of jarosite, thermodynamic data for phases in the K-Fe-S-O-(H) system, including yavapaiite, are needed. A synthetic sample of yavapaiite was characterized in this work by X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), and thermal analysis. Based on X-ray diffraction pattern refinement, the unit cell dimensions for this sample were found to be a = 8.152 ± 0.001 Å, b = 5.151 ± 0.001 Å, c = 7.875 ± 0.001 Å, and β = 94.80°. Thermal decomposition indicates that the final breakdown of the yavapaiite structure takes place at 700°C (first major endothermic peak), but the decomposition starts earlier, around 500°C. The enthalpy of formation from the elements of yavapaiite, KFe(SO₄)₂, ΔH°_f = −2042.8 ± 6.2 kJ/mol, was determined by high-temperature oxide melt solution calorimetry. Using literature data for hematite, corundum, and Fe/Al sulfates, the standard entropy and Gibbs free energy of formation of yavapaiite at 25°C (298 K) were calculated as S°(yavapaiite) = 224.7 ± 2.0 J.mol⁻¹.K⁻¹ and ΔG°_f = −1818.8 ± 6.4 kJ/mol. The equilibrium decomposition curve for the reaction jarosite = yavapaiite + Fe₂O₃ + H₂O has been calculated, at pH₂O = 1 atm, the phase boundary lies at 219 ± 2°C.  相似文献   

Dualite, Na₃₀(Ca,Na,Ce,Sr)₁₂(Na,Mn,Fe,Ti)₆Zr₃Ti₃MnSi₅₁O₁₄₄(OH,H₂O,Cl)₉, a new zircono-titanosilicate with a modular eudialyte-like structure from the Lovozero alkaline Pluton, Kola Peninsula, Russia     

A. P. Khomyakov  G. N. Nechelyustov  R. K. Rastsvetaeva 《Geology of Ore Deposits》2008,50(7):574-582

Dualite has been found at Mount Alluaiv, the Lovozero Pluton, the Kola Peninsula in peralkaline pegmatoid as sporadic, irregularly shaped grains up to 0.3–0.5 mm across. K-Na feldspar, nepheline, sodalite, cancrinite, aegirine, alkaline amphibole, eudialyte, lovozerite, lomonosovite, vuonnemite, lamprophyllite, sphalerite, and villiaumite are associated minerals. Dualite is yellow, transparent or translucent, with conchoidal fracture. The new mineral is brittle, with vitreous luster and white streaks. The Mohs hardness is 5. The measured density is 2.84(3) g/cm₃ (volumetric method); the calculated density is 2.814 g/cm₃. Dualite dissolves and gelates in acid at room temperature. It is nonfluorescent. The new mineral is optically uniaxial and positive; ω = 1.610(1), ɛ = 1.613(1). Dualite is trigonal, space group R3m. The unit cell dimensions are a = 14.153(9), c = 60.72(5) ?, V = 10533(22) ?, Z = 3. The strongest reflections in the X-ray powder pattern [d, ? (I,%)(hkl)] are as follows: 7.11(40)(110), 4.31(50)(0.2.10), 2.964(100)(1.3.10), 2.839(90)(048), 2.159(60)(2.4.10, 0.4.20), 1.770(60)(2.4.22, 4.0.28, 440), 1362(50)(5.5.12, 3.0.42). The chemical composition (electron microprobe, H₂O calculated from X-ray diffraction data) is as follows, wt %: 17.74 Na₂O, 0.08 K₂O, 8.03 CaO, 1.37 SrO, 0.29 BaO, 2.58 MnO, 1.04 FeO, 0.79 La₂O₃, 1.84 C₂O₃, 0.88 Nd₂O₃, 0.20 Al₂O₃, 51.26 SiO₂, 4.40 TiO₂, 5.39 ZrO₂, 1.94 Nb₂O₅, 0.58 Cl, 1.39 H₂O,-O = 0.13 Cl₂; they total is 99.67. The empirical formula calculated on the basis of 106 cations as determined by crystal structure is (Na_29.79Ba_0.1K_0.10)_Σ30(Ca_8.55Na_1.39REE_1.27Sr_0.79)_Σ12 · (Na_3.01Mn_1.35Fe_0.87²⁺Ti_0.77)_Σ6(Zr_2.61Nb_0.39)_Σ3 (Ti_2.52Nb_0.48)_Σ3(Mn_0.82Si_0.18)_Σ1(Si_50.77Al_0.23)_Σ51 O₁₄₄[(OH)_6.54(H₂O)_1.34·Cl_0.98]_Σ8.86). The simplified formula is Na₃₀(Ca,Na,Ce,Sr)₁₂(Na,Mn,Fe,Ti)₆Zr₃Ti₃ MnSi₅₁O₁₄₄ (OH,H₂O,Cl)₉). The name dualite is derived from Latin dualis (dual) alluding to the dual taxonomic membership of this mineral, which is at the same time zirconosilicate and titanosilicate. The crystal structure is characterized by two module types (alluivite-like and eudialyte-like) alternating along a threefold axis with a doubled c period relative to eudialyte and close chemical affinity to rastsvetaevite (Khomyakov et al., 2006a) and labyrynthite (Khomyakov et al., 2006b). According to the authors’ crystal chemical taxonomy of the eudialyte group, the new mineral belongs to one of three subgroups characterized by a 24-layered structural framework. Dualite is a mineral formed during the final stages of peralkaline pegmatite formation. The type material of dualite is deposited at the Fersman Mineralogical Museum, Russian Academy of Sciences, Moscow. Original Russian Text ? A.P. Khomyakov, G.N. Nechelyustov, R.K. Rastsvetaeva, 2007, published in Zapiski Rossiiskogo Mineralogicheskogo Obshchestva, 2007, Pt CXXXVI, No. 4, pp. 68–73. Approved by the Commission on New Minerals and Mineral Names, International Mineralogical Association, July 8, 2005.  相似文献   

Oxyphlogopite K(Mg,Ti,Fe)₃[(Si,Al)₄O₁₀](O,F)₂: A new mineral species of the mica group     

N. V. Chukanov  A. A. Mukhanova  R. K. Rastsvetaeva  D. I. Belakovsky  S. M?ckel  O. V. Karimova  S. N. Britvin  S. V. Krivovichev 《Geology of Ore Deposits》2011,53(7):583-590

Oxyphlogopite is a new mica-group mineral with the idealized formula K(Mg,Ti,Fe)₃[(Si,Al)₄O₁₀](O,F)₂. The holotype material came from a basalt quarry at Mount Rothenberg near Mendig at the Eifel volcanic complex in Rhineland-Palatinate, Germany. The mineral occurs as crystals up to 4 × 4 × 0.2 mm in size encrusting cavity walls in alkali basalt. The associated minerals are nepheline, plagioclase, sanidine, augite, diopside, and magnetite. Its color is dark brown, its streak is brown, and its luster is vitreous. D _meas = 3.06(1) g/cm³ (flotation in heavy liquids), and D _calc = 3.086 g/cm³. The IR spectrun does not contain bands of OH groups. Oxyphlogopite is biaxial (negative); α = 1.625(3), β = 1.668(1), and γ = 1.669(1); and 2V _meas = 16(2)° and 2V _calc = 17°. The dispersion is strong; r < ν. The pleochroism is medium; X > Y > Z (brown to dark brown). The chemical composition is as follows (electron microprobe, mean of 5 point analyses, wt %; the ranges are given in parentheses; the H₂O was determined using the Alimarin method; the Fe²⁺/Fe³⁺ was determined with X-ray emission spectroscopy): Na₂O 0.99 (0.89–1.12), K₂O 7.52 (7.44–7.58), MgO 14.65 (14.48–14.80), CaO 0.27 ((0.17–0.51), FeO 4.73, Fe₂O₃ 7.25 (the range of the total iron in the form of FeO is 11.09–11.38), Al₂O₃ 14.32 (14.06–14.64), Cr₂O₃ 0.60 (0.45–0.69), SiO₂ 34.41 (34.03–34.66), TiO₂ 12.93 (12.69–13.13), F 3.06 (2.59–3.44), H₂O 0.14; O=F₂ −1.29; 99/58 in total. The empirical formula is (K_0.72Na_0.14Ca_0.02)(Mg_1.64Ti_0.73Fe_0.30²⁺ Fe_0.27³⁺Cr_0.04)_Σ2.98(Si_2.59Al_1.27Fe_0.14³⁺ O₁₀) O_1.20F_0.73(OH)_0.07. The crystal structure was refined on a single crystal. Oxyphlogopite is monoclinic with space group C2/m; the unit-cell parameters are as follows: a = 5.3165(1), b = 9.2000(2), c = 10.0602(2) ?, β = 100.354(2)°. The presence of Ti results in the strong distortion of octahedron M(2). The strongest lines of the X-ray powder diffraction pattern [d, ? (I, %) [hkl]] are as follows: 9.91(32) [001], 4.53(11) 110], 3.300(100) [003], 3.090(12) [112], 1.895(21) [005], 1.659(12) [−135], 1.527(16) [−206, 060]. The type specimens of oxyphlogopite are deposited at the Fersman Mineralogical Museum in Moscow, Russia; the registration numbers are 3884/2 (holotype) and 3884/1 (cotype).  相似文献   

Solid-solution aqueous-solution reactions between jarosite (KFe₃(SO₄)₂(OH)₆) and its chromate analog   总被引：1，自引：0，他引：1  

Dirk Baron  Carl D. Palmer 《Geochimica et cosmochimica acta》2002,66(16):2841-2853

  相似文献   

Residence times for protons bound to three oxygen sites in the AlO₄Al₁₂(OH)₂₄(H₂O)₁₂ polyoxocation     

Jacqueline R. Houston  William H. Casey 《Geochimica et cosmochimica acta》2006,70(7):1636-1643

Although, the kinetic reactivity of a mineral surface is determined, in part, by the rates of exchange of surface-bound oxygens and protons with bulk solution, there are no elementary rate data for minerals. However, such kinetic measurements can be made on dissolved polynuclear clusters, and here we report lifetimes for protons bound to three oxygen sites on the AlO₄Al₁₂(OH)₂₄(H₂O)₁₂⁷⁺ (Al₁₃) molecule, which is a model for aluminum-hydroxide solids in water. Proton lifetimes were measured using ¹H NMR at pH ∼ 5 in both aqueous and mixed solvents. The ¹H NMR peak for protons on bound waters (η-H₂O) lies near 8 ppm in a 2.5:1 mixture of H₂O/acetone-d₆ and broadens over the temperature range −20 to −5 °C. Extrapolated to 298 K, the lifetime of a proton on a η-H₂O is τ²⁹⁸ ∼ 0.0002 s, which is surprisingly close to the lifetime of an oxygen in the η-H₂O (∼0.0009 s), but in the same general range as lifetimes for protons on fully protonated monomer ions of trivalent metals (e.g., Al(H₂O)₆³⁺). The lifetime is reduced somewhat by acid addition, indicating that there is a contribution from the partly deprotonated Al₁₃ molecule in addition to the fully protonated Al₁₃ at self-buffered pH conditions. Proton lifetimes on the two distinct sets of hydroxyls bridging two Al(III) (μ₂-OH) differ substantially and are much shorter than the lifetime of an oxygen at these sites. The average lifetimes for hydroxyl protons were measured in a 2:1 mixture of H₂O/dmso-d₆ over the temperature range 3.7-95.2 °C. The lifetime of a hydrogen on one of the μ₂-OH was also measured in D₂O. The τ²⁹⁸ values are ∼0.013 and ∼0.2 s in the H₂O/dmso-d₆ solution and the τ²⁹⁸ value for the μ₂-OH detectable in D₂O is τ²⁹⁸ ∼ 0.013 s. The ¹H NMR peak for the more reactive μ₂-OH broadens slightly with acid addition, indicating a contribution from an exchange pathway that involves a proton or hydronium ion. These data indicate that surface protons on minerals will equilibrate with near-surface waters on the diffusional time scale.  相似文献   

The kinetics of oxygen exchange between the GeO₄Al₁₂(OH)₂₄(OH₂)₁₂(aq) molecule and aqueous solutions     

Alasdair P. LeeBrian L. Phillips  William H. Casey 《Geochimica et cosmochimica acta》2002,66(4):577-587

We report rates of oxygen exchange with bulk solution for an aqueous complex, ^IVGeO₄Al₁₂(OH)₂₄(OH₂)₁₂⁸⁺(aq) (GeAl₁₂), that is similar in structure to both the ^IVAlO₄Al₁₂(OH)₂₄(OH₂)₁₂⁷⁺(aq) (Al₁₃) and ^IVGaO₄Al₁₂(OH)₂₄(OH₂)₁₂⁷⁺(aq) (GaAl₁₂) molecules studied previously. All of these molecules have ε-Keggin-like structures, but in the GeAl₁₂ molecule, occupancy of the central tetrahedral metal site by Ge(IV) results in a molecular charge of +8, rather than +7, as in the Al₁₃ and GaAl₁₂. Rates of exchange between oxygen sites in this molecule and bulk solution were measured over a temperature range of 274.5 to 289.5 K and 2.95 < pH < 4.58 using ¹⁷O-NMR.Apparent rate parameters for exchange of the bound water molecules (η-OH₂) are k_ex²⁹⁸ = 200 (±100) s⁻¹, ΔH^‡ = 46 (±8) kJ · mol⁻¹, and ΔS^‡ = −46 (±24) J · mol⁻¹ K⁻¹ and are similar to those we measured previously for the GaAl₁₂ and Al₁₃ complexes. In contrast to the Al₁₃ and GaAl₁₂ molecules, we observe a small but significant pH dependence on rates of solvolysis that is not yet fully constrained and that indicates a contribution from the partly deprotonated GeAl₁₂ species.The two topologically distinct μ₂-OH sites in the GeAl₁₂ molecule exchange at greatly differing rates. The more labile set of μ₂-OH sites in the GeAl₁₂ molecule exchange at a rate that is faster than can be measured by the ¹⁷O-NMR isotopic-equilibration technique. The second set of μ₂-OH sites have rate parameters of k_ex²⁹⁸ = 6.6 (±0.2) · 10⁻⁴ s⁻¹, ΔH^‡ = 82 (±2) kJ · mol⁻¹, and ΔS^‡ = −29 (±7) J · mol⁻¹ · K⁻¹, corresponding to exchanges ≈40 and ≈1550 times, respectively, more rapid than the less labile μ₂-OH sites in the Al₁₃ and GaAl₁₂ molecules. We find evidence of nearly first-order pH dependence on the rate of exchange of this μ₂-OH site with bulk solution for the GeAl₁₂ molecule, which contrasts with Al₁₃ and GaAl₁₂ molecules.  相似文献   

Synthesis, characterization, and thermochemistry of K-Na-H₃O jarosites     

Christophe Drouet 《Geochimica et cosmochimica acta》2003,67(11):2063-2076

The thermochemistry of well-characterized synthetic K-H₃O, Na-H₃O and K-Na-H₃O jarosites was investigated. These phases are solid solutions that obey Vegard’s law. Electron probe microanalyses indicated lower alkali and iron contents than predicted from the theoretical end-member compositions, in agreement with thermal analyses, suggesting the presence of hydronium and “additional” water. The standard enthalpies of formation (ΔH°_f) of K-H₃O, Na-H₃O and K-Na-H₃O jarosites were determined by high-temperature oxide melt solution calorimetry. These enthalpies vary linearly with the K/H₃O, Na/H₃O and K/Na ratio, respectively. The enthalpy of formation of pure hydronium jarosite was also determined experimentally (ΔH°_f = −3741.6 ± 8.3 kJ.mol⁻¹), and it was used to evaluate ΔH°_f for the end-members KFe₃(SO₄)₂(OH)₆ (ΔH°_f = −3829.6 ± 8.3 kJ.mol⁻¹) and NaFe₃(SO₄)₂(OH)₆ (ΔH°_f = −3783.4 ± 8.3 kJ.mol⁻¹). Finally, enthalpies of dehydration (loss of the “additional” water) of some jarosites were determined and found to be near the enthalpy of vaporization of water, suggesting that the “additional” water is weakly bonded in the structure.  相似文献   

Dissolution of jarosite [KFe₃(SO₄)₂(OH)₆] at pH 2 and 8: Insights from batch experiments and computational modelling   总被引：1，自引：0，他引：1  

Adrian M.L. Smith  Karen A. Hudson-Edwards  William E. Dubbin 《Geochimica et cosmochimica acta》2006,70(3):608-621

Jarosite [KFe₃(SO₄)₂(OH)₆] is a mineral that is common in acidic, sulphate-rich environments, such as acid sulphate soils derived from pyrite-bearing sediments, weathering zones of sulphide ore deposits and acid mine or acid rock drainage (ARD/AMD) sites. The structure of jarosite is based on linear tetrahedral-octahedral-tetrahedral (T-O-T) sheets, made up from slightly distorted FeO₆ octahedra and SO₄ tetrahedra. Batch dissolution experiments carried out on synthetic jarosite at pH 2, to mimic environments affected by ARD/AMD, and at pH 8, to simulate ARD/AMD environments recently remediated with slaked lime (Ca(OH)₂), suggest first order dissolution kinetics. Both dissolution reactions are incongruent, as revealed by non-ideal dissolution of the parent solids and, in the case of the pH 8 dissolution, because a secondary goethite precipitate forms on the surface of the dissolving jarosite grains. The pH 2 dissolution yields only aqueous K, Fe, and SO₄. Aqueous, residual solid, and computational modelling of the jarosite structure and surfaces using the GULP and MARVIN codes, respectively, show for the first time that there is selective dissolution of the A- and T-sites, which contain K and SO₄, respectively, relative to Fe, which is located deep within the T-O-T jarosite structure. These results have implications for the chemistry of ARD/AMD waters, and for understanding reaction pathways of ARD/AMD mineral dissolution.  相似文献   

Density functional theory study and kinetic analysis of the formation mechanism of Al₃₀O₈(OH)₅₆(H₂O)₂₆ (Al₃₀) in aqueous solution     

Wenjing Yang 《Geochimica et cosmochimica acta》2010,74(4):1220-1032

The formation mechanism of Al₃₀O₈(OH)₅₆(H₂O)₂₆¹⁸⁺ (Al₃₀) has been investigated by the density functional theory based on the supermolecule model and kinetic analysis on the ²⁷Al nuclear magnetic resonance (NMR) experimental results in monitoring Al₃₀ synthesis process. The theoretical chemistry calculations on the four possible schemes show that δ-Na-Al₁₃ is the reasonable intermediate followed by the substitution of Na with Al to form δ-Al₁₄, and Na⁺ plays an important role in stabilizing the intermediate (δ-Na-Al₁₃) in the transformation. The kinetic analysis on the ²⁷Al NMR experimental data indicates that ε-Al₁₃ decomposes and isomerizes in the formation of Al₃₀, while Al monomers facilitate the decomposition of ε-Al₁₃ and so the isomerization of ε-isomers to δ-isomers effectively. The favorable formation mechanism of Al₃₀ includes three steps: (1) ε-Al₁₃ decomposes and rearranges into the isomer δ-Al₁₃; (2) Na⁺ reacts with δ-Al₁₃ to stabilize the intermediate δ-Na-Al₁₃, followed by Al monomers replacing Na to form δ-Al₁₄; (3) δ-Al₁₄ reacts with the Al monomers in the solution to finally form Al₃₀. Both Al monomers and Na⁺ are important in the transformation. Al monomers are the basic building units and helpful to the isomerization while Na⁺ can well stabilize the isomer δ-Al₁₃ to yield intermediate δ-Na-Al₁₃. The results also show that other isomers of ε-Al₁₃ (β-Al₁₃ and α-Al₁₃) form in the formation of Al₃₀, and their calculated ²⁷Al NMR tetrahedral resonance shifts are consistent with the experimental ²⁷Al NMR tetrahedral signals in the preparation process of Al₃₀.  相似文献   

Free energy of formation for green rust sodium sulphate (NaFe₆Fe₃(OH)₁₈(SO₄)_2(s))     

E. Davesne  K. Dideriksen  B.C. Christiansen  K.B. Ayala-Luis  H.C.B. Hansen 《Geochimica et cosmochimica acta》2010,74(22):6451-6467

In a recent study, sulphate-bearing green rust (GR_SO4) was shown to incorporate Na⁺ in its structure (NaFe^II₆Fe^III₃(OH)₁₈(SO₄)_2(s); GR_Na,SO4). The compound was synthesised by aerial oxidation of Fe(OH)_2(s) in the presence of NaOH. This paper reports on its free energy of formation .Freshly synthesised GR_Na,SO4 was titrated with 0.5 M H₂SO₄ in an inert atmosphere at 25 °C, producing dissolved Fe²⁺ and magnetite or goethite. Solution concentrations, PHREEQC and the MINTEQ database were used to calculate reaction constants for the reactions: