Partitioning of boron among melt, brine and vapor in the system haplogranite–H2O–NaCl at 800 °C and 100 MPa

Fluid-saturated experiments were conducted to investigate the partitioning of boron among haplogranitic melt, aqueous vapor and brine at 800 °C and 100 MPa. Experiments were carried out in cold-seal pressure vessels for 1 to 21 days, and utilized powdered synthetic subaluminous haplogranite glass doped with 1000 ppm B (crystalline H₃BO₃) and variable amounts of NaCl and H₂O at a fluid/haplogranite mass RATIO=1:1. Run-product glasses were analyzed for boron concentration by secondary ion mass spectrometry (SIMS) and for major elements and chlorine by electron microprobe. The composition of the coexisting fluid was calculated by mass balance. Boron partition coefficients between aqueous vapor and hydrous granitic melt range from 3.1 to 6.3, and demonstrate a clear preference of boron for the vapor over the hydrous melt. Partition coefficients between brine and hydrous granitic melt vary from 0.45 to 1.1, suggesting that boron has no preference for the brine or the melt. The bulk fluid–melt partition coefficients for low-salinity and high-salinity experiments are D_B^(vapor/melt)=4.6±1.3 and D_B^(brine/melt)=0.91±0.49, respectively. The corresponding vapor–brine partition coefficient is 5.0±3.1, demonstrating that boron partitions preferentially into the vapor over the brine at the conditions of this study. The preferential incorporation of boron in the aqueous vapor is controlled by borate speciation and solution mechanism. The dominant borate species in aqueous fluids, H₃BO₃^o, is highly soluble in aqueous vapor (X_B2O3=0.187); however, B₂O₃ is immiscible in NaCl liquid. Consequently, concentrations of boron in aqueous vapor are significantly higher than in the coexisting brine. Furthermore, Na–B complexing in the melt at high chlorine fluid contents stabilizes boron in the melt thereby contributing to the non-preferential partitioning of boron between brine and melt. The commonly observed association of tourmalinization (boron metasomatism), brecciation and ore deposition in nature is consistent with the preferential partitioning of boron into aqueous vapor of magmatic-hydrothermal systems predicted by this study.     

Identifying sources of salinization using hydrochemical and isotopic techniques, Konarsiah, Iran

Konarsiah salt diapir is situated in the Simply Folded Zone of the Zagros Mountain, south Iran. Eight small permanent brine springs emerge from the Konarsiah salt body, with average total dissolved solids of 326.7 g/L. There are numerous brackish to saline springs emerging from the alluvial and karst aquifers adjacent to the diapir. Concerning emergence of Konarsiah diapir in the study area, halite dissolution is the most probable source of salinity in the adjacent aquifers. However, other sources including evaporation and deep brines through deep Mangerak Fault are possible. The water samples of the study area were classified based on their water-type, salinity, and the trend of the ions concentration curves. The result of this classification is in agreement with the hydrogeological setting of the study area. The hydrochemical and isotopic evaluations show that the groundwater samples are the result of mixing of four end members; Gachsaran sulfate water, Sarvak and Asmari carbonate fresh waters, and diapir brine. The molar ratios of Na/Cl, Li/Cl, Br/Cl, and SO₄/Cl; and isotopic signature of the mixed samples justify a groundwater mixing model for the aquifers adjacent to the salt diapir. The share of brine in each adjacent aquifer was calculated using Cl mass balance. In addition, concentrations of 34 trace elements were determined to characterize the diapir brine and to identify the possible tracers of salinity sources in the mixed water samples. B, Mn, Rb, Sr, Cs, Tl, and Te were identified as trace elements evidencing contact of groundwater with the salt diapir.     

云南勐野井钾盐矿床特征,微量元素地球化学及成因探讨

勐野井钾盐矿床位于云南兰坪、恩茅拗陷带的南部。该带地处藏滇印支地槽褶皱系中段,点苍山、哀牢山断裂带以西,澜沧江断裂带以东。区内发育有巨厚的中新生代红色碎屑岩和含盐建造,本区的主要含盐层为晚白垩世至老第三纪勐野井组。 勐野井组有上下两套含盐层,中部为棕红色钙泥质粉砂岩,下含盐层在区域上是含膏层;上含盐层为石盐岩夹钾盐透镜体。下覆地层是上白垩统扒沙河紫红色石英砂岩,上覆为老第三系等黑组棕红色粉砂岩。矿区为一向斜构造呈北西—南东向分布,盐矿体呈穹窿状,石盐层平均厚196米,钾盐厚29米,NaCl平均含量71.67％ KCl 8.70％,为混有碎屑物的氯化物型钾盐矿床。 本文研究了富钾盐层剖面结构、碎屑物沉积特征、溴、铷、锶、硼等微量元素赋存规律及其在寻找钾盐矿床工作中的标志意义,并探讨了盐矿床的成因。全文蒙袁见齐教授审阅,并提出修改意见,在此表示感谢。     

Hydrosilicate liquids in the system rare-metal granite–Na<Subscript>2</Subscript>O–SiO<Subscript>2</Subscript>–H<Subscript>2</Subscript>O as accumulators of ore components at high pressure and temperature

Experimental investigations in the system rare-metal granite–Na₂O–SiO₂–H₂O with the addition of aqueous solutions containing Rb, Cs, Sn, W, Mo, and Zn at 600°C and 1.5 kbar showed that the typical elements of rare-metal granites (Li, Rb, Cs, Be, Nb, and Ta) are preferentially concentrated in hydrosilicate liquids coexisting with aqueous fluid. The same behavior is characteristic of Zn and Sn, the minerals of which are usually formed under hydrothermal conditions. In contrast, Mo and W are weakly extracted by hydrosilicate liquids and almost equally distributed between them and aqueous fluids. Liquids similar to those described in this paper are formed during the final stages of magmatic crystallization in granite and granitepegmatite systems. The formation of hydrosilicate liquids in late magmatic and postmagmatic processes will be an important factor controlling the redistribution of metal components between residual magmatic melts, minerals, and aqueous fluids and, consequently, the mobility of these components in fluid-saturated magmatic systems enriched in rare metals.     

Geochemical Characteristics of the Ore-forming Fluids of the Haigou Gold Deposit, Jilin

The quartz in the Haigou gold deposit contains a great abundance of three-phase CO2-NaCl-H2O and two-phase CO2-rich inclusions, which are associated with two-phase NaCl-H2O ones. The ore-forming fluids, which were rich in CO2, are classified into two types with two different sources: the high-salinity CO2-rich NaCl-H2O fluid derived from magmatic hydrothermal solution, and the low-salinity NaCl-H2O fluid from ancient meteoric water. The optimum conditions for gold mineralization are 220-300℃ for the temperature, 4-20 MPa for the fluid static pressure, 1-3 km for the mineralization depth, 2-7 w (NaCl)/10-2 for the fluid salinity, and 0.644 g/cm3 for the total density. The fluid was in a critical or supercritical state at the initial stage of mineralization, and it boiled and was unmixed with CO2 and NaCl-H2O in the climax of mineralization, leading to the decomposition of Au-chlorine complexes and the bulk precipitation of Au.The type, association, homogenization temperature and composition (CO2/H2O val     

四川盆地三叠系蒸发岩的变质作用与富钾卤水的成因

在四川盆地三叠系蒸发岩建造中已发现钾盐镁矾、无水钾镁矾、软钾镁矾、杂卤石、钾石膏、多钙钾石膏、钙芒硝等矿物,并在多处发现富钾卤水。已有的资料表明,这些矿物组合是已沉积的固体钾盐层在成岩期水溶变质作用过程中形成的变质矿物组合。在此过程中大量的钾质转入水溶液,形成了富钾卤水。这种富钾卤水是可综合利用的ＫＣｌ、ＮａＣｌ和Ｌｉ、Ｓｒ、Ｃｓ、Ｒｂ、Ｂ、Ｂｒ、Ｉ的优质盐化工业原料卤水。     

中瑞合作利用“许氏法”开发盐湖卤水中锂资源

自 70年代以来 ,利用传统方法在青海进行的盐湖卤水提锂未见成效。利用“许氏法”(“蒸发泵原理”及“原地化学反应池法”)对青海察尔汗盐湖的高镁含锂老卤进行室内及野外提锂试验 ,均获得成功。不但富集了锂卤水 (LiCl含量自 0 .72 1 2 g/L富集至 45 .1 8g/L) ,而且还得到了大量的副产品水氯镁石 (MgCl2 ·6H2 O) ,同时查明Br、I、B、Rb、Sr、Cs等微量元素赋存在锂卤水中。“许氏法”不但成本低、效益高、方法可行、工艺合理 ,而且保护了盐湖区的生态环境 ,实为一种值得推广的盐湖卤水提锂的加工工艺     

Major and trace element compositions (including REE) of mineral,thermal, mine and surface waters in SW Germany and implications for water–rock interaction

The near-surface water cycle in a geologically complex area comprises very different sources including meteoric, metamorphic and magmatic ones. Fluids from these sources can react with sedimentary, magmatic and/or metamorphic rocks at various depths. The current study reports a large number of major, minor and trace element analyses of meteoric, mineral, thermal and mine waters from a geologically well-known and variable area of about 200 × 150 km in SW Germany. The geology of this area comprises a Variscan granitic and gneissic basement overlain in parts by Triassic and Jurassic shales, sandstones and limestones. In both the basement and the sedimentary rocks, hydrothermal mineralization occurs (including Pb, Cu, As, Zn, U, Co and many others) which were mined in former times. Mineral waters, thermal waters and meteoric waters flowing through abandoned mines (mine waters) are distributed throughout the area, although the mine waters concentrate in and around the Schwarzwald.The present analyses show, that the major element composition of a particular water is determined by the type of surrounding rock (e.g., crystalline or sedimentary rocks) and the depth from which the water originates. For waters from crystalline rocks it is the origin of the water that determines whether the sample is Na–Cl dominant (deeper origin) or Ca–HCO₃ dominant (shallow origin). In contrast, compositions of waters from sedimentary rocks are determined by the availability of easily soluble minerals like calcite (Ca–HCO₃ dominant), halite (Na–Cl dominant) or gypsum (Ca–SO₄ dominant). Major element data alone cannot, therefore, be used to trace the origin of a water. However, the combination of major element composition with trace element data can provide further information with respect to flow paths and fluid–rock interaction processes. Accordingly, trace element analyses showed, that:

• −Ce anomalies can be used as an indicator for the origin of a water. Whereas surface waters have negative or strongly negative Ce anomalies, waters originating from greater depths show no or only weak negative Ce anomalies.
• −Eu anomalies can be used to differentiate between host rocks. Waters from gneisses display positive Eu anomalies, whereas waters from granites have negative ones. Waters from sedimentary rocks do not display any Eu anomalies.
• −Rb and Cs can also be indicators for the rock with which the fluid interacted: Rb and Cs correlate positively in most waters with Rb/Cs ratios of ∼2, which suggests that these waters are in equilibrium with the clay minerals in the rocks. Rb/Cs ratios >5 indicate reaction of a water with existing clay minerals, whereas Rb/Cs ratios <2 are probably related to host rock alteration and clay mineral formation.

The chemical compositions of carbonate precipitates from thermal waters indicate that rare earth elements (REEs), Rb and Cs concentrations in the minerals are controlled by the incorporation of clay particles that adsorb these elements.     

Immiscible separation of metalliferous Fe/ Ti-oxide melts from fractionating alkali basalt: P-T-f O2 conditions and two-liquid elemental partitioning

Globules of iron-dominated (59–69 wt% FeO_tot) and titanium-dominated (43.5 wt% TiO₂) oxide melts have been detected in igneous xenoliths from Pliocene-to-Pleistocene alkali basalts of the Western Carpathians. Fluid inclusion and mineral composition data indicate immiscible separation of the high-iron-oxide melt (HIM) at magmatic temperatures. The HIM separation occurred during clinopyroxene (augite) accumulation in an alkali trachybasalt and continued during crystallization of amphibole (kaersutite) and K-feldspar (anorthoclase), the latter coexisting with trachyte and alkalic rhyolite residual melts. Some HIM was also expelled from sub-alkalic rhyolite (70–77% SiO₂), coexisting with An_27–45 plagioclase and quartz in granitic (tonalite-trondhjemite) xenoliths. Oxygen fugacities during HIM separation range from −1.4 to +0.6 log units around the QFM buffer. A close genetic relationship between HIM-hosted xenoliths and mantle-derived basaltic magma is documented by mineral ¹⁸O values ranging from 4.9 to 5.9‰ V-SMOW. δD values of gabbroic kaersutite between −61 and −86‰ V-SMOW are in agreement with a presumed primary magmatic water source. Most trace elements, except Li, Rb and Cs, have preferentially partitioned into the HIM. The HIM/Si-melt partition coefficients for transition elements (Sc, V, Cr, Co, Ni) and base metals (Zn, Cu, Mo) are between 2–160, resulting in extreme enrichment in the HIM. La and Ce also concentrate in the silicic melt, whereas Tb-Tm in the HIM. Hence, the immiscible separation causes REE fractionation and produces residual silicic melt enriched in LREE and depleted in HREE. The weak fractionation among Tb-Tm and Yb, Lu can be attributed to recurrent extraction of the HIM from the magmatic system, while flat HREE chondrite-normalized patterns are interpreted to indicate no or little loss of the HIM. Received: 30 September 1997 / Accepted: 23 March 1998     

老挝甘蒙省钾镁盐矿床含矿段的矿物学和地球化学特征及成因

老挝甘蒙省钾镁盐矿床位于呵叻盆地的东隅,本文以该矿床ZK318钻孔的含矿段———下盐层为研究对象,对其开展了系统的矿物学和地球化学特征研究。结果表明,矿石矿物以石盐、钾石盐和光卤石为主,含少量方硼石和硬石膏。根据矿物与主量元素的分布特征,将下盐层分为5个次层,由下至上顺序为:盐岩层(石盐为主)→钾盐岩层(钾石盐为主)→光卤石岩层(光卤石为主)→薄盐岩层(石盐为主)→钾盐岩层(钾石盐为主)。微量元素Br值均大于200×10-6,表明卤水来源于海水;由盐岩层→钾盐岩层→光卤石岩层,B含量呈现出逐渐升高的趋势,表明B含量与卤水盐度呈线性关系。但顶部钾盐岩层的B含量高达890×10-6,与少量方硼石的存在相吻合,指示成矿卤水除了海水外,还有深部热液的贡献。按照卤化物卤水蒸发浓缩的顺序,光卤石是该卤水浓缩的最后阶段,但在光卤石沉积之后,又晶出一薄层石盐,表明曾经历过一次短暂的淡水补给。上、下两层钾石盐具有基本相同的Br含量,分别为1 790×10-6和1 792×10-6,且均直接沉积在石盐之上,故为原生钾石盐,而非光卤石的次生淋滤产物。认为甘蒙省钾镁盐矿床为海源陆相沉积,海水和深部热液是成钾物质的主要来源,钻孔中出露的两层钾石盐均为原生沉积。     

流体包裹体及石英LA-ICP-MS分析方法的建立及其在矿床学中的应用

流体包裹体LA-ICP-MS(激光剥蚀-电感耦合等离子体质谱仪)分析具有高精度、低检测限、多元素同时微区原位检测的特点,因此在精细刻画成矿过程、深入揭示成矿机理方面具有传统方法无可比拟的优势。通过人工合成石英Na Cl-H2O-Rb-Cs和Na Cl-KCl-Ca Cl2-H2O-Rb-Cs流体包裹体,使用NIST610为外标、显微测温Na Cl等效盐度(电价平衡方法)为内标,建立了流体包裹体L A-ICP-MS分析方法。分析结果的相对误差在±16%以内,绝大部分在±10%以内,相对标准偏差(RSD)小于7%。同时结合国际上推荐的石英标样,使用NIST610为外标、无内标法,建立了石英微量元素LA-ICP-MS分析方法。分析结果表明,石英中主要元素Li、Al和Ti的相对误差在±10%以内,相对标准偏差小于5%。利用建立的方法对鲁西早白垩世王家庄Cu-Mo矿开展了应用研究,结果显示该矿富气相包裹体更富Cu,而含子矿物包裹体富Mo,暗示Cu和Mo可能具有不同的搬运机制,Cu更倾向于气相,Mo则倾向于进入液相,结合流体沸腾现象的存在,这可能是导致该矿上铜下钼分带沉淀的重要因素。此外,从早期岩浆成因石英到成矿期热液石英以及成矿期后石英,微量元素具有明显的Ti降低而Al升高的趋势,暗示成矿元素Cu、Mo的沉淀可能同时还受到温度和流体酸碱度变化的控制。     

Geochemistry of diffuse low-temperature hydrothermal fluids in the North Fiji basin

Low-temperature (<13°C) diffuse hydrothermal fluids were sampled directly at the seafloor with a specially designed Hydro Bottom Station in the North Fiji Basin and analyzed for gases, major and minor elements, and a large number of trace metals. The fluids were significantly enriched in CO₂, Si, Li, Rb, Cs, Ba, Mn, and several trace metals compared to ambient seawater, had high CH₄ and H₂S concentrations, and had a slightly decreased salinity. Calculated end-member concentrations of the low-temperature fluids show a strong similarity to the neighboring hot vents, implying that the diffuse fluids are hot vent waters diluted by seawater. According to the chemical composition, the sampled fluids derive from vapor-phase fluids produced by subseafloor boiling and phase separation. Compared to hot vents from other regions, Mn, Fe, and other trace metal concentrations are low. Subsurface metal sulfide precipitation during cooling and dilution with seawater has further decreased the dissolved metal contents of the diffuse fluids, thus creating a very favorable environment for the hydrothermal fauna, as indicated by a very low Fe/H₂S ratio. Therefore, the fluids support high bioproductivity but no hydrothermal mineral precipitation. The emanation of the condensed vapor phase appears to have been stable during the past 10 years; however, the occurrence of metal sulfide particles in some fluid and sediment samples and small areas of dead fauna indicate that the hydrothermal system may be evolving toward the emanation of the stored brine phase.     

Henry’s and non-Henry’s law behavior of Br in simple marine systems

Experimental studies for the partitioning of Br as a trace element between aqueous and solid solutions were carried out in simple marine systems. The evaporation experiments were performed at 25°C and 1 atm in the systems of halite (NaCl), sylvite (KCl), kainite (KMgClSO₄ · 2.75H₂O), carnallite (KMgCl₃ · 6H₂O), and bischofite (MgCl₂ · 6H₂O). The partition coefficients for the systems investigated are constant only at a restricted concentration range. For concentrations lower than 100 to 300 μg Br/g aqueous solutions, D_Br increases with decreasing concentrations. Various evaporation experiments indicate that this observation is not due to kinetic effects (evaporation rates). To find a link between the partition coefficient and the Henry’s law behavior, the activity coefficients of the trace components in the solid solutions were recalculated from the experimentally derived data. It can be shown from these calculations that constant activity coefficients or Henry’s law behavior is reached for higher mole fractions of the trace component in the solid solution in halite and sylvite and thus correspond to constant partition coefficients. For bischofite and carnallite, Henry’s law behavior is restricted to the lower mole fractions, where D_Br is not constant. This behavior is caused by the activity of the trace component in the aqueous solution, which is powered by the stoichiometric factor of this component in the Br-end-member solid solution. For halite, sylvite, and kainite, this factor equals 1 and is 2 for bischofite and 3 for carnallite. However, it is thus impossible to correlate Henry’s law behavior with constant partition coefficients for solid solution systems where the stoichiometric factor of the trace component is greater than 1.     

四川雪宝顶W-Sn-Be矿床中矿物化学组成及矿床成因

雪宝顶矿床位于四川省的松潘甘孜造山带中,以出产大颗粒含W-Sn-Be-F-P的矿物而闻名,前人对该矿床已经开展了大量的研究,但缺乏对粗粒矿物的主次痕量元素研究.本次研究采用X射线荧光光谱(XRF)、电子探针(EMPA)和电感耦合等离子体质谱(ICP-MS)技术对矿床中各矿物的主次痕量元素进行测试分析.结果显示,雪宝顶矿...     

西藏扎北盐湖秋季卤水(硫酸钠亚型)5℃等温蒸发实验研究

西藏扎北盐湖硫酸钠亚型卤水中富含元素Li、B、K和微量元素Rb、Cs等.为了更好地了解卤水在自然条件下的蒸发结晶规律,需对相应卤水进行低温室内等温蒸发实验研究.本文对该盐湖卤水进行了5℃等温蒸发试验,并利用Na+、K+、Mg2+//Cl-、SO42--H2O五元水盐体系0℃相图,构筑了从干基立体图Na2SO4角顶的放射...     

In situ analyses of micas in the Yashan granite,South China: Constraints on magmatic and hydrothermal evolutions of W and Ta–Nb bearing granites

Most rare-metal granites in South China host major W deposits with few or without Ta–Nb mineralization. However, the Yashan granitic pluton, located in the Yichun area of western Jiangxi province, South China, hosts a major Nb–Ta deposit with minor W mineralization. It is thus important for understanding the diversity of W and Nb–Ta mineralization associated with rare-metal granites. The Yashan pluton consists of multi-stage intrusive units, including the protolithionite (-muscovite) granite, Li-mica granite and topaz–lepidolite granite from the early to late stages. Bulk-rock REE contents and La/Yb ratios decrease from protolithionite granite to Li-mica granite to topaz–lepidolite granite, suggesting the dominant plagioclase fractionation. This variation, together with increasing Li, Rb, Cs and Ta but decreasing Nb/Ta and Zr/Hf ratios, is consistent with the magmatic evolution. In the Yashan pluton, micas are protolithionite, muscovite, Li-mica and lepidolite, and zircons show wide concentration ranges of ZrO₂, HfO₂, UO₂, ThO₂, Y₂O₃ and P₂O₅. Compositional variations of minerals, such as increasing F, Rb and Li in mica and increasing Hf, U and P in zircon are also in concert with the magmatic evolution from protolithionite granite to Li-mica granite to topaz–lepidolite granite. The most evolved topaz–lepidolite granite has the highest bulk-rock Li, Rb, Cs, F and P contents, consistent with the highest contents of these elements and the lowest Nb/Ta ratio in mica and the lowest Zr/Hf ratio in zircon. Ta–Nb enrichment was closely related to the enrichment of volatile elements (i.e. Li, F and P) in the melt during magmatic evolution, which raised the proportion of non-bridging oxygens (NBOs) in the melt. The rims of zoned micas in the Li-mica and topaz–lepidolite granites contain lower Rb, Cs, Nb and Ta and much lower F and W than the cores and/or mantles, indicating an exotic aqueous fluid during hydrothermal evolution. Some columbite-group minerals may have formed from exotic aqueous fluids which were originally depleted in F, Rb, Cs, Nb, Ta and W, but such fluids were not responsible for Ta–Nb enrichment in the Yashan granite. The interaction of hydrothermal fluids with previously existing micas may have played an important role in leaching, concentrating and transporting W, Fe and Ti. Ta–Nb enrichment was associated with highly evolved magmas, but W mineralization is closely related to hydrothermal fluid. Thus these magmatic and hydrothermal processes explain the diversity of W and Ta–Nb mineralizations in the rare-metal granites.     

Trace element partitioning between apatite and silicate melts

We present new experimental apatite/melt trace element partition coefficients for a large number of trace elements (Cs, Rb, Ba, La, Ce, Pr, Sm, Gd, Lu, Y, Sr, Zr, Hf, Nb, Ta, U, Pb, and Th). The experiments were conducted at pressures of 1.0 GPa and temperatures of 1250 °C. The rare earth elements (La, Ce, Pr, Sm, Gd, and Lu), Y, and Sr are compatible in apatite, whereas the larger lithophile elements (Cs, Rb, and Ba) are strongly incompatible. Other trace elements such as U, Th, and Pb have partition coefficients close to unity. In all experiments we found D_Hf > D_Zr, D_Ta ≈ D_Nb, and D_Ba > D_Rb > D_Cs. The experiments reveal a strong influence of melt composition on REE partition coefficients. With increasing polymerisation of the melt, apatite/melt partition coefficients for the rare earth elements increase for about an order of magnitude. We also present some results in fluorine-rich and water-rich systems, respectively, but no significant influence of either H₂O or F on the partitioning was found. Furthermore, we also present experimentally determined partition coefficients in close-to natural compositions which should be directly applicable to magmatic processes.     

The partitioning of copper between silicate melts and two-phase aqueous fluids: An experimental investigation at 1 kbar, 800° C and 0.5 kbar, 850° C

 Experiments were performed in the three phase system high-silica rhyolite melt+low-salinity aqueous vapor+hydrosaline brine, to investigate the partitioning equilibria for copper in magmatic-hydrothermal systems at 800° C and 1 kbar, and 850° C and 0.5 kbar. D^aqm/mlt _Cu and apparent equilibrium constants, K^aqm/mlt _Cu,Na, between the aqueous mixture (aqm=quenched vapor+brine) and the silicate melt (mlt) are calculated. D^aqm/mlt _Cu increases with increasing aqueous chloride concentration and is a function of pressure. K^aqm/mlt _Cu,Na=215(±73) at 1 kbar and 800° C and K^aqm/mlt _Cu,Na=11(±6) at 0.5 kbar and 850°C. Decreasing pressure from 1 to 0.5 kbar lowers K^aqm/mlt _Cu,Na by a factor of approximately 20. Data revealed no difference in K^aqm/mlt _Cu,Na or D^aqm/mlt _Cu as a function of the melt aluminium saturation index. Within the 2-phase field the K^aqm/mlt _Cu,Na show no variation with total aqueous chloride, indicating that copper-sodium exchange between the vapor, brine and silicate melt is independent of the mass proportion of vapor and brine. Model copper-sodium apparent equilibrium constants for the hydrosaline brine and the silicate melt revealed a negative dependence on pressure. Model apparent equilibrium constants for copper-sodium exchange between the brine and vapor were close to unity at 1 kbar and 800° C. Received: 27 June 1994/Accepted: 30 March 1995     

The partitioning behavior of As and Au in S-free and S-bearing magmatic assemblages

The partitioning of As and Au between rhyolite melt and low-salinity vapor (2 wt% NaCl eq.) in a melt-vapor-Au metal ± magnetite ± pyrrhotite assemblage has been quantified at 800 °C, 120 MPa and f_O2=NNO. The S-bearing runs have calculated values for the fugacities of H₂S, SO₂ and S₂ of logf_H2S=1.1, logf_SO2=-1.5, and logf_S2=-3.0. The ratio of H₂S to SO₂ is on the order of 400. The experiments constrain the effect of S on the partitioning behavior of As and Au at magmatic conditions. Calculated average Nernst-type partition coefficients (±1σ) for As between vapor and melt, , are 1.0 ± 0.1 and 2.5 ± 0.3 in the S-free and S-bearing assemblages, respectively. These results suggest that sulfur has a small, but statistically meaningful, effect on the mass transfer of As between silicate melt and low-salinity vapor at the experimental conditions. Efficiencies of removal, calculated following Candela and Holland (1986), suggest that the S-free and S-bearing low-salinity vapor can scavenge approximately 41% and 63% As from water-saturated rhyolite melt, respectively, during devolatilization assuming that As is partitioned into magnetite and pyrrhotite during second boiling. The S-free data are consistent with the presence of arsenous acid, As(OH)₃ in the vapor phase. However, the S-bearing data suggest the presence of both arsenous acid and a As-S complex in S-bearing magmatic vapor. Apparent equilibrium constants, , describing the partitioning of As between melt and vapor are −1.3 (0.1) and −1.1 (0.1) for the S-free and S-bearing runs, respectively. The increase in the value of with the addition of S suggests a role for S in complexing and scavenging As from the melt during degassing.The calculated vapor/melt partition coefficients (±1σ) for Au between vapor and melt, , in S-free and S-bearing assemblages are 15 ± 2.5 and 12 ± 0.3, respectively. Efficiencies of removal (Candela and Holland, 1986) for the S-free melt, calculated assuming that magnetite is the dominant Au-sequestering solid phase during crystallization (Simon et al., 2003), suggest that magmatic vapor may scavenge on the order of 72% Au from a water-saturated melt. Efficiencies of removal calculated for the S-bearing assemblage, assuming pyrrhotite and magnetite are the dominant Au-sequestering solid phases, indicate that vapor may scavenge on the order of 60% Au from the melt. These model calculations suggest that the loss of pyrrhotite and magnetite from a melt, owing to punctuated differentiation during ascent and emplacement, does not prohibit the ability of a rhyolite melt to generate a large-tonnage Au deposit. Apparent equilibrium constants describing the partitioning of Au between melt and vapor were calculated using the mean values for the S-free and S-bearing assemblages; only S-bearing data from runs longer than 400 h were used as shorter runs may not have reached equilibrium with respect only to vapor/melt partitioning of Au. The values for are −4.4 (0.1) and −4.2 (0.2) for the S-free and S-bearing runs, respectively. These data suggest that the presence of S does not affect the mass transfer of Au from degassing silicate melt to an exsolved, low-salinity vapor in a low-f_S2 assemblage (i.e., pyrrhotite-magnetite at NNO) at the experimental conditions reported here. Efficiencies of removal are calculated and used to model the mass transfer of Au from a crystallizing silicate melt to an exsolved, low-salinity vapor phase. The calculations suggest that the model, absolute tonnage of Au scavenged and transported by S-free and S-bearing vapors, from a crystallizing melt, would be comparable and that the time-integrated flux of low-salinity vapor could be responsible for a significant quantity of the Au in magmatic-hydrothermal ore deposits.     

NaCl-X-H2O三元体系25℃等温蒸发石盐流体包裹体均一温度实验研究

复杂卤水组分对于石盐流体包裹体均一温度的影响尚不明确,文章基于NaCl-X-H_2O(X=KCl, MgCl_2,CaCl_2, Na_2SO_4)三元卤水体系,尝试探讨K~+、Mg~(2+)、Ca~(2+)、SO_4~(2-)对石盐流体包裹体均一温度测试结果的影响。不同卤水体系最大均一温度分析结果表明,K~+、Mg~(2+)、Ca~(2+)的存在总体上会导致石盐流体包裹体均一温度偏大,SO_4~(2-)的存在对均一温度的影响很小。以NaCl-H_2O体系为参照,NaCl-Na_2SO_4-H_2O体系平均均一温度较之要低,而NaCl-KCl-H_2O、NaCl-MgCl_2-H_2O和NaCl-CaCl_2-H_2O体系与其相反。NaCl-KCl-H_2O体系中的KCl浓度与平均均一温度呈现负相关关系,NaCl-MgCl_2-H_2O、NaCl-CaCl_2-H_2O、NaCl-Na_2SO_4-H_2O体系中的w(MgCl_2)、w(CaCl_2)和w(Na_2SO_4)与平均均一温度则呈现正相关关系。平均和最大均一温度分析结果都显示出复杂卤水体系中不同离子及其浓度对石盐流体包裹体均一温度会产生影响。本研究对于具有复杂化学组分卤水结晶析出石盐均一温度的研究具有重要的参考价值。