叶蜡石化蚀变过程中的元素活动性与流体性质:以山西五台地区白云叶蜡石矿为例

热液蚀变过程中的元素活动性与流体性质对深入理解矿物稳定性和成矿作用具有重要的意义。本文以华北克拉通中北部山西五台地区的白云叶蜡石矿为例,研究了蚀变过程中元素迁移特征和流体性质。该矿体围岩以绿片岩相酸性火山岩为主,岩性为绢云钠长石英片岩并夹有少量的绿泥钠长片岩。矿区内蚀变分带明显,可分为早期的黄铁绢英岩化(绢云母-石英-黄铁矿)和晚期叠加的叶蜡石化(叶蜡石-伊利石-高岭石-石英),而金矿化则主要发育于黄铁绢英岩化带内。Log fo2-pH相图模拟结果显示,早期黄铁绢云岩化蚀变热液具有弱酸性至偏中性(pH=5.24~5.87)和较低氧逸度(位于黄铁矿+黄铜矿稳定相区内)特征;而引起叶蜡石化蚀变的热液具有强酸性(pH=2.07~2.20)和高氧逸度(位于HM缓冲线以上)特征。质量平衡迁移分析结果显示,随着叶蜡石化蚀变作用的增强,叶蜡石矿石中的Al2O3行为较稳定,SiO2、Na2O和K2O含量相对于围岩绢云钠长石英片岩呈不同程度的迁入,而其余氧化物大量活化迁出。微量元素Nb、Ta、Th、U、Rb和Ga含量相对升高,Th/U比值略有升高;Sr、Ba、Zr、Hf明显亏损,Zr/Hf比值从34~41下降到17~22。稀土元素均发生一定程度的活化迁移,且轻稀土迁出程度更高。Y/Ho比值(28~32)高于球粒陨石的Y/Ho(26~28),表明Y-Ho在叶蜡石化蚀变过程中表现出不同的地球化学行为。Eu负异常明显增大,这可能与长石的分解关系密切。围岩绢云钠长石英片岩中金属元素含量较高且Au与As含量之间呈明显正相关性,但在叶蜡石矿石中大部分金属元素含量均低于检出限,说明金属元素在叶蜡石化蚀变作用过程中发生了强烈的活化迁移,这与岩相学上叶蜡石矿石中可见港湾状细粒赤铁矿而缺乏黄铁矿的特征吻合。本文研究结果表明叶蜡石化过程中,大量的所谓不活动元素(如P、Ti、Zr、Hf、Y和Ho等)发生了显著迁移并导致Zr/Hf和Y/Ho比值的解耦,并伴随着大量金属元素的迁出,说明叶蜡石化不利于金矿化的形成。     

Chadormalu Kiruna-type magnetite-apatite deposit,Bafq district,Iran: Insights into hydrothermal alteration and petrogenesis from geochemical,fluid inclusion,and sulfur isotope data

The Chadormalu is one of the largest known iron deposits in the Bafq metallogenic province in the Kashmar-Kerman belt, Central Iran. The deposit is hosted in Precambrian-Cambrian igneous rocks, represented by rhyolite, rhyodacite, granite, diorite, and diabasic dikes, as well as metamorphic rocks consisting of various schists. The host rocks experienced Na (albite), calcic (actinolite), and potassic (K-feldspar and biotite) hydrothermal alteration associated with the formation of magnetite–(apatite) bodies, which are characteristic of iron oxide copper-gold (IOCG) and iron oxide-apatite (IOA) systems. Iron ores, occurring as massive-type and vein-type bodies, consist of three main generations of magnetite, including primary, secondary, and recrystallized, which are chemically different. Apatite occurs as scattered irregular veinlets in various parts of the main massive ore-body, as well as apatite-magnetite veins and disseminated apatite grains in marginal parts of the deposit and in the immediate wall rocks. Minor pyrite occurs as a late phase in the iron ores. Chemical composition of magnetite is representative of an IOA or Kiruna-type deposit, which is consistent with other evidence.Whole rock geochemical data from various host rocks confirm the occurrence of Na, Ca, and K alteration consistent with the formation of albite, actinolite, and K-feldspar, respectively. The geochemical investigation also includes the nature of calc-alkaline igneous rocks, and helps elaborating on the spatial and temporal association, and possible contribution of mafic to felsic magmas to the evolution of ore-bearing hydrothermal fluids.Fluid inclusion studies on apatites from massive- and vein-type ores show a range of homogenization temperatures from 266 to 580 °C and 208–406 °C, and salinities from 0.5 to 10.7 wt.% and 0.3–24.4 wt.% NaCl equiv., respectively. The fluid inclusion data suggest the involvement of evolving fluids, from low salinity-high temperature, to high salinity-low temperature, in the formation of the massive- and vein-type ores, respectively. The δ³⁴S values obtained for pyrite from various parts of the deposit range between +8.9 and +14.4‰ for massive ore and +18.7 to +21.5‰ for vein-type ore. A possible source of sulfur for the ³⁴S-enriched pyrite would be originated from late Precambrian-early Cambrian marine sulfate, or fluids equilibrated with evaporitic sulfates.Field observations, ore mineral and alteration assemblages, coupled with lithogeochemical, fluid inclusion, and sulfur isotopic data suggest that an evolving fluid from magmatic dominated to surficial brine-rich fluid has contributed to the formation of the Chadormalu deposit. In the first stages of mineralization, magmatic derived fluids had a dominant role in the formation of the massive-type ores, whereas a later brine with higher δ³⁴S contributed to the formation of the vein-type ores.     

Exploring the ocean for hydrothermal venting: New techniques,new discoveries,new insights

Enumerating active hydrothermal fields on the seafloor has been a challenge since their discovery almost 40 years ago. High-temperature hydrothermal fields are readily discoverable, primarily by detecting mineral-laden plumes, but low-temperature, particle-poor vent fields resist discovery. Decades of exploration for vent fields have covered, though often cursorily, about one-third of the global lengths of both oceanic spreading ridges (OSRs) and volcanic arcs, identifying some 630 active vent fields. About 80% of these fields are on OSRs, and the spatial frequency of those fields is currently estimated as ∼0.5–5/100 km, generally increasing with spreading rate. Over the last decade, however, a few detailed surveys have added sensors capable of detecting ephemeral chemical tracers (oxidation-reduction potential) in addition to standard sensors that detect quasi-conservative optical tracers (such as light backscattering). This approach has revealed a new view of the distribution of venting fields along fast-spreading (>55 mm/yr) OSRs. Studies of four such ridge sections totaling 1470 km length suggest that the present inventory of vent fields may underestimate the true global population of vent fields on fast-spreading OSRs by a factor of 3–6. This increase implies that ridge axes are unexpectedly “leaky” reservoirs, from which hydrothermal fluids escape at far more sites than presently assumed; that the supply of dissolved hydrothermal iron, which may be fertilizing the primary production of the Southern Ocean, is higher than now calculated; and that present estimates of recoverable sulfide tonnage from ridge axes may be too low. Along slow-spreading ridges, which account for 60% of the global OSR length and 86% of known sulfide tonnage, expansive axial valleys present special exploration challenges that will not be easily overcome.     

Submarine hydrothermal contribution for the extreme element accumulation during the early Cambrian,South China

Throughout the geological history of the Earth, submarine hydrothermal activity has played an important role in seawater chemistry, biological evolution and enrichment of metals in the Earth crust. However, the prospect of hydrothermal activity for extreme element accumulation during the early Cambrian, a key geological period, in South China has not been well-constrained. This study reports geochemical (e.g. REE and Sr isotope) investigations of a coarse-grained limestone layer and associated calcite veins in Zunyi and Nayong areas, Guizhou Province, to constrain the hydrothermal activity and evaluate the significance of hydrothermal contribution to extreme element accumulation during the early Cambrian, South China. Our results reveal positive Eu anomalies and higher initial ⁸⁷Sr/⁸⁶Sr ratios (0.7083–0.7150) for carbonate samples than those of early Cambrian seawater, indicating the presence of hydrothermal processes. Combined with constraints from the spatial relationships and coincidence with adjacent mineralization, these hydrothermal processes provide the most probable contribution for polymetallic Ni–Mo–PGE mineralization. Furthermore, there are abundant hydrothermal dolomite and barite-calcite veins in the dolostone of the Dengying Formation, indicating the occurrence of a variety of hydrothermal fluids. Overall, multi-stage hydrothermal pulses with different fluid compositions spanned the Ediacaran–Cambrian transition in South China. In particular, these hydrothermal fluids with positive Eu anomalies and enriched radiogenic Sr, originating from Proterozoic mafic/ultramafic rocks, may have flowed through the underlying Precambrian silicate clastic rocks (e.g., Xiajiang, Banxi and Lengjiaxi Groups) and may have been crucial for the marine environment, biological diversity and extreme element accumulation during the early Cambrian, South China.     

Ore petrology,hydrothermal alteration,fluid inclusions,and sulfur stable isotopes of the Milin Kamak intermediate sulfidation epithermal Au-Ag deposit in Western Srednogorie,Bulgaria

The Milin Kamak gold-silver deposit is located in Western Srednogorie zone, 50 km west of Sofia, Bulgaria. This zone belongs to the Late Cretaceous Apuseni-Banat-Timok-Srednogorie magmatic and metallogenic belt. The deposit is hosted by altered trachybasalt to andesitic trachybasalt volcanic and volcanoclastic rocks with Upper Cretaceous age, which are considered to be products of the Breznik paleovolcano. Milin Kamak is the first gold-silver intermediate sulfidation type epithermal deposit recognized in Srednogorie zone in Bulgaria. It consists of eight ore zones with lengths ranging from 400 to 1000 m, widths from several cm to 3–4 m, rarely to 10–15 m, an average of 80–90 m depth (a maximum of 200 m) and dip steeply to the south. The average content of gold is 5.04 g/t and silver – 13.01 g/t. The styles of alteration are propylitic, sericite, argillic, and advanced argillic. Ore mineralization consists of three stages. Quartz-pyrite stage I is dominated by quartz, euhedral to subhedral pyrite, trace pyrrhotite and hematite in the upper levels of the deposit. Quartz-polymetallic stage II is represented by major anhedral pyrite, galena, Fe-poor sphalerite; minor chalcopyrite, tennantite, bournonite, tellurides and electrum; and trace pyrrhotite, arsenopyrite, marcasite. Gangue minerals are quartz and carbonates. The carbonate-gold stage III is defined by deposition of carbonate minerals and barite with native gold and stibnite.Fluid inclusions in quartz are liquid H₂O-rich with homogenization temperature (T_h) ranging from 238 to 345 °C as the majority of the measurements are in the range 238–273 °C. Ice-melting temperatures (T_m) range from −2.2 to −4.1 °C, salinity – from 3.7 to 6.6 wt.% NaCl equiv. These measurements imply an epithermal environment and low- to moderate salinity of the ore-forming fluids.δ³⁴S values of pyrite range from −0.49 to +2.44‰. The average calculated δ³⁴S values are 1.35‰. The total range of δ³⁴S values for pyrite are close to zero suggesting a magmatic source for the sulfur.     

Gold mineralizing efficiency during hydrothermal alteration of the Mesozoic granitoids in the northwest Jiaodong Peninsula: Contrasting conditions between the Guojialing and Linglong plutons

Mesozoic granitoids were extensively altered by hydrothermal fluids in the northwest Jiaodong Peninsula, and gold precipitated from the fluids developing prevalent mineralization in this district. The 160–158 Ma Linglong granite and 130–120 Ma Guojialing granodiorite are the major Mesozoic granitoids in this district, both of which are hydrothermally altered and intimately associated with gold mineralization. Although numerous studies were carried out by previous researchers, mainly focusing on tectonics, lithology, mineralogy, geochronology, and fluid geochemistry, knowledge about hydrothermal alteration processes of these granitoids and their gold mineralization efficiency (i.e. which one is more effective to precipitate the gold from its parent solution) is far beyond clear illumination. Geochemical simulation software GEM-Selektor (based on the Gibbs energy minimization algorithm) was applied in this study, which aims to test the gold mineralization efficiency of these two granitoids during the hydrothermal alteration processes. Simulation results indicate that solutions in equilibrium with the Linglong granite are capable of hosting more sulfur than that with the Guojialing granodiorite, since the latter contains more Fe. However, the solutions with these two granitoids display similar gold solubility. “Bulk cooling” simulation results show that the gold mineralization pattern is similar between the Linglong and Guojialing case; “Rock titration” simulation results reveal that the Guojialing granodiorite is prone to precipitate gold more strongly than the Linglong granite, as gold-bearing solutions (or ore-forming fluids) flowing-through at high temperature, equivalent to a deeper level, implying that if the gold mineralization is developed at depth, the Guojialing rock will precipitate more gold. If the gold-bearing solution flow-through the wall rocks relatively fast, and gold mineralization fails to take place, then the Guojialing granodiorite is probably unfavorable for subsequent gold enrichment of the ore-forming fluid. The Linglong granite will precipitate the gold more efficiently from its parent solution at low temperature or at a shallower level, and this is consistent with previous mining prospecting results. Therefore, we suggest that the Guojialing granodiorite should be treated as the main target during future deep prospecting project.     

Reactions between olivine and CO2-rich seawater at 300 °C: Implications for H2 generation and CO2 sequestration on the early Earth

To understand the influence of fluid CO₂ on ultramafic rock-hosted seafloor hydrothermal systems on the early Earth, we monitored the reaction between San Carlos olivine and a CO₂-rich NaCl fluid at 300 °C and 500 bars. During the experiments, the total carbonic acid concentration (ΣCO₂) in the fluid decreased from approximately 65 to 9 mmol/kg. Carbonate minerals, magnesite, and subordinate amount of dolomite were formed via the water-rock interaction. The H₂ concentration in the fluid reached approximately 39 mmol/kg within 2736 h, which is relatively lower than the concentration generated by the reaction between olivine and a CO₂-free NaCl solution at the same temperature. As seen in previous hydrothermal experiments using komatiite, ferrous iron incorporation into Mg-bearing carbonate minerals likely limited iron oxidation in the fluids and the resulting H₂ generation during the olivine alteration. Considering carbonate mineralogy over the temperature range of natural hydrothermal fields, H₂ generation is likely suppressed at temperatures below approximately 300 °C due to the formation of the Mg-bearing carbonates. Nevertheless, H₂ concentration in fluid at 300 °C could be still high due to the temperature dependency of magnetite stability in ultramafic systems. Moreover, the Mg-bearing carbonates may play a key role in the ocean-atmosphere system on the early Earth. Recent studies suggest that the subduction of carbonated ultramafic rocks may transport surface CO₂ species into the deep mantle. This process may have reduced the huge initial amount of CO₂ on the surface of the early Earth. Our approximate calculations demonstrate that the subduction of the Mg-bearing carbonates formed in komatiite likely played a crucial role as one of the CO₂ carriers from the surface to the deep mantle, even in hot subduction zones.     

柬埔寨柏威夏罗文德邦铜矿地质特征及找矿标志

对柬埔寨柏威夏罗文德邦已发现的铜矿体进行区域成矿地质条件、矿区地质特征、矿体特征及矿石特征进行分析研究;认为矿区含矿岩石为闪长玢岩类,含矿岩体与围岩同为二叠系的火山岩—次火山岩;含矿岩体受NWW向的构造控制;岩浆的侵入成岩和含矿热液作用,使近矿围岩受到广泛的交代蚀变,在岩浆沿构造上升交代蚀变过程中,岩浆中的黄铜矿、黄铁矿开始结晶熔离,岩浆上升达到赋存空间,使岩石绢英岩化,同时使有益元素黄铜矿、黄铁矿形成工业矿体,有局部的地段沿微型裂隙充填形成含矿石英脉和黄铜矿细脉;该矿床属热液交代-充填型;磁铁矿化、黄铁矿化、钾长石化、蚀变带等标志是该区的主要找矿标志。结合柏威夏罗文德邦铜矿床特征与区域上已发现的矿点综合分析,认为该区有着良好的找矿前景。     

Geochemistry of granitic aplite-pegmatite dykes and sills and their minerals from the Gravanho-Gouveia area in Central Portugal

Two distinct series of Variscan granitic rocks have been distinguished in the Gravanho-Gouveia area of Portugal, based on field work, variation diagrams for major and trace elements, rare earth patterns and δ¹⁸O versus total FeO diagram of rocks, anorthite content of plagioclase, BaO and P₂O₅ contents of feldspars and Al^VI versus Fe²⁺ diagram for magmatic muscovite. One series consists of a late-orogenic porphyritic biotite > muscovite granite (G1), less evolved beryl-columbite pegmatites and more evolved beryl-columbite pegmatites showing gradational contacts. The other series consists of post-orogenic porphyritic muscovite > biotite granodiorite to granite (G2), slightly porphyritic muscovite > biotite granite (G3) and lepidolite pegmatites. In each series, pegmatites are derived from the parent granite magma by fractional crystallization of quartz, plagioclase, K-feldspar, biotite and ilmenite. Some metasomatic effects occur like muscovite replacing feldspars, chlorite in pegmatites of the first series and a late muscovite in pegmatites of the second series, probably due to hydrothermal fluids. The lepidolite pegmatites contain cassiterite and two generations of rutile. The first magmatic generation consists of homogeneous crystals and the second generation occurs as heterogeneous zoned crystals derived from hydrothermal fluids. The beryl-columbite pegmatites and lepidolite pegmatites also contain the first magmatic generation and the late hydrothermal generation of zoned columbite-group minerals. More evolved beryl-columbite pegmatites were converted into episyenite by intense hydrothermal alteration and regional circulation of fluids in the granitic rocks.     

胶西北寺庄金矿床热液蚀变作用

胶东是我国最重要的金矿集区,其中"焦家式"破碎带蚀变岩型金矿是区内最重要的金矿床类型。寺庄金矿床位于胶东金矿集区焦家金矿田南部,是典型的"焦家式"金矿,沿NE向焦家断裂发育大规模的热液蚀变带,金矿体均产于这些蚀变带内。热液蚀变空间分带明显,距离焦家断裂由近到远向下盘依次发育黄铁绢英岩化、绢英岩化、钾长石化蚀变带。时间上,钾长石化为成矿前蚀变,绢英岩化和黄铁绢英岩化叠加在钾长石化蚀变之上,为成矿期蚀变,伴随金矿化。质量平衡计算表明:钾长石化过程,主量元素SiO_2、Al_2O_3、Fe_2O_3、FeO、MgO、CaO、Na_2O、P_2O_5,成矿元素Au、Ag,亲铜元素As、Hg、Sb、Bi和稀土元素均从玲珑黑云母花岗岩中迁出;而K_2O、MnO和Cu从流体中迁入玲珑黑云母花岗岩。绢英岩化和黄铁绢英岩化过程元素迁移行为高度相似,主量元素SiO_2、Fe_2O_3、FeO、MgO、CaO、K_2O、MnO,成矿元素Au、Ag,亲铜元素As、Hg、Cu、Sb、Bi和轻稀土元素均从流体中迁入钾长石化花岗岩,而主量元素Al_2O_3、Na_2O和重稀土元素均从钾长石化花岗岩中迁出。二长石温度计估算钾长石化蚀变形成的温度约为392～449℃。玲珑黑云母花岗岩(δEu=1.45)和钾长石化花岗岩(δEu=1.38)具有明显的Eu正异常,绢英岩(δEu=0.97)和黄铁绢英岩(δEu=0.93)具有轻微的Eu负异常,指示钾长石化发生于相对氧化环境下,而绢英岩化和黄铁绢英岩化发生于相对还原环境下。综合分析表明,成矿前高温、氧化、碱性流体作用于玲珑黑云母花岗岩形成大范围面状钾长石化蚀变;成矿期中低温、还原、弱酸性的流体与钾长石化花岗岩发生水岩反应,形成绢英岩化和黄铁绢英岩化,在此过程中硫化作用引起金硫络合物分解,导致金沉淀富集成矿。