The Escanaba Trough, Gorda Ridge hydrothermal system: Temporal stability and subseafloor complexity

The composition and temperature of vent fluids sampled from the active hydrothermal system in Escanaba Trough, Gorda Ridge in 2000 and 2002 remain unchanged from the only time this field was previously sampled, in 1988. ODP Leg 169 drilled nine bore holes at this site in 1996, some within meters of the vents, yet this disturbance has not impacted the measured compositions or temperatures of the fluids exiting at the seafloor. The fluids have maximum measured temperatures of 218°C and contain ∼20% more chloride than local ambient seawater. Our interpretation is that the fluid compositions are generated by supercritical phase separation of seawater, with much of the water-rock reaction occurring within the ∼400m thick sedimentary section that overlies the basalt at this site. The ODP drilling results provide information on the mineralogy and composition of materials below the seafloor, as well as direct constraints not typically available on the physical conditions occurring below the seafloor hydrothermal system. Calculations utilizing geochemical modeling software suggest the fluids are close to saturation with a suite of minerals found subsurface, suggesting equilibrium between the fluids and substrate. These results provide an explanation for why the fluids have remained chemically stable for 14 yrs. The pore water data from drilling suggest that the hydrology and chemistry of the hydrothermal system are much more complex within the sediment cover than would be expected from the surface manifestations of the hydrothermal system. While the pore waters have chloride contents both greater and less than the local seawater, only fluids with higher chloride contents vent at the seafloor. Our calculations suggest that at the current conditions the “brines” (fluids with chlorinity greater than seawater) are actually less dense than the “vapors” (fluids with chlorinity less than seawater). These density relationships may provide an explanation for why the “brines” are now venting preferentially to the “vapors,” a situation opposite to what is usually observed or inferred.     

Carbon isotope systematics of individual hydrocarbons in hydrothermal petroleum from Escanaba Trough, northeastern Pacific Ocean

We submitted individual aliphatic and polycyclic aromatic hydrocarbons in samples of hydrothermal petroleum from Escanaba Trough to compound specific isotope analysis to trace their origins. The carbon isotope compositions of the alkanes and polycyclic aromatic hydrocarbons (means -27.5 and -24.7%, respectively) reflect a primarily terrestrial organic matter source.     

Lithium isotope geochemistry of marine pore waters - Insights from cold seep fluids

Lithium concentration and isotope data (δ⁷Li) are reported for pore fluids from 18 cold seep locations together with reference fluids from shallow marine environments, a sediment-hosted hydrothermal system and two Mediterranean brine basins. The new reference data and literature data of hydrothermal fluids and pore fluids from the Ocean Drilling Program follow an empirical relationship between Li concentration and δ⁷Li (δ⁷Li = −6.0(±0.3) · ln[Li] + 51(±1.2)) reflecting Li release from sediment or rocks and/or uptake of Li during mineral authigenesis. Cold seep fluids display δ⁷Li values between +7.5‰ and +45.7‰, mostly in agreement with this general relationship. Ubiquitous diagenetic signals of clay dehydration in all cold seep fluids indicate that authigenic smectite-illite is the major sink for light pore water Li in deeply buried continental margin sediments. Deviations from the general relationship are attributed to the varying provenance and composition of sediments or to transport-related fractionation trends. Pore fluids on passive margins receive disproportionally high amounts of Li from intensely weathered and transported terrigenous matter. By contrast, on convergent margins and in other settings with strong volcanogenic input, Li concentrations in pore water are lower because of intense Li uptake by alteration minerals and, most notably, adsorption of Li onto smectite. The latter process is not accompanied by isotope fractionation, as revealed from a separate study on shallow sediments. A numerical transport-reaction model was applied to simulate Li isotope fractionation during upwelling of pore fluids. It is demonstrated that slow pore water advection (order of mm a⁻¹) suffices to convey much of the deep-seated diagenetic Li signal into shallow sediments. If carefully applied, Li isotope systematics may, thus, provide a valuable record of fluid/mineral interaction that has been inherited several hundreds or thousands of meters below the actual seafloor fluid escape structure.     

Dissolved organic carbon in interstitial waters from sediments of Middle Valley and Escanaba Trough,Northeast Pacific,ODP Legs 139 and 169

Oxidation measurements of nonvolatile dissolved organic carbon (DOC) have been determined by high temperature combustion for pore waters from sediments of Middle Valley and Escanaba Trough, Northeastern Pacific, sampled by the Ocean Drilling Program (ODP) Legs 139 and 169, as well as for overlying and near bottom seawater. The DOC values in the interstitial waters are generally greater than those in the overlying water column, ranging from 0.1 to 158 mg of C per liter (mg C/L). Some of the profiles of DOC in the pore waters are similar to total organic C and total inorganic C profiles. DOC maxima at shallow depths of Site 858 are probably enriched due to higher temperature alteration of organic matter. At Sites 856 and 1035, the DOC increases at greather depths due to the hydrothermal activity. The DOC values correlate with MnO and MgO profiles in Hole 856B. The changes below 30 mbsf in the DOC depth profiles of Sites 858 and 1036 parallel those of the volatile hydrocarbon gases. The reference Site 1037 in Escanaba Trough has DOC values that increase with depth according to the increase in thermal stress.     

Noble gas and carbon isotopes in Mariana Trough basalt glasses

Noble gas elemental and isotopic compositions have been measured as well as the abundance of C and its isotopic ratios in 11 glasses from submarine pillow basalts collected from the Mariana Trough. The ³He/⁴He ratios of 8.22 and 8.51 R_atm of samples dredged from the central Mariana Trough (∼18°N) agree well with that of the Mid-Ocean Ridge Basalt (MORB) glasses (8.4±0.3 R_atm), whereas a mean ratio of 8.06±0.35 R_atm in samples from the northern Mariana Trough (∼20°N) is slightly lower than those of MORB. One sample shows apparent excess of ²⁰Ne and ²¹Ne relative to atmospheric Ne, suggesting incorporation of solar-type Ne in the magma source. There is a positive correlation between ³He/⁴He and ⁴⁰Ar/³⁶Ar ratios, which may be explained by mixing between MORB-type and atmospheric noble gases. Excess ¹²⁹Xe is observed in the sample which also shows ²⁰Ne and ²¹Ne excesses. Observed δ¹³C values of ∼20°N samples vary from −3.76‰ to −2.80‰, and appear higher than those of MORB, and the corresponding CO₂/³He ratios are higher than those of MARA samples at ∼18°N, suggesting C contribution from the subducted slab.     

Origin of ore fluids in the Muruntau gold system: Constraints from noble gas, carbon isotope and halogen data

Hydrothermal vein minerals directly associated with native gold mineralization in the Muruntau vein system (Uzbekistan) have been studied for noble gas, carbon isotope and halogen chemistry of the trapped ore-related fluids. Helium trapped in early arsenopyrite 1, which has preserved the original fluid signature better than associated scheelite and quartz, indicates a small input from a mantle source (?5% of total He). However, the overwhelming majority of the He in the fluid (∼95%) is from crustal sources. The noble gases Ne, Kr and Xe in the sample fluids are dominated by gases of atmospheric origin. The carbon isotope (δ¹³C: −2.1‰ to −5.3‰) and halogen characteristics of the fluids (log Br/Cl: −2.64 to −3.23) lend further support for the activity of juvenile fluids during the main ore stage. The high proportion of crustal components in the ore-forming fluids may be explained by intense fluid-rock interaction and is also supported by previous Nd and Sr isotope studies. The involvement of a juvenile fluid component during the main stage of hydrothermal activity at Muruntau (∼275 Ma) can be linked to the emplacement of lamprophyric dikes at Muruntau, due to apparently overlapping ages for high-temperature alteration, related ore vein formation and intrusion of the dikes. The input of mantle-derived fluids, possibly related to the Hercynian collisional event in the western Tien Shan, stimulated intense fluid-rock interaction in the crust. In this context, the mantle-derived fluid should be considered as one possible carrier of metals. Significant amounts of external meteoric fluids circulating in fracture systems are interpreted to have modified the noble gas signature of fluid in quartz, mostly during late, low temperature fluid circulation.     

Argon and halogen geochemistry of hydrothermal fluids in the Loch Ainort granite,Isle of Skye,Scotland

Highly turbid alkali feldspars from the Loch Ainort granite (59 Ma), Isle of Skye, have been analysed using the ⁴⁰Ar-³⁹Ar method to obtain chronological and chemical (K, Cl, Br, I) information concerning their origin and hydrothermal alteration. Three methods of gas extraction have been applied to neutron-irradiated samples: laser probe spot fusion of feldspars, in vacuo crushing of a feldspar/quartz separate, and laser stepped heating of the crushed residue. Apparent ages obtained by laser probe spot fusion are mostly similar to the 59 Ma intrusion age. Analyses of relatively pristine regions give some high apparent ages (>59 Ma) indicating the presence of small amounts of ⁴⁰Ar_E (excess ⁴⁰Ar). Crushing releases significant amounts of ⁴⁰Ar_E, but is dominated by an ⁴⁰Ar_A (atmospheric ⁴⁰Ar) component. ⁸⁴Kr/³⁶Ar values obtained by crushing are higher than air and are consistent with air equilibration with fresh water at low temperature 20°C). Therefore, ⁴⁰Ar_A was most probably introduced as palaeoatmospheric argon dissolved in the circulating hydrothermal fluids that interacted with the granite, thus supporting a meteoric origin for the fluids. Stepped heating gives a flat age spectrum and an age of 56±4 Ma. Crushing and stepped heating both released significant amounts of halogens with high Br/Cl and I/Cl ratios; excess Xe is also present as indicated by the high ¹³²Xe/³⁶Ar values. It seems likely that the halogen (and possibly Xe) enrichments resulted from interaction of the meteoric fluids with Jurassic sedimentary country rocks.     

Helium measurements of pore fluids obtained from the San Andreas Fault Observatory at Depth (SAFOD, USA) drill cores

⁴He accumulated in fluids is a well established geochemical tracer used to study crustal fluid dynamics. Direct fluid samples are not always collectable; therefore, a method to extract rare gases from matrix fluids of whole rocks by diffusion has been adapted. Helium was measured on matrix fluids extracted from sandstones and mudstones recovered during the San Andreas Fault Observatory at Depth (SAFOD) drilling in California, USA. Samples were typically collected as subcores or from drillcore fragments. Helium concentration and isotope ratios were measured 4?C6 times on each sample, and indicate a bulk ⁴He diffusion coefficient of 3.5?±?1.3?×?10^?C8 cm²?s^?C1 at 21°C, compared to previously published diffusion coefficients of 1.2?×?10^?C18 cm²?s^?C1 (21°C) to 3.0?×?10^?C15 cm²?s^?C1 (150°C) in the sands and clays. Correcting the diffusion coefficient of ⁴He_water for matrix porosity (??3%) and tortuosity (??6?C13) produces effective diffusion coefficients of 1?×?10^?C8 cm^2?s^?C1 (21°C) and 1?×?10^?C7 (120°C), effectively isolating pore fluid ⁴He from the ⁴He contained in the rock matrix. Model calculations indicate that <6% of helium initially dissolved in pore fluids was lost during the sampling process. Complete and quantitative extraction of the pore fluids provide minimum in situ porosity values for sandstones 2.8?±?0.4% (SD, n?=?4) and mudstones 3.1?±?0.8% (SD, n?=?4).     

Partition geochemistry of hydrothermal precipitates from submarine hydrothermal fields in the Hellenic Volcanic Island Arc

The geochemical study of 5 sediment cores obtained from different shallow hydrothermal fields along the volcanic arc (Methana, Milos, Kos and Yali), revealed that the degree of rock hydrothermal alteration from one area to another is different and is influenced by the physical and geochemical properties of the hydrothermal venting fluids and the type of the rocks in the substrate. The submarine hydrothermal fields in the central Aegean Sea are linked with the Hellenic Volcanic Arc and imprint their hydrothermal influence on the local marine sediments. Hydrothermal venting fluids differ in pH, temperature, gas and metallic element content, intensity of gas and water flux, while rock substrate is variable in terms of thickness and chemistry of the marine sediments and the mineral deposits. The analytical results showed that the lowest values of Fe are observed in Palaeochori Bay (0.72%) and the highest values are found in Bros Thermi (2.72%). The highest Mn concentrations are found in Bros Thermi (407 ppm) and the lowest are found in Yali (29 ppm). Cu and Pb highest concentrations are found in Bros Thermi (21 ppm) and Thiafi Bay (16 ppm), and the lowest in Yali (1 ppm). Zn highest values are found in Bros Thermi (56 ppm) and the lowest values in Kephalos Bay (10 ppm). Finally, the Ca and Mg-richest layers are observed in Kephalos 7.5 and 0.98% respectively and the lowest are observed in Milos (0.01% for Ca) and Yali (0.12% for Mg). The hydrothermal activity presented variations with geological time and hydrothermal suspended particulate matter coming out from the vent outlets also influence the sediment geochemistry. As an example in Methana, high concentrations of Cu and Zn in SPM result in high levels of Cu and Zn in the sediments.     

页岩气储层孔隙分类与表征

页岩气储层作为一种非常规储集体,对于其孔隙类型,目前国际上尚没有统一分类方案。由于其孔隙结构的特殊性,常规孔隙表征方法也难以对页岩气储层的孔隙特征进行有效的表征。为此,在充分调研和系统总结国际上有关页岩气储层孔隙分类现状的基础上,结合页岩储层的特殊性,提出了页岩气储层孔隙的产状结构综合分类方案。该方案综合考虑了孔隙定性观察和定量测定的信息。根据定性观察的孔隙产状,把页岩气储层的孔隙类型划分为与岩石颗粒发育无关的和与岩石颗粒发育有关的两个大类。前者即为裂缝孔隙,后者为岩石基质孔隙。岩石基质孔隙大类又进一步分成了发育在颗粒和晶体之间的粒间孔隙、包含在颗粒边界以内的粒内孔隙和发育在有机质内的有机质孔隙。年轻的浅埋藏沉积物中只含有粒间和粒内孔隙,这些孔隙随着埋藏和压实而大大减少。随着埋深的增加,伴随着烃类的热成熟,有机孔隙开始发育,同时,随着烃类热成熟过程中有机酸的排放,导致溶解孔隙的形成。再结合定量测定的孔隙结构信息,把孔隙划分为微孔隙、中孔隙和宏孔隙。综合上述不同产状孔隙类型的结构特征,即构成了文中的产状结构综合分类。同时,鉴于页岩气储层的特殊性以及难以用研究常规油气储层的方法和手段进行表征,文中介绍了目前最常用的页岩气储层孔隙表征的定性半定量观测和定量检测方法。前者包括透射电子显微镜、聚焦离子束抛光和场发射扫描电子显微镜方法,后者包括压汞分析、低压氮气吸附、低压二氧化碳吸附和核磁共振等方法。     

Helium and neon isotope geochemistry of some ground waters from the Canadian Precambrian Shield

Ground waters in a Precambrian granitic batholith at the Whiteshell Nuclear Research Establishment (WNRE) in Pinawa, Manitoba contain between 5 × 10^?5 and 10^?1 cc STP/g_H2O of radiogenic helium-4 but have relatively uniform ³He/⁴He ratios of between 0.6 × 10^?8 and 2.3 × 10³. The highest helium samples also contain radiogenic ^21,22Ne produced by (α,n) or (n,α) reactions with other isotopes. As much as 1.8 × 10^?9ccSTP/g_H2O of excess ²¹Ne and 3.8 × 10^?9ccSTP/gH₂O of excess ²²Ne have been measured. Helium and ²¹Ne ages of these ground waters, calculated on the basis of known crustal production rates of ⁴He and ²¹Ne, are unreasonably high (up to 2 × 10⁵ years) and incompatible with the ¹⁴C ages and other isotopic and hydrogeologic data. Uranium enrichment in the flow porosity of the granite may dominate ⁴He and ^21,22Ne production in this granite and mask the contributions from more typical U and Th concentrations in the rock matrix.At the Chalk River Nuclear Laboratories in Ontario helium concentrations in ground waters in a Precambrian monzonitic gneiss range from 1.5 × 10^?7 to 8.7 × 10^?4ccSTP/g_H2O with the ³He/⁴He ratios ranging from 2.0 × 10^?3 to 1.5 × 10^?7. The highest helium concentrations may be attributable to the presence of a thick uraniferous pegmatite vein and yield helium ages more than two orders of magnitude higher than the ¹⁴C ages. Application of He age dating equations to ground waters from Precambrian granitic rocks requires knowledge of the nature of uranium and thorium enrichment in the subsurface in order to select appropriate values for porosity and uranium and thorium concentration in the rock.     

Mineralogy and geochemistry of a Late Permian coal in the Dafang Coalfield, Guizhou, China: influence from siliceous and iron-rich calcic hydrothermal fluids

This paper describes the influence of siliceous and iron-rich calcic low-temperature hydrothermal fluids (LTHF) on the mineralogy and geochemistry of the Late Permian No. 11 Coal (anthracitic, R_r=2.85%) in the Dafang Coalfield in northwestern Guizhou Province, China. The No. 11 Coal has high contents of vein ankerite (10.2 vol.%) and vein quartz (11.4 vol.%), with formation temperatures of 85 and 180 °C, respectively, indicating that vein ankerite and vein quartz were derived from low-temperature calcic and siliceous hydrothermal fluids in two epigenetic episodes. The vein quartz appears to have formed earlier than vein ankerite did, and at least three distinct stages of ankerite formation with different Ca/Sr and Fe/Mn ratios were observed.The two types of mineral veins are sources of different suites of major and trace metals. Scanning electron microscope and sequential extraction studies show that, in addition to Fe, Mg, and Ca, vein ankerite is the dominant source of Mn, Cu, Ni, Pb, and Zn in the coal, and the contents of these five elements are as high as 0.09% and 74.0, 33.6, 185, and 289 μg/g, respectively. In contrast, vein quartz is the main carrier mineral for platinum-group elements (PGEs) Pd, Pt, and Ir in the coal, and the contents of Pd, Pt, and Ir are 1.57, 0.15, and 0.007 μg/g, respectively. Sequential extraction showed a high PGE content in the silicate fraction, up to 10.4 μg/g Pd, 1.23 μg/g Pt, and 0.05 μg/g Ir, respectively. It is concluded that the formation of ankerite and quartz and the anomalous enrichment of trace elements in the No. 11 Coal in the Dafang Coalfield, Guizhou, result from the influx of calcic and siliceous low-temperature hydrothermal fluids.     

Participation of hydrothermal fluids in the formation of deposits of the proterozoic Udokan-Chineysky ore system

Numerous Cu deposits of the Udokan-Chineysky ore district (Udokan deposit of cupriferous sandstones, deposits of the Chineysky pluton, etc.), which occur in sedimentary and igneous rocks, are similar in many genetic features. One of these features is the similar parameters of fluid inclusions (hydrothermal fluids) in quartz of the Udokan deposit, rich chalcopyrite ores from the Rudnyi (Rudnyie deposit, and veins of the Pravoingamakitsky deposit studied previously. Fluid inclusions have the same range of high salinity and homogenization temperatures. These studies combined with geological data allow us to consider the formation of contact sulfide ores from the Chineisky pluton and Pravoingamakitsky and Udokan deposits as a common compound fluid-magmatic ore-generating system. The sedimentary rocks primarily enriched in chalcopyrite, pyrite, and pyrrhotite of the entire section of the Udokan complex served as the host media for the hydrothermal fluids and deposits of various scales.     

Halogen concentrations in pore waters and sediments of the Nankai Trough,Japan: Implications for the origin of gas hydrates

Presented here are halogen concentrations (Cl, Br and I) in pore waters and sediments from three deep cores in gas hydrate fields of the Nankai Trough area. The three cores were drilled between 1999 and 2004 in different geologic regions of the northeastern Nankai Trough hydrate zone. Iodine concentrations in all three cores increase rapidly with depth from seawater concentrations (0.00043 mmol/L) to values of up to 0.45 mmol/L. The chemical form of I was identified as I⁻, in accordance with the anaerobic conditions in marine sediments below the SO₄ reduction depth. The increase in I is accompanied by a parallel, although lesser increase in Br concentrations, while Cl concentrations are close to seawater values throughout most of the profiles. Large concentration fluctuations of the three halogens in pore waters were found close to the lower boundary of the hydrate stability zone, related to processes of formation and dissociation of hydrates in this zone. Generally low concentrations of I and Br in sediments and the lack of correlation between sediment and pore water profiles speak against derivation of I and Br from local sediments and suggest transport of halogen rich fluids into the gas hydrate fields. Differences in the concentration profiles between the three cores indicate that modes of transportation shifted from an essentially vertical pattern in a sedimentary basin location to more horizontal patterns in accretionary ridge settings. Because of the close association between organic material and I and the similarity of transport behavior for I⁻ and CH₄, the results suggest that the CH₄ in the gas hydrates also was transported by aqueous fluids from older sediments into the present layers.     

Hydrothermal alteration of organic matter in sediments of the Northeastern Pacific Ocean: Part 2. Escanaba Trough,Gorda Ridge

Samples from the Ocean Drilling Program Leg 169 in Escanaba Trough, Gorda Ridge, NE Pacific Ocean, were analyzed to study maturation by accelerated diagenesis and/or by catagenesis of the sedimentary organic matter to hydrothermal petroleum. At Site 1038 the hydrothermal petroleums have migrated after generation to shallower horizons. The n-alkane maturation was indicated by the strong even C number preference (i.e., CPI <1.0) as in the case of Middle Valley. All samples contained admixed organic matter of terrigenous and marine components as indicated by the distributions of the biomarkers. The biological precursors were catagenetically altered to their equivalent mature compounds. The presence of high molecular weight PAHs in some sediment sections at Site 1038 reflected the high temperature alteration and reworking of organic matter into mature hydrothermal petroleum. At Site 1037, the reference hole in the Escanaba Trough, the n-alkanes with a strong predominance of odd C number homologs reflected immature non-marine lipid components essentially throughout the hole. Maturation of organic matter was only observed below 450 mbsf with n-alkanes showing a CPI <1.0. The strong even C number predominance in those intervals was attributed to initial maturation by high heat flow during the early rifting process.     

海底热水成矿系统中的流体端员与混合过程：来自白银厂和呷村VMS矿床的流体包裹体证据

古今海底热液流体系统是人们关注的重要科学问题,正确识别流体系统中不同来源的流体端员及其混合-分离过程,是深刻理解海底流体系统及火山成因块状硫化物(VMS)矿床成因的关键。本文选择了我国境内两个典型的VMS矿床:甘肃白银厂矿床和四川呷村矿床,分别对上部块状矿带和下部脉状-网脉状矿带进行了系统的流体包裹体研究。研究表明,海底热液成矿流体系统是一个富集CO_2和CH_4的NaCl-H_2O流体系统。在此系统中,至少已鉴别出5种端员流体,即(1)低温 (12wt％NaCl)卤水;(2)高温(>320℃)高盐度(>14.5wt％NaCl)流体和(3)高温(>350℃)中盐度(10～16wt％Nacl)富气流体,以及(4)低温(～100℃)低盐度(2～5wt％NaCl)流体和(5)中温低盐度流体,它们构成了3个相互分离的温度-盐度演变趋势或混合途径。)低温高盐度卤水封存于卤水池中,在呷村矿床,卤水池发育在海底凹陷盆地热液区内,在白银厂矿床,卤水池则发育在海底之下的多孔火山碎屑岩单元及穿透性断裂破碎带内。高温高盐度流体和高温中盐度富气流体均来自矿区下部浅位岩浆房,前者以液态富金属H_2O流体为主,通常与冷海水发生混合;后者以富CO_2和CH_4的气体为主,高温(>450℃)下呈相对独立的气流存在,至到250～260℃才作为液相混入成矿热液流体中。低温低盐度     

Carbon-oxygen isotopic geochemistry of the Yangla Cu skarn deposit,SW China: Implications for the source and evolution of hydrothermal fluids

The Yangla Cu deposit is the largest Cu skarn deposit in the Jinshajiang tectonic belt. Based on the detailed observation of crosscutting relationships, three mineralization stages (i.e., pre-ore, ore and supergene) have been identified in the Yangla deposit. The pre-ore stage is dominated by prograde skarn. The ore stage is characterized by the precipitation of hydrous silicate minerals, Fe-oxides, Fe-Cu-Mo-sulfides, quartz and calcite, whose mineral assemblages were formed in the early and late sub-ore stages. The early sub-ore stage is marked by retrograde alteration with the deposition of hydrous silicate minerals (e.g., actinolite, epidote and chlorite), Fe-oxides, abundant Fe-Cu-Mo-sulfides, quartz and minor calcite. Whilst, the late sub-ore stage, associated with silicic and carbonate alteration, is represented by widespread thick quartz or calcite veins with disseminated pyrite, chalcopyrite, galena and sphalerite. We present new carbon-oxygen (C-O) isotopic compositions of the ore-hosting marble and hydrothermal calcite of this deposit. The hydrothermal calcite in the Yangla deposit was precipitated from both the early and late sub-ore stages. Calcite I from the early sub-ore stage is anhedral, and occurs as spot in the skarn or locally replaces the skarn minerals. Calcite II from the late sub-ore stage is distinguished by being coarse-grained, subhedral to euhedral and its occurrence in thick veins. Calcite I contains lower δ¹³C_PDB (−7.0‰ to −5.0‰) and δ¹⁸O_SMOW (7.2‰ to 12.7‰) than Calcite II (δ¹³C_PDB = −4.5‰ to −2.3‰; δ¹⁸O_SMOW = 10.7‰ to 19.4‰). In the δ¹³C_PDB vs. δ¹⁸O_SMOW diagram, the Calcite I and Calcite II data fall close to the igneous carbonatite field and between the fields of igneous carbonatite and marine carbonates, respectively. This suggests a dominantly magmatic origin for the early sub-ore fluids, and there might have been increasing carbonate wall rock involvement towards the late sub-ore stage. The ore-hosting marble (δ¹³C_PDB = −4.8‰ to −0.3‰; δ¹⁸O_SMOW = 10.2‰ to 23.9‰) also shows a positive δ¹³C_PDB vs. δ¹⁸O_SMOW correlation, which is interpreted to reflect the decreasing alteration intensity during the interactions between the hydrothermal fluids and ore-hosting carbonates. Simulated calculation suggests that both the Calcite I and Calcite II precipitated at 350 °C to 250 °C and 250 °C to 150 °C, respectively. We proposed that CO₂ degassing and water/rock interactions were likely the two major processes that precipitated the calcite and led to the observed C-O isotopic features of the Yangla Cu deposit.     

苏鲁超高压变质岩区深部流体He-Ar的系统关系：中国大陆科学钻探工程在线流体监测的解析

中国大陆科学钻探工程在线监测从泥浆中分离出的气体地球化学组成揭示了一段重要的气体异常,从2004年12月24日夜里开始到12月29日晚上结束。从12月10日到24日晚上11点30分的气体的Ar、He和N2基本上沿着趋势A分布,而12月26日早上7点半到29日晚上7点半的数据沿趋势C分布。相对于趋势A,趋势C中的气体含有相对升高的Ar,Ar/He和Ar/N2的平均值分别为3653和0.0142,明显高于空气的比值1800和0.0119。趋势A中的气体的Ar/He和Ar/N2比值分别围绕1851和0.0118变化,其中的Ar/He比值稍微高于空气的比值,但Ar/N2比值近似于空气比值,表明背景地下流体含非常低的Ar,而He和N2主要是大气组分。在趋势A和趋势C之间的数据(时间段B)具有和空气接近的Ar/N2比值,但平均Ar/He比值为3265,明显高于空气比值,反映了该段气体具有相对亏损的He。苏鲁-大别山地区的热年代学研究已经表明云母和角闪石的Ar/Ar的冷却年龄大大地高于磷灰石或锆石的He的冷却年龄,说明Ar在超高压变质地体折返早期就已封闭,而He一直保持开放状态,直到超高压变质岩接近地表。这种Ar和He对温度变化的不同反应,导致大部分的He在超高压岩石折返过程中脱气并释放到空气中,Ar则相对圈闭在固体岩石或封闭的断裂带中。在He-Ar的系统关系上,表现为来自于超高压岩石或断裂带中的流体具有富集Ar、亏损He及升高的Ar/He比值。气体组分从趋势A向趋势C的骤然跳跃,反映了地下流体组分的强烈变化,即具有相对富集Ar的深部流体的贡献大大增强。     

Generation of fluorine-bearing fluids in hydrothermal experiments

Fluorine-bearing fluids can be generated by breakdown of PdF₂ in hydrothermal experiments. This promising technique allows addition of a fixed amount of F without affecting the composition of the rest of the system. The method is simpler, more flexible and potentially yields better results than most other techniques of F addition. Melting and crystallization experiments using natural starting materials are particularly well suited to application of this method.