四元体系K+,Na+//Clˉ,Brˉ-H2O348K相平衡

用等温溶解平衡法研究了四元体系K+,Na+∥Clˉ,Brˉ-H2O 348 K条件下的相平衡关系,测定了该交互四元体系在相应温度条件下平衡溶液的溶解度和密度,并根据相平衡实验数据绘制了相应的相图.研究结果表明:四元体系K+,Na+∥Clˉ,Brˉ-H2O348 K条件下属于固溶体型,相图中含有1条单变量曲线,2个平衡固相结晶区,无共饱和点.其平衡固相分别为固溶体K(Cl,Br)和Na(Cl,Br),其中固溶体K(Cl,Br)结晶区较大,固溶体Na(Cl,Br)结晶区较小.与同体系313 K条件下的相图相比,348 K时固溶体Na(Cl,Br)·2H2O结晶区消失.     

The solubility of gold and silver in the system AuAgSO2H2O at 25°C and 1 atm.

During supergene alteration of auriferous carbonate ore, the weathering fluids formed are likely to be alkaline and therefore unsuitable as a medium for gold transport as a chloride complex. Secondary gold remobilization in such deposits can often be attributed instead to gold complexing by sulphur-bearing ligands. Gold and silver solubility in the systems AuSO₂H₂O and AgSO₂H₂O respectively, from the thermodynamic data available, is due to complex formation with thiosulphate and bisulphide ligands. The most stable gold complexes, Au(S₂O₃)₂³⁻ (at φO₂ > 10⁻⁶⁰) and Au(HS)⁻₂ (atφO₂ < 10⁻⁶⁰), exist in neutral or alkaline solutions. Like gold, silver forms a stable thiosulphate complex, Ag(S₂O₃)³⁻₂ in moderately oxidizing, and bisulphide complexes, AgHS⁰ and Ag(HS)⁻₂ in reducing, alkaline media. Silver solubility in highly oxidized, neutral or acid solutions is increased by formation of AgS₂O₃⁻, Ag⁺ and AgSO₄⁻ complexes.Colloidal, crystalline and alloyed gold and silver reacted with 0.1 M Na₂S₂O₃ do not, however, demonstrate independent solubility. The rate of gold solubility in 0.1 M Na₂S₂O₃, for example, is increased both by the presence of silver-thiosulphate complexes and alloyed silver. It is possible that such behaviour is due to the formation a mixed metal complex of the type (Au, Ag)(S₂O₃)₂³⁻.The nature and mineral association of secondary gold in the oxidized zone of carbonate ore at Wau. in Papua New Guinea, is consistent with prior remobilization as a thiosulphate complex. Here the secondary gold is coarsely crystalline, alloyed with 50–75 at% Ag and enriched at the watertable and with manganese dioxide in the oxidized zone.     

Changes in the HOAr isotope composition of clays during retrograde alteration

K-Ar ages of illite alteration associated with Middle Proterozoic Athabasca unconformity-type U deposits in Saskatchewan range from 414 to 1493 Ma. The K-Ar ages correlate with water contents and δD values such that illites with young K-Ar ages have δD values as low as −169 and water contents as high as 7.7 wt.% whereas illites with older ages have δD values near −70 and water contents near 4 wt.%. Water extracted at 400°C from illites with low δD values and high water contents has low δD and δ¹⁸O values similar to those of modern meteoric water suggesting that some of the illites associated with the original deposition of the ore underwent varying degrees of retrograde alteration. The alteration is initiated by hydration of sites in the interlayer region of the illite which results in the partial resetting of the K-Ar ages and introduction of excess structural water in the form of interlamellar water. The interlamellar water is enriched in ¹⁸O by about 7 per mil relative to the water that physically surrounded the clay particle. Further alteration decreases the δD value and increases the δ¹⁸O value of the illite by isotopic exchange between the mineral and the interlamellar water. Although the chemical compositions and XRD patterns of the altered illites indicate that no detectable smectite component is present in the samples, the isotopic results suggest that the altered illites may be an early precursor in the formation of mixed-layer illite/smectite by retrograde alteration of pure illite. The wide variation of δD values of chlorite and kaolinite from these U deposits is analogous to that of the illite suggesting that retrograde alteration of clays by meteoric water can be substantial. The general association of altered clays with areas containing the highest concentrations of U is probably related to localized permeability within the ore zone.     

FeMgMn relations of ureilite olivines and pyroxenes and the genesis of ureilites

The Fe/Mn-Fe/Mg relations of published microprobe analyses of ureilite olivine cores suggest that FeO reduction in the magmatic stage was important in the genesis of some of these meteorites. Consideration of Mg/Mn and Fe/Mn partitioning between olivine and pigeonite cores shows that these two phases are not in equilibrium. The data are consistent with combined fractional crystallization and FeO reduction being the major processes of ureilite genesis. Few, if any, of the analyzed ureilites are consistent with a partial melting residue model.     

Evaluation of KAr isochron methods

The KAr isochron method is an attempt to obtain the initial age or reset age and the extraneous argon isotopic ratio of a suite of cogenetic samples of different K-contents. Some samples contain excess argon-40 and others lose argon-40. The resultant ages on single samples are not significant geologically. We have discussed the principles of three types of isochrons commonly used, the ⁴⁰Ar vs ⁴⁰K isochron, the ⁴⁰Ar/³⁶Ar vs ⁴⁰K/³⁰Ar isochron, and the ⁴⁰Ar/³⁶Ar vs ³⁹Ar/³⁶Ar isochron, and evaluated the first two types for ten different hypothetical cases. If a straight line is obtained in the ⁴⁰Ar vs ⁴⁰K isochron, a positive intercept indicates an approximately constant amount of excess argon, whereas a negative intercept indicates argon loss. A curved line or scattering of points indicates that the basic assumptions are not valid for the set of samples under consideration. The ⁴⁰Ar/³⁶Ar vs ⁴⁰K/³⁶Ar isochron method is valid, rigorously, only when all samples of the system under consideration have the same non-radiogenic argon isotope composition. This requires that either no excess argon is present in the system, or else each analysis contains the same proportion of excess and atmospheric argon. If these conditions do not hold, approximately, invalid ages and invalid intercepts are obtained. Any KAr isochron needs to be used with caution.     

Na 元素的EPMA 定量分析：矿物晶体结构对Na 行为的制约

Na 属于热扩散元素,具有不稳定性,准确测定有难度。前人对含Na 玻璃和具有不同晶体结构的含Na 矿物的电子探针定量分析发现,随着分析时间的延长,Na 的计数明显下降,并且含Na 玻璃计数的下降要比含Na 矿物相比更为明显,表明Na 计数与试样的结构有关,但对其内在控制因素还不太明确。文章在前人研究的基础上,选择具有代表性不同结构含Na 硅酸盐矿物和非晶质含Na 玻璃作为研究对象,通过对不同晶体结构中Na 元素所处的位置、配位数、键性类型的特征进行总结,针对不同晶体结构中Na 原子扩散条件和是否存在附加阴离子与之相伴等因素,对比分析不同晶体结构中Na 计数下降的程度,深入探讨了导致Na 计数下降的内在原因。结果显示,试样分析过程中Na 计数下降顺序为：非晶质> 架状>层状> 环状> 单链状> 双链,且有附加阴离子的含Na 矿物要大于无附加阴离子的矿物。通过对不同测试条件下Na 计数的对比分析发现,加速电压、束流、束斑直径等改变,都会对Na 计数产生一定的影响。最终总结得出了准确测定含Na 硅酸盐矿物的最佳分析条件,为准确测定含Na 矿物和玻璃中的Na 含量提供参考。     

Interpretation of Na–Cl–Br Systematics in Sedimentary Basin Brines: Comparison of Concentration, Element Ratio, and Isometric Log-ratio Approaches

Mathematicians and geochemists have long realized that compositional data intrinsically exhibit a structure prone to spurious and induced correlations. This paper demonstrates, using the Na–Cl–Br system, that these mathematical problems are exacerbated in the study of sedimentary basin brines by such processes as the evaporation or dissolution of salts owing to their high salinities. Using two published datasets of Na–Cl–Br data for fluids from the Appalachian Basin, it is shown that log concentration and Na/Br versus Cl/Br methods for displaying solute chemistry may lead to misinterpretation of mixing trends between meteoric waters (for example shallow drinking water aquifers) and basinal brines, partially due to spurious mathematical relationships. An alternative approach, based on the isometric log-ratio transformation of molar concentration data, is developed and presented as an alternative method, free from potential numerical problems of the traditional methods. The utility, intuitiveness, and potential for mathematical problems of the three methods are compared and contrasted. Because the Na–Cl–Br system is a useful tool for sourcing solutes and investigating the evolution of basinal brines, results from this research may impact such critical topics as evaluating sources of brine contamination in the environment (possibly related to oil and gas production), evaluating the behavior of fluids in the reservoir during hydraulic fracturing, and tracking movement of fluids as a result of geologic CO₂ sequestration.     

埃达克岩的Na亏损及其对地幔Na交代的指示意义

埃达克岩是玄武质洋壳部分熔融的产物。然而,与实验室玄武岩部分熔融产生的埃达克质熔体相比,天然埃达克岩明显地高Mg、Cr和Ni,这表明埃达克岩浆在上升过程中有地幔成分的加入。本文的观察结果表明,全球新生代埃达克岩的Na2O含量低于5.8%,大约95%的新生代埃达克岩样品Na2O含量小于5.0%。然而,在埃达克岩产生的压力范围(1.5～3.0GPa),实验的玄武岩部分熔体大多数Na2O含量超过5.0%,最高达到9.0%,显示埃达克岩具有明显的Na亏损现象。我们认为这是埃达克熔体在热的地幔楔中与地幔橄榄岩反应的结果。在俯冲带,大洋板片熔融产生的熔体(埃达克熔体)上升并与地幔橄榄岩发生反应,原始的埃达克熔体获得MgO、Cr及Ni等地幔组分,但其Na2O和SiO2等通过反应进入地幔,导致地幔交代作用。根据长英质熔体与橄榄岩反应体系的相关系,我们认为,地幔单斜辉石、橄榄石、尖晶石的混染作用以及钠质角闪石和斜方辉石的分离结晶作用,是改变埃达克熔体组成并导致其Na亏损的一个重要的过程。埃达克岩的Na亏损为地幔Na交代作用和一些富Na的弧岩浆成因提供了重要证据。     

The effects of sulfur intercalation on the optical properties of artificial ‘hackmanite’, Na8[Al6Si6O24]Cl1.8S0.1; ‘sulfosodalite’, Na8[Al6Si6O24]S; and natural tugtupite, Na8[Be2Al2Si8O24](Cl,S)2?δ

The minerals ??hackmanite?? and tugtupite exhibit tenebrescence (reversible photochromism) and photoluminescence. These features are generally attributed to the presence of sulfide species within their structures. But how these optical properties might be affected by intercalating additional amounts of sulfur into their structures was until now unknown. Artificial ??hackmanite??, Na₈[Al₆Si₆O₂₄]Cl_1.8S_0.1, and ??sulfosodalite??, Na₈[Al₆Si₆O₂₄]S, were heated with sulfur in evacuated quartz-glass ampoules over the temperature range 450?C1,050°C. This work has shown that sulfur intercalation into Na₈[Al₆Si₆O₂₄]Cl_1.8S_0.1 destroys the tenebrescence and induces a permanently pale blue and, at higher temperature, a pale green coloration. The effect on Na₈[Al₆Si₆O₂₄]S induced similar colorations but of a deeper hue. Annealing tugtupite, Na₈[Be₂Al₂Si₈O₂₄](Cl,S)_2??? under a sulfur atmosphere over the range 600?C700°C, destroyed the tenebrescence and resulted in a colorless tugtupite; but did not effect the photoluminescence. This suggests that the chemical species responsible for the tenebrescence in tugtupite is unlikely to be the same as that for the luminescence.     

鄂尔多斯白垩系盆地地下水的形成与演化：来自Cl及其同位素36Cl的证据

鄂尔多斯自垩系地下水盆地地处中国西部干旱-半干旱地区,其南部和北部分别被黄土和沙漠覆盖,地下水水化学组成在区域上差异显著,北部以淡水为主,南部以微咸-半咸水为主.在沙漠区和黄土区的深层含水层中(埋深大于400 m)分别采集了5组和3组水化学同位素样品.T和14C的分析结果表明,地下水的滞留时间在20343 a内,并且未...     

Kar and RbSr whole-rock ages reset during pan african event in the sinai peninsula (Ataqa Area)

A low pressure metamorphic Pan African terrain, composed mainly of schists and hornfels, ranging from high greenschist to low amphibolite facies, is exposed west of Dahab, southeastern Sinai, located between the metamorphic Kid Complex and the Feirani Volcanics.The studied metamorphic unit was dated using RbSr and KAr methods. A RbSr whole-rock isochron (based on seven samples) yields an age of 602 ± 11 Ma with an initial (⁸⁷Sr/⁸⁶Sr) ratio of 0.7041 ± 4. The RbSr age is assumed to be the age of a metamorphic phase (600 ± 10 Ma) well known in the area. On the other hand, KAr whole-rock ages (based on nine samples) show different values ranging from 590 to 526 Ma. These low KAr ages are due to the resetting of the KAr system by a thermal event, before 530 Ma affecting the Ar behaviour without disturbing the RbSr system. The Ar escape took place mainly from K-bearing feldspars, which were not affected by later textural, crystallographic or mineralogic variations.     

The RbSr age dating of some Carboniferous shales

The RbSr age dating method has been applied to a sequence of Carboniferous shales for which some geochemical information was already available. In the marine shales, the Rb/Sr ratio is higher than in the non-marine and brackish water shales. Although the range of values can be attributed to depositional processes, the range of Rb/Sr values is too small to give a depositional isochron, and thus the age of deposition can not be determined. If samples with a variable mineralogy had been selected for the isotope study, the range of Rb/Sr could have been extended. Only by chance, however, would the depositional age have been obtained.A comparison of the RbSr isotope values in the Carboniferous shales with those in probable source rocks shows that a reduction in the Sr⁸⁷/Sr⁸⁶ ratio relative to the Rb⁸⁷/Sr⁸⁶ ratio may have taken place. Such a reduction could have occurred on the Carboniferous land-mass during the formation of the clay minerals.     

Über das anoniale Mischsystem Kryolith Na3AIF6-Thenardit Na2SO4.

Ohne Zusammenfassung     

An Experimental Study on Picromerite Equilkibrium in the Five—Component Brine System K—Na—Mg—Cl—SO4—H2O

This paper presents the results of experiments on the physicochemical conditions for the formation of picaromerite in the five-component brine system K-Na-Mg-Cl-SO4-H2O and the process of isothermal evaporation-crystallization of picromerite from brines.The metastable phase fields of picromerite at 15,10 and 5℃and its stable equilibrium phase field at -5℃ have been established.In addition,the phase equilibrium relationships have also been established for other salt minerals.The lower limit of formation temperature of picromerite has been deduced on the basis of experi-mental results.The isothermal evaporation crystallization path of the invariant assemblage(point D) of picromerite,epsomite,sylvite and halite at 25,15,10 and 5℃ has been revealed.Furthermore,some controversial problems are approached concerning the 25℃“solar” diagram and the 25℃ metastable phase diagram of this system.