Oxidative dissolution of pyritic sludge from the Aznalcóllar mine (SW Spain)

As a result of the collapse of a mine tailing dam, a large extension of the Guadiamar valley was covered with a layer of pyritic sludge. Despite the removal of most of the sludge, a small amount remained in the soil, constituting a potential risk of water contamination. The kinetics of the sludge oxidation was studied by means of laboratory flow-through experiments at different pH and oxygen pressures. The sludge is composed mainly of pyrite (76%), together with quartz, gypsum, clays, and sulphides of zinc, copper, and lead. Trace elements, such as arsenic and cadmium, also constitute a potential source of pollution. The sludge is fine grained (median of 12 μm) and exhibits a large surface (BET area of 1.4±0.2 m² g⁻¹).

The dissolution rate law of sludge obtained is r=10^{−6.1(±0.3)} [O₂(aq)]^0.41(±0.04) a_H+^0.09(±0.06) g_sludge m⁻² s⁻¹ (22 °C, pH=2.5–4.7). The dissolution rate law of pyrite obtained is r=10^{−7.8(±0.3)} [O₂(aq)]^0.50(±0.04) a_H+^0.10(±0.08) mol m⁻² s⁻¹ (22 °C, pH=2.5–4.7). Under the same experimental conditions, sphalerite dissolved faster than pyrite but chalcopyrite dissolves at a rate similar to that of pyrite. No clear dependence on pH or oxygen pressure was observed. Only galena dissolution seemed to be promoted by proton activity. Arsenic and antimony were released consistently with sulphate, except at low pH conditions under which they were released faster, suggesting that additional sources other than pyrite such as arsenopyrite could be present in the sludge. Cobalt dissolved congruently with pyrite, but Tl and Cd seemed to be related to galena and sphalerite, respectively.

A mechanism for pyrite dissolution where the rate-limiting step is the surface oxidation of sulphide to sulphate after the adsorption of O₂ onto pyrite surface is proposed.     

Formation of Al-rich titanite (CaTiSiO4O–CaAlSiO4OH) reaction rims on ilmenite in metamorphic rocks as a function of fH2O and fO2

Reaction rims of titanite on ilmenite are described in samples from four terranes of amphibolite-facies metapelites and amphibolites namely the Tamil Nadu area, southern India; the Val Strona area of the Ivrea-Verbano Zone, northern Italy, the Bamble Sector, southern Norway, and the northwestern Austroalpine Ötztal Complex. The titanite rims, and hence the stability of titanite (CaTiSiO₄O) and Al–OH titanite, i.e. vuaganatite (hypothetical end-member CaAlSiO₄OH), are discussed in the light of fH₂O- and fO₂-buffered equilibria involving clinopyroxene, amphibole, biotite, ilmenite, magnetite, and quartz in the systems CaO–FeO/Fe₂O₃–TiO₂–SiO₂–H₂O–O₂ (CFTSH) and CaO–FeO/Fe₂O₃–Al₂O₃–SiO₂–H₂O–O₂ (CFASH) present in each of the examples. Textural evidence suggests that titanite reaction rims on ilmenite in rocks from Tamil Nadu, Val Strona, and the Bamble Sector originated most likely due to hydration reactions such as clinopyroxene + ilmenite + quartz + H₂O = amphibole + titanite and oxidation reactions such as amphibole + ilmenite + O₂ = titanite + magnetite + quartz + H₂O during amphibolite-facies metamorphism, or, as in the case of the Ötztal Complex, during a subsequent greenschist-facies overprint. Overstepping of these reactions requires fH₂O and fO₂ to be high for titanite formation, which is also in accordance with equilibria involving Al–OH titanite. This study shows that, in addition to P, T, bulk–rock composition and composition of the coexisting fluid, fO₂ and fH₂O also play an important role in the formation of Al-bearing titanite during amphibolite- and greenschist-facies metamorphism.     

Experimental abiotic synthesis of methanol in seafloor hydrothermal systems during diking events

The abiotic synthesis of organic compounds in seafloor hydrothermal systems is one mechanism through which the subsurface environment could be supplied with reduced carbon. A flow-through, fixed-bed laboratory reactor vessel, the Catalytic Reactor Vessel (CRV) system, has been developed to investigate mineral–surface promoted organic synthesis at temperatures up to 400°C and pressures up to 30 MPa, conditions relevant to seafloor hydrothermal systems. Here we present evidence that metastable methanol can be directly synthesized from a gas-rich CO₂–H₂–H₂O mixture in the presence of a mineral substrate. Experiments have been performed without a substrate, with quartz, and with a mixture of quartz and magnetite. Temperatures and pressures in the experiments ranged from 200°C to 350°C and from 15 to 18 MPa, respectively. Maximum conversion of 5.8×10⁻⁴% CO₂ to CH₃OH per hour was measured using a mixture of magnetite and quartz in the reactor. After passivation of the stainless steel reactor vessel, experiments demonstrate that methanol is formed at temperatures up to 350°C in the presence of magnetite, and that the formation rate decreases over time. The experiments also show a loss of surface reactivity at 310°C and a regeneration of surface reactivity with increased temperature up to 350°C. Concentrations of CO₂ and H₂ used in the experiments simulate periodic, localized and dynamic conditions occurring within the seafloor during and immediately following magmatic diking events. High concentrations of CO₂ and H₂ may be generated by dike injection accompanied by exsolution of CO₂ and reaction of dissolved H₂O with FeO in the magma to form H₂. The experiments described here examine how the ephemeral formation of an H₂–CO₂-rich vapor phase within seafloor hydrothermal systems may supply reactants for abiotic organic synthesis reactions. These experiments show that the presence of specific minerals can promote the abiotic synthesis of simple organic molecules from common inorganic reactants such H₂O, CO₂ and H₂ under geologically realistic conditions.     

Comprehensive chemical analyses of natural cordierites: implications for exchange mechanisms

Cordierite samples from pegmatites and metamorphic rocks have been analysed for major [electron microprobe analysis (EMPA)] and trace elements [inductively coupled plasma mass spectrometry (ICP-MS), secondary ion mass spectrometry analyses (SIMS)] as well as for H₂O and CO₂ (coulometric titration), and the results evaluated in conjunction with published data in order to determine which exchange mechanisms are significant. Apart from the homovalent substitutions FeMg₋₁ and MnMg₋₁ on the octahedral site, some minor KNa₋₁ on the Ch0 channel site, and Fe³⁺Al₋₁ on the T₁1 tetrahedral site, the three most important substitution mechanisms are those for the incorporation of Li on the octahedral sites (NaLi□₋₁Mg₋₁), and of Be and other divalent cations on the tetrahedral T₁1 site (NaBe□₋₁Al₋₁ and Na(Mg,Fe²⁺)□₋₁Al₋₁). The dominant role of the last vector is clearly demonstrated. We propose a new generalized formula for cordierite: ^Ch(Na,K)_0–1 ^VI(Mg,Fe²⁺,Mn,Li)₂ ^IVSi₅ ^IVAl₃ ^IV(Al, Be, Mg, Fe²⁺, Fe³⁺)O₁₈ *x^Ch(H₂O, CO₂…). Our results show that the population of (Mg, Fe²⁺) on the T₁1-site is limited to about 0.08 a.p.f.u. Other exchange mechanisms that were encountered in experiments operate only under P–T conditions or in bulk compositions that are rarely realized in nature. Routine analyses by electron microprobe in which Li and Be are not determined can be plotted as (Mg+Fe+Mn) versus (Si+Al) to assess whether significant amounts of Li and Be could be present. These amounts can be calculated as Li (a.p.f.u.)=Al+Na–4 and Be (a.p.f.u.)=10–2Al–M²⁺–Na.     

俄罗斯极地乌拉尔硬玉岩成因矿物学研究

俯冲带是壳-幔物质循环的重要场所,硬玉岩可以记录这一循环过程。文中总结了俄罗斯极地乌拉尔硬玉岩的研究进展。硬玉岩呈脉状或透镜状产在蛇纹石化的方辉橄榄岩中,主要由硬玉和绿辉石组成。根据结构和颜色,硬玉可识别出两个世代。硬玉韵律环带发育,含有H₂O和CH₄流体包裹体,显示从流体中结晶的特征。硬玉岩中的锆石为热液锆石,锆石稀土元素中La_N/Yb_N=0.001~0.01,Lu_N/Gd_N=10~83,Ce/Ce^*=2.8~72,显示正异常,δEu=0.53~1.02,类似于岩浆锆石。锆石的¹⁷⁶Hf/¹⁷⁷Hf=0.282 708~0.283 017,ε_Hf(t)=+6~+17,类似于N-MORB的Hf同位素组成,锆石δ¹⁸O组成为5.03‰~6.04‰,平均δ¹⁸O为(5.45±0.11)‰,类似于岩浆热液和地幔的氧同位素组成。这可能反映了锆石是被俯冲带流体从途经火成岩中捕获的或者形成锆石的流体与寄主岩(方辉橄榄岩)达到了平衡。硬玉岩稀土元素配分模式近平坦或轻稀土元素略显富集,La_N/Yb_N比值为0.82~2.42,δEu为1.2~1.6,显示正异常,这与寄主岩稀土元素配分模式相似。富集Sr、Ba、Zr、Hf,Nb为负异常,与岛弧岩浆特征类似。(⁸⁷Sr/⁸⁶Sr)_t为0.703 400~0.703 519(t=368 Ma),变化较小,与古海水差别明显;ε_Nd(t)值为+0.77~+5.61,变化较大,与寄主岩(方辉橄榄岩)的Nd同位素组成类似,但不同于海水及沉积物的Nd同位素组成,表明硬玉岩的物质来源与寄主岩有明显继承关系,海水与沉积物的贡献不是主要的。矿物学和岩石学证据支持极地乌拉尔的硬玉岩主要是俯冲带流体与橄榄岩相互作用后并在其中结晶的产物。     

Status report on stability of K-rich phases at mantle conditions

Experimental research on K-rich phases and observations from diamond inclusions, UHP metamorphic rocks, and xenoliths provide insights about the hosts for potassium at mantle conditions. K-rich clinopyroxene (Kcpx–KM³⁺Si₂O₆) can be an important component in clinopyroxenes at P>4 GPa, dependent upon coexisting K-bearing phases (solid or liquid) but not, apparently, upon temperature. Maximum Kcpx content can reach 25 mol%, with 17 mol% the highest reported in nature. Partitioning ^(K)D_(cpx/liquid) above 7 GPa=0.1–0.2 require ultrapotassic liquids to form highly potassic cpx or critical solid reactions, e.g., between Kspar and Di. Phlogopite can be stable to about 8 GPa at 1250 °C where either amphibole or liquid forms. When fluorine is present, it generally increases in Phl upon increasing P (and probably T) to about 6 GPa, but reactions forming amphibole and/or KMgF₃ limit F content between 6 and 8 GPa. The perovskite KMgF₃ is stable up to 10 GPa and 1400 °C as subsolidus breakdown products of phlogopite upon increasing P. ^(M4)K-substituted potassic richterite (ideally K(KCa)Mg₅Si₈O₂₂(OH,F)₂) is produced in K-rich peridotites above 6 GPa and in Di+Phl from 6 to 13 GPa. K content of amphibole is positively correlated with P; Al and F content decrease with P. In the system 1Kspar+1H₂O K-cymrite (hydrous hexasanidine–KAlSi₃O₈·nH₂O–Kcym) is stable from 2.5 GPa at 400 to 1200 °C and 9 GPa; Kcym can be a supersolidus phase. Formation of Kcym is sensitive to water content, not forming within experiments with H₂O2O>Kspar. Phase X, a potassium di-magnesium acid disilicate ((K_1−x−n)₂(Mg_1−nM_n³⁺)₂Si₂O₇H_2x), forms in mafic compositions at T=1150–1400 °C and P=9–17 GPa and is a potential host for K and H₂O at mantle conditions with a low-T geotherm or in subducting slabs. The composition of phase-X is not fixed but actually represents a solid solution in the stoichiometries □₂Mg₂Si₂O₇H₂–(K□)Mg₂Si₂O₇H–K₂Mg₂Si₂O₇ (□=vacancy), apparently stable only near the central composition. K-hollandite, KAlSi₃O₈, is possibly the most important K-rich phase at very high pressure, as it appears to be stable to conditions near the core–mantle boundary, 95 GPa and 2300 °C. Other K-rich phases are considered.     

Thermodynamic modelling of C–O–H fluids

H₂O, CO₂, CH₄, CO, H₂ and O₂ are the most important species in crustal fluids. The composition of these C–O–H fluids can be calculated if the pressure, temperature, carbon activity, and either the oxygen fugacity or the atomic H/O ratio of the fluid is known. The calculation methods are discussed and calculation results are illustrated with isobaric T–X_i, P–T, and isobaric–isothermal ternary C–O–H diagrams. Fluid inclusion compositions, in particular, the X_CO2/(X_CO2+X_CH4) ratio, can be used for C–O–H model calculations. However, care should be taken about possible post-entrapment changes, which may have modified the chemical composition of the fluid inclusion.     

An experimental study of calcite dissolution rates at acidic conditions and 25 °C in the presence of NaPO3 and MgCl2

Dissolution rates of single calcite crystals were determined from sample weight loss using free-drift rotating disk techniques. Experiments were performed at 25 °C in aqueous HCl solutions over the bulk solution pH range −1 to 3 and in the presence of trace concentrations of aqueous NaPO₃ and MgCl₂. These salts were chosen for this study because aqueous magnesium and phosphate are known to strongly inhibit calcite dissolution at neutral to basic pH. Reactive solutions were undersaturated with respect to possible secondary phases. Neither an inhibition or enhancement of calcite dissolution rates was observed in the presence of aqueous MgCl₂ at pH 1 and 3. The presence of trace quantities of NaPO₃, which dissociates in solution to Na⁺ and H₂PO₄⁻, decreased the overall calcite dissolution rate at pH≤2. This contrasting behavior could be attributed to the different adsorption behavior of these dissolved species. As calcite surfaces are positively charged in acidic solutions, aqueous Mg²⁺ may not adsorb, whereas aqueous phosphate, present as either the anion H₂PO₄⁻ or the neutral species H₃PO₄⁰, readily adsorbs on calcite surfaces leading to significant dissolution inhibition.     

广西渐新世宁明组三种植物碳同位素与古气候分析

渐新世代表地球一个早期的“冰室”期,是地球气候演化和生物演替过程中一段特殊的时期。渐新世植物化石的碳同位素可为研究该时期的古气候提供依据。对广西渐新世宁明组三种植物及其最近现生亲缘种的碳同位素进行分析,化石种Buxus ningmingensis,Chuniophoenix slenderifolia和Cephalotaxus ningmingensis的碳同位素组成（δ13C）分别为-29.0‰,-28.3‰,-28.0‰;碳同位素分馏（Δ13C）分别为23.48‰,22.74‰,22.43‰;叶内细胞间和外界大气的CO₂分压比（C_植物/C_空气）分别为0.84,0.81,0.80;水分利用效率（WUE）分别为42.63μmol CO₂/mol H₂O,51.56μmol CO₂/mol H₂O,55.38 μmol CO₂/mol H₂O。其对应的最近现生亲缘种（NLRs）的δ13C分别为-27.9‰,-29.7‰,-28.8‰;Δ13C分别为20.47‰,22.36‰,21.42‰;C_植物/C_空气分别为0.71,0.79,0.75;WUE分别为72.22 μmol CO₂/mol H₂O,51.28μmol CO₂/mol H₂O,61.76 μmol CO₂/mol H₂O。化石种δ13C值均落在现代C₃植物相应的数值范围内,其Δ13C和C_植物/C_空气均高于相应的NLRs数值;而Buxus ningmingensis和Cephalotaxus ningmingensis的WUE低于相应的NLRs数值;其中Chuniophoenix slenderifolia的WUE稍高于相应的最近现生亲缘种C. hainanensis,推测可能与其NLR标本的母本植物生长在水源充足、空气潮湿的湖溪边湿地环境有关。基于Δ13C、C_植物/C_空气和WUE结果,推测化石种可能生活在一种比现在更为温暖湿润的气候环境中;化石种及同层位化石的古气候重建支持了当前古气候分析结果。     

青海双朋西金铜矿床的成矿流体特征及流体来源

通过对双朋西金铜矿床流体包裹体岩相学、测温学及铅、硫同位素等的分析,研究其成矿流体性质和演化,并探讨矿床成矿流体来源,结果表明:①流体包裹体主要为气液两相包裹体;包裹体液相成分阳离子以Na+、K+、Ca2+为主,阴离子主要以SO2-4、Cl-为主;气相以H,2O、CO2为主.②双朋西金铜矿床成矿流体为中高温、中等盐度、中等密度、中等压力的流体.③铅同位素206Pb/204Pb为18.058～18.710,207Pb/204Pb为15.581～15.641,208Pb/204Ph为38.191～38.531;δ34S值(‰)变化范围为+3.1～+6.2,平均值为+4.42;综合分析认为,本区铅、硫同位素来源应为壳幔混合源.     

基于DFT方法的注热蒸汽开采CH4吸附机理

为探究不同煤阶煤吸附CH₄和H₂O吸附机理,采用量子化学方法中的密度泛函理论（DFT）,在B3LYP/6-31G基组上计算了不同煤阶煤的大分子稳定构型及煤分别吸附CH₄、H₂O及CH₄与H₂O共存条件下的吸附能和电荷转移情况。研究结果表明:煤吸附CH₄为物理吸附,随着煤阶升高,煤吸附CH₄能力增强;吸附H₂O时以氢键形式作用,其中煤中含氧官能团为氢键供体,H₂O中-OH为氢键受体,随着煤阶升高,吸附H₂O能力减弱;当H₂O与CH₄共存时,H₂O抢占CH₄吸附位,导致煤优先吸附H₂O,使吸附态CH₄减少,游离态CH₄增多。从分子水平完善了煤吸附甲烷和H₂O的吸附机理,为注热蒸汽开发煤层气奠定了吸附理论基础。      

Seepage and consolidation of bentonite saturated with pure- or salt-water by the method of unified molecular dynamics and homogenization analysis

Bentonite clay is a micro-inhomogeneous material, which consists of clay minerals (mainly montmorillonite), macro-grains (mainly quartz), water, air and others. Properties of the saturated bentonite clay are essentially characterized by the montmorillonite and water (i.e. montmorillonite hydrate). We analyze the molecular behavior of sodium montmorillonite hydrate Na_1/3Al₂[Si_11/3Al_1/3]O₁₀(OH)₂·nH₂O by applying a molecular dynamics (MD) simulation method. And by using the MD results we calculate the swelling property of the montmorillonite hydrate, and compare with an experimental result. Next, by using the same MD procedure we treat a montmorillonite mineral with a large number of external water molecules to check the properties of the water. Here we treat pure- and salt-water. Then we calculate the diffusivity and viscosity of water molecules and Na⁺ and Cl⁻ ions.

For extending the microscopic characteristics of constituent materials to a macroscopic seepage behavior of the micro-inhomogeneous material we apply a homogenization analysis (HA). That is, starting with the Navier–Stokes equation with distributed viscosity that is calculated by the former MD procedure we determine macroscopic permeability characteristics of bentonite for both cases of pure- and salt-water. Then, by using the permeability property we calculate long-term consolidation behavior of buffering clay, which is planed to be used for high-level radioactive waste (HLRW) management. Here the deformation is treated under the well-defined Cam clay model.     

内蒙古乌拉山地区沙德盖岩体年代学、地球化学特征及成因探讨

沙德盖岩体位于华北克拉通北缘中段、哈达门沟大型金（钼）矿田范围内。首次利用锆石 SHRIMP U-Pb法对其定年,获得15个锆石颗粒²⁰⁶Pb/²³⁸U年龄的加权平均值（221.6±2.1） Ma（MSWD=1.6）,表明岩体侵位于印支中期。岩石地球化学特征表现为高硅（SiO₂质量分数为71.21%～73.67%）、富钾（K₂O/Na₂O为1.01～1.37）、富碱（K₂O+Na₂O为8.23%～9.96%）、弱过铝质（Al₂O₃为13.11%～14.31%）,里特曼指数σ=2.43～3.52,钙碱性-碱性;富集轻稀土（LREE/HREE为17.68～14.92,（La/Yb）|_N为22.85～16.58）和Eu略亏损（δEu=0.95～0.93）;微量元素亏损Nb、Ta、P、Ti、Sr,富集K、La、Ce、Hf等元素,具有A型花岗岩特征;(⁸⁷Sr/⁸⁶Sr)i=0.705 31～0.702 29,(¹⁴³Nd/¹⁴⁴Nd)_i=0.511 682～0.511 620,ε_Nd(t)=-13.1～-14.3,具有壳源特点;钕两阶段模式年龄T_2DM=2 061～2 160 Ma,在铅构造模式图上样品投点于地幔与下地壳之间。综合分析认为其形成于同碰撞向后碰撞构造体制转换,伸展构造和幔源基性岩浆的底侵导致早期古老基底地壳部分熔融,很可能是形成沙德盖岩体的主要动力机制。华北克拉通北缘印支期构造岩浆活动及成矿作用是普遍存在的。     

Marcasite precipitation from hydrothermal solutions

Pyrite and marcasite were precipitated by both slow addition of aqueous Fe²⁺ and SiO₃²⁻ to an H₂S solution and by mixing aqueous Fe²⁺ and Na₂S₄ solutions at 75°C. H₂S₂ or HS₂⁻ and H₂S₄ or HS₄⁻ were formed in the S₂O₃²⁻ and Na₂S₄ experiments, respectively. Marcasite formed at pH < pK₁ of the polysulfide species present (for H₂S₂, pK₁ = 5.0; for H₂S₄, pK₁ = 3.8 at 25°C). Marcasite forms when the neutral sulfane is the dominant polysulfide, whereas pyrite forms when mono-or divalent polysulfides are dominant. In natural solutions where H₂S₂ and HS₂ are likely to be the dominant polysulfides, marcasite will form only below pH 5 at all temperatures.

The pH-dependent precipitation of pyrite and marcasite may be caused by electrostatic interactions between polysulfide species and pyrite or marcasite growth surfaces: the protonated ends of H₂S₂ and HS₂ are repelled from pyrite growth sites but not from marcasite growth sites. The negative ions HS₂ and S₂²⁻ are strongly attracted to the positive pyrite growth sites. Masking of 1π_g^* electrons in the S₂ group by the protons makes HS₂ and H₂S₂ isoelectronic with AsS²⁻ and As₂²⁻, respectively ( et al., 1981). Thus, the loellingitederivative structure (marcasite) results when both ends of the polysulfide are protonated.

Marcasite occurs abundantly only for conditions below pH 5 and where H₂S₂ was formed near the site of deposition by either partial oxidation of aqueous H₂S by O₂ or by the reaction of higher oxidation state sulfur species that are reactive with H₂S at the conditions of formation e.g., S₂O₃²⁻ but not SO₄²⁻. The temperature of formation of natural marcasite may be as high as 240°C ( and , 1985), but preservation on a multimillion-year scale seems to require post-depositional temperatures of below about 160°C ( , 1973; and , 1985).     

Pyrolyse de complexes organo-métalliques formés entre un matériau organique actuel d''origine algaire et divers cations métalliques divalents (UO2, Cu, Pb, Ni, Mn, Zn et Co

The thermal decomposition of complexes formed by reactions of various divalent cations (UO₂²⁺, Cu²⁺, Pb²⁺, Ni²⁺, Mn²⁺, Zn²⁺ and Co²⁺) with a Recent sedimentary organic matter of algal origin has been studied by thermogravimetric analyses carried out under an inert atmosphere. Results of these experiments show that metals fixed by the organic matter delay the beginning of the decomposition of that latter one. The importance of this retardating effect depends on: (1) the nature of the metal (Mn > Pb > Ni > Co > Zn > U > Cu > pure organic matter); and, to a lesser degree, (2) its content in the tested complex.

Chromatographic analyses of gases (H₂O, CO₂, light hydrocarbons) produced during the experiments show that carbon dioxide is the main decomposition product of the complexes. As a matter of fact, carbon dioxide is formed all along the thermal decomposition of the organic matter. For the uranium-containing complex, a sudden emission of CO₂ may be related to the reduction of this metal which passes from oxidation state VI to IV during the pyrolysis.

These observations support the hypothesis that metals associated with sedimentary organic complexes may affect their diagenetic evolution.

Résumé

La décomposition thermique de composés formés par réaction de différents cations divalents (UO²⁺₂, Cu²⁺, Pb²⁺, Ni²⁺, Mn²⁺, Zn²⁺, Co²⁺) avec une matière sédimentaire actuelle d'origine algaire a été suivie par analyse thermogravimétrique, en opérant à atmosphère inerte. les résultats de ces expériences montrent que les métaux associés à la matière organique retardent le début de la décomposition de celle-ci. Cet effect retardateur dépend: (1) de la nature du métal étudié (Mn > Pb > Ni > Co > Zn > U > Cu); et dans une moindre mesure, (2) de la teneur de celui-ci dans le produit considéré.

L'analyse chromatographique des principaux composés gazeux (CO₂, H₂O, hydrocarbures légers) émis durant les expériences, montre que l'anhydride carbonique est un produit majeur de la décomposition des échantillons étudiés. En effet, contrairement aux autres composés analysés, le CO₂ est émis durant toute la durée de la pyrolyse de la matière organique. Les courbes d'émission du CO₂ obtenues à partir des complexes contenant de l'U montrent un dégagement soudain de CO₂ qui est peut-être à relier à la réduction du métal qui passe de l'état d'oxydation VI à IV au cours de la pyrolyse.

Ces observations appuient l'hypothèse selon laquelle des métaux associés à des matériaux organiques sédimentaires pourraient influer sur les transformations subies par ceux-ci au cours de leur évolution diagénétique.     

Antimony in hydrothermal processes: solubility, conditions of transfer, and metal-bearing capacity of solutions

Based on data on the composition of ore-bearing hydrothermal solutions and parameters of ore-forming processes at various antimony and antimony-bearing deposits, which were obtained in studies of fluid inclusions in ore minerals, we investigated the behavior of Sb(III) in the system Sb–Cl–H₂S–H₂O describing the formation of these deposits.

We also performed thermodynamic modeling of native-antimony and stibnite dissolution in sulfide (m_HS⁻ = 0.0001−0.1) and chloride (m_Cl⁻ = 0.1−5) solutions and the joint dissolution of Sb_(s)⁰ and Sb₂S_3(s) in sulfide-chloride solution (m_HS⁻ = 0.01; m_Cl⁻ = 1) depending on Eh, pH, and temperature. All thermodynamic calculations were carried out using the Chiller computer program. Under the above conditions, stibnite precipitates in acid, weakly acid to neutral, and medium redox solutions, whereas native antimony precipitates before stibnite under more reducing conditions in neutral to alkaline solutions.

The metal-bearing capacity of hydrothermal solutions (200–250 °C) of different compositions and origins has been predicted. We have established that the highest capacity is specific for acid (pH = 2–3) high-chloride solutions poor in sulfide sulfur and alkaline (pH = 7–8) low-chloride low-sulfide solutions.     

The nature of the sub-continental mantle: constraints from the major-element composition of continental flood basalts

Many continental flood basalts (CFB) have isotope and trace-element signatures that differ from those of oceanic basalts and much interest concerns the extent to which these reflect differences in their upper mantle source regions. A review of selected data sets from the Mesozoic and Tertiary CFB confirms significant differences in their major- and trace-element compositions compared with those of basalts erupted through oceanic lithosphere. In general, those CFB suites characterised by low Nb/La, high (⁸⁷Sr/⁸⁶Sr)_i and low εNd_i tend to exhibit relatively low TiO₂, CaO/Al₂O₃, Na₂O and/or Fe₂O₃, and relatively high SiO₂. In contrast, those which have high Nb/La, low (⁸⁷Sr/⁸⁶Sr)_i and high εNd_i ratios, like the upper units in the Deccan Traps, have major- and trace-element compositions similar to oceanic basalts. It would appear that those CFB that have distinctive isotope and trace-element ratios also exhibit distinctive major-element contents, suggesting that major and trace elements have not been decoupled significantly during magma generation and differentiation.

When compared (at 8% MgO) with oceanic basalt trends, the displacement of many CFB to lower Na₂O, Fe₂O₃^*, TiO₂ and CaO/Al₂O₃, but higher SiO₂, at similar Mg#, is not readily explicable by crustal contamination. Rather, it reflects source composition and/or the effects of the melting processes. The model compositions of melts produced by decompression of mantle plumes beneath continental lithosphere have relatively low SiO₂ and high Fe₂O₃^*. In contrast, the available experimental data indicate that partial melts of peridotite have low TiO₂, Na₂O and Fe₂O₃^*CaO/Al₂O₃, if the peridotite has been previously depleted by melt extraction. Moreover, melting of hydrated, depleted peridotite yields SiO₂-rich, Fe₂O₃- and CaO-poor melts. Since anhydrous, depleted peridotite has a high-temperature solidus, it is argued that the source of these CFB was variably melt depleted and hydrated mantle, inferred to be within the lithosphere. Isotope data suggest these source regions were often old and relatively enriched in incompatible trace elements, and it is envisaged that H₂O±CO₂ were added at the same time as the incompatible elements. An implication is that a significant proportion of the new continental crust generated since the Permian reflected multistage processes involving mobilization of continental mantle lithosphere that was enriched in minor and trace elements during the Proterozoic.     

Some Opinions on Rock-Weathering-Related Carbon Sinks from the IPCC Fifth Assessment Report

Many recent researches show that rock-weathering-related carbon sink, especially carbonate-weathering-related carbon sink, actively takes part in the modern global carbon cycle, which might greatly contribute to balancing global carbon budget. Some new opinions on flux, time scale and effect of rock-weathering-related carbon sink were released in IPCC fifth Assessment Report (AR5). The flux of global rock-weathering-related carbon sink is about 0.4 Pg C/a in AR5 report, which accounts for about 1/2~1/3 of unbalanced global carbon budget. New time scale of global rock-weathering-related carbon sink was released. Time scale of silicate-weathering-related carbon sink is 10⁴~ 10⁶ year, while carbonate-weathering-related carbon sink (karst processes) is 10³~10⁴ year. A highlight is that rock-weathering-related carbon sink is listed as one of four carbon dioxide removal methods in AR5 report, whose time scale is 10²~ 10³ year. Although AR5 report released these new opinions, it is still thought that the rate of global rock-weathering-related carbon sink is currently too small to offset the rate at which fossil fuel CO₂ is being emitted. According to many researches in the field of rock weathering science in the past decades, this review discussed the shortage in carbon flux, time scale and effect of rock-weathering-related carbon sink in AR5 report. Many recent researches indicated that the carbon sink originated from carbonate rock weathering was a fast and sensitive geochemical process, which showed multiple time scales (diel, seasonal, annual or storm event). A new model based on H₂O carbonate-CO₂-aquatic phototroph interaction was established, which coupled geological, land surface water, and submerged phototroph carbon cycle process. The global carbon sink from carbonate rock weathering in new model is 0.477 Pg C/a,which accounts for about 39%~59% of unbalanced global carbon budget. Some key scientific issues on rate, stability, controlling mechanisms and scaling of rock-weathering-related carbon sink should be vitally concerned in the future, which could greatly contribute to balancing the global carbon budget.     

松辽盆地北部上二叠统林西组地球化学特征及地质意义

为探讨松辽盆地北部林西组地球化学特征、沉积环境及构造背景,对该区黑富地1井所钻遇的上二叠统林西组暗色泥质板岩进行主量元素、微量元素和稀土元素测试分析,结果表明：样品主量元素平均质量分数SiO₂为65.05%、Al₂O₃为17.23%、CaO为2.58%、Na₂O为2.84%、K₂O为3.29%,K₂O/Na₂O值为0.20~3.48,A1₂O₃/（CaO+Na₂O）值为0.41~8.01;稀土元素w（∑REE）值介于80.68×10^-6~215.59×10^-6之间,平均值为173.41×10^-6,δEu值介于0.61~0.88之间,平均值为0.70,表现为Eu的负异常,δCe值介于0.91×10^-6~1.01×10^-6之间,为微弱的Ce负异常,LREE富集,HREE亏损;微量元素以亏损Nb、Ta、Sr,相对富集Rb、Ba、La、Ce、Pb、Nd、Sm为特征。样品元素分析和物源w（TiO₂）-w（Ni）、La/Th-w（Hf）等判别图解表明,林西组沉积物源具有多样性,主要来源于上地壳长英质物源,还有少量来自中、基性岩火成岩物源区。样品微量元素标准化蛛网图,稀土元素球粒陨石标准化配分模式图,K₂O/Na₂O-w（SiO₂）、Th-Co-Zr/10、F₂-F₁构造背景判别图及地球化学参数对比结果表明,松辽盆地北部林西组物源构造背景主要为活动大陆边缘和大陆岛弧,可能形成于靠近大陆岛弧的活动大陆边缘构造背景。林西组应形成于海陆过渡相到陆相环境,水体由半咸水逐渐转变为淡水。     

南天山南缘下二叠统玄武质岩浆的地球化学特征及其构造意义

南天山造山带南缘发育大量的下二叠统火山岩。地球化学指标显示南天山南缘西段拜城县宿相厄肯沟出露的下二叠统小提坎立克组玄武岩为拉斑玄武岩(里特曼指数δ=2.93)。 该套岩石低FeO^T、MgO和全碱(Na₂O+K₂O),高CaO和Al₂O₃,相对高钠,低钾; Rb、K、U和Ba 等大离子亲石元素富集; 稀土配分曲线整体协调一致,为向右缓倾的曲线,轻稀土元素(LREE)相对富集; 微量元素配分型式呈"驼峰状"; 玄武岩的母岩浆经历了以单斜辉石为主的分离结晶作用和强烈的陆壳混染作用。同位素组成 ¹⁴³ Nd/¹⁴⁴ Nd =0.512 849±0.000 005, ⁸⁷ Sr/⁸⁶ Sr =0.706 845±0.000 014; -10<ε_Nd(t)<0,且ε_Sr(t)>0,模式年龄T_DM 为1.463 279 765 Ga。 结合区域地质资料表明,小提坎立克组玄武岩形成于板内伸展环境,具有主动裂谷作用性质,说明南天山造山带南缘当时处于碰撞后伸展背景。