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1.
Analyses of co-existing silicate melt and fluid inclusions, entrapped in quartz crystals in volatile saturated magmatic systems, allowed direct quantitative determination of fluid/melt partition coefficients. Investigations of various granitic systems (peralkaline to peraluminous in composition, log fO2 = NNO−1.7 to NNO+4.5) exsolving fluids with various chlorinities (1-14 mol/kg) allowed us to assess the effect of these variables on the fluid/melt partition coefficients (D). Partition coefficients for Pb, Zn, Ag and Fe show a nearly linear increase with the chlorinity of these fluid (DPb ∼ 6 ∗ mCl, DZn ∼ 8 ∗ mCl, DAg ∼ 4 ∗ mCl, DFe ∼ 1.4 ∗ mCl, where mCl is the molinity of Cl). This suggests that these metals are dissolved primarily as Cl-complexes and neither oxygen fugacity nor the composition of the melt affects significantly their fluid/melt partitioning. By contrast, partition coefficients for Mo, B, As, Sb and Bi are highest in low salinity (1-2 mol/kg Cl) fluids with maximum values of DMo ∼ 20, DB ∼ 15, DAs ∼ 13, DSb ∼ 8, DBi ∼ 15 indicating dissolution as non-chloride (e.g., hydroxy) complexes. Fluid/melt partition coefficients of copper are highly variable, but highest between vapor like fluids and silicate melt (DCu ? 2700), indicating an important role for ligands other than Cl. Partition coefficients for W generally increase with increasing chlorinity, but are exceptionally low in some of the studied brines which may indicate an effect of other parameters. Fluid/melt partition coefficients of Sn show a high variability but likely increase with the chlorinity of the fluid (DSn = 0.3-42, DW = 0.8-60), and decrease with decreasing oxygen fugacity or melt peraluminosity.  相似文献   
2.
Many modern seafloor tectonic environments are host to hydrothermal systems and associated polymetallic sulfide deposits. Metal transport and precipitation are controlled by magmatic processes such as pre-eruptive degassing and the hydrothermal cycle. The original availability of Pb and other ore metals in a given setting is dependent on concentrations in the original magmatic source or additional enrichment processes. We have examined the Pb budget of melt inclusions from nine modern seafloor settings representing back-arcs, mid-ocean ridges and seamounts. Melt inclusions provide information on the characteristics of parental magmas, including insights into metal budgets. Trace element data in melt inclusions hosted in plagioclase, olivine and pyroxene were obtained by laser-ablation inductively-coupled mass-spectrometry.Results from back-arcs emphasize the impact of slab-subduction and dehydration processes on the chemical characteristics of generated magmas. Volatile- and fluid-mobile element-rich melt inclusions at Manus basin and Okinawa trough reflect a robust contribution of elements from the subducting slab as evidenced by relatively low Ce/Pb ratios. At Bransfield strait, on the other hand, melt inclusions are volatile poor, and fluid-mobile element ratios are similar to mid-ocean ridge values indicating little or no contribution from the slab. High Cu concentrations at Manus basin and Okinawa trough can be explained by fluxing of ferric iron from the subducting slab benefiting the production of sulfate over sulfide.Metal budgets for seamounts located on and nearby the axis of mid-ocean ridge segments appear to be independent of any input of mantle plume material. Results from the southern Explorer ridge (strong lower mantle influence, transitional- and enriched-MORBs), Pito and Axial seamounts (moderate lower mantle influence, transitional-MORBs) and a Foundation near-ridge seamount (little to no mantle influence, normal-MORB) show that, despite similar tectonic environments and varying contributions of mantle plume material, Cu, Zn and Pb values do not vary significantly between the enriched and non-enriched magma components of a given setting.  相似文献   
3.
Experiments were conducted to determine the extent and mechanism by which the composition of quartz-hosted silicate melt inclusions (SMI) and aqueous fluid inclusions (FI) can undergo post-entrapment modification via diffusion. Quartz slabs containing assemblages of SMI and FI were reacted with synthetic HCl bearing and metalliferous aqueous fluids at T = 500-720 °C and P = 150-200 MPa. SMI from the single inclusion assemblages were analyzed by laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS) and electron probe microanalysis (EPMA) before and after the experiments. Analyses revealed that rapid diffusion of the univalent cations Na+, Li+, Ag+, Cu+ and H+ occurred through the quartz from the surroundings, resulting in significant changes in the concentrations of these elements in the inclusions. Concentrations of other elements with an effective ionic radius larger than that of Ag+, or multiple valence states were not modified in the inclusions during the experiments. Our results warn inclusion‘‘ researchers that the interpretation of Na, Li, Cu and Ag concentrations from quartz-hosted SMI and FI should be treated critically.  相似文献   
4.
We conducted experiments to determine the effect of various chemical components (NaCl, KCl, HCl, FeCl2, H2S, SO2) on the solubility of Cu in single phase aqueous vapors at 1000 °C and 150 MPa. The experiments were conducted in Au97Cu3 alloy capsules buffering Cu activities at 0.01. The volatile phase was sampled at run conditions by the entrapment of synthetic fluid inclusions in quartz. To test if the volatile phase had reached equilibrium before the isolation of the inclusions by fracture healing, we trapped two inclusion generations, one in an initially prefractured chip and another in a quartz chip that was fractured in situ during the experiments. The synthetic fluid inclusions were subsequently analyzed by laser ablation inductively coupled plasma mass spectrometry. In pure water, the apparent solubility of Cu is below the limits of detection of 6 μg/g, showing the low stability of hydroxy Cu complexes at our experimental conditions. The presence of alkali chlorides supports modest Cu solubility likely in the form of NaCuCl2 and KCuCl2 complexes. In the H2O-H2S (+SiO2 and Au97Cu3) system at an fH2S of 10.4 MPa the apparent solubility of Cu is lower by a factor of ∼5 than that in a S-free 0.5 m NaCl solution, showing that copper hydrosulfide complexes are only moderately stable at these conditions. Addition of 4.7 mol% of sulfur to the H2O-NaCl system at an fO2 of 0.4 log units below the Ni-NiO buffer, yielding dominantly H2S species, results in only a moderate increase in apparent Cu solubility, which diminishes in the presence of HCl. The addition of KCl results in a strong increase of apparent Cu solubility in the presence of H2S. The solubility of Cu increases with the fugacity of oxygen in both the H2O-NaCl and the H2O-S-NaCl system following an approximately fourth root relationship as expected based on the stoichiometry of the involved redox reactions. Replacement of NaCl by FeCl2 exerted only a minor effect on the Cu solubility.Results of our experiments, combined with thermochemical data obtained by ab initio quantum chemical calculations, suggest dissolution of Cu dominantly as Na(/K)CuCl2, Na(/K)Cu(HS)2, H2SCuHS, and Na(/K)ClCuHS, the relative abundance of which are dictated by the H2S/total chloride and HCl/alkali chloride ratios.  相似文献   
5.
Csaba  Szabó  Károly  Hidas  Enik&#;  Bali  Zoltán  Zajacz  István  Kovács  Kyounghee  Yang  Tibor  Guzmics  Kálmán  Török 《Island Arc》2009,18(2):375-400
In this paper we present a detailed textural and geochemical study of two equigranular textured amphibole-bearing spinel lherzolite xenoliths from Szigliget, Bakony–Balaton Highland Volcanic Field (BBHVF, western Hungary) containing abundant primary silicate melt inclusions (SMIs) in clinopyroxene rims and secondary SMIs in orthopyroxene (and rarely spinel) along healed fractures. The SMIs are dominantly composed of silicate glass and CO2-rich bubbles. Clinopyroxene and orthopyroxene are zoned in both studied xenoliths, especially with respect to Fe, Mg, Na, and Al contents. Cores of clinopyroxenes in both xenoliths show trace element distribution close to primitive mantle. Rims of clinopyroxenes are enriched in Th, U, light rare earth elements (LREEs) and medium REEs (MREEs). Amphiboles in the Szg08 xenolith exhibit elevated Rb, Ba, Nb, Ta, LREE, and MREE contents. The composition of silicate glass in the SMIs covers a wide range from the basaltic trachyandesite and andesite to phonolitic compositions. The glasses are particularly rich in P2O5. Both primary and secondary SMIs are strongly enriched in incompatible trace elements (mostly U, Th, La, Zr) and display a slight negative Hf anomaly. The development of zoned pyroxenes, as well as the entrapment of primary SMIs in the clinopyroxene rims, happened after partial melting and subsequent crystallization of clinopyroxenes, most probably due to an interaction between hot volatile-bearing evolved melt and mantle wall-rocks. This silicate melt filled microfractures in orthopyroxenes (and rarely spinels) resulting in secondary SMIs.  相似文献   
6.
Xenoliths from the upper mantle and lower crust are abundant in Plio–Pleistocene alkali basalts of the Nógrád-Gömör Volcanic Field (NGVF; northern Pannonian Basin, northern Hungary/southern Slovakia), representing a valuable ‘probe’ of lithospheric structures and processes. Ultramafic xenoliths have been divided into two groups: (1) Type-I, composed mostly of olivine with subsidiary orthopyroxene, clinopyroxene and spinel, and (2) Type-II, containing mostly Al- and Ti-rich clinopyroxene with subordinate olivine, spinel and plagioclase. Both types often contain amphibole and, to a lesser extent, mica. The refractory character of Type-I xenoliths suggests they represent mantle depleted by prior episodes of partial melting. In contrast, Type-II series (wehrlites, olivine clinopyroxenites, clinopyroxenites and plagioclase-bearing ultramafic lithologies), on the basis of their textural features, thermobarometric histories and major and trace element variation, appear to have formed as magmatic cumulates. Petrologic and geochemical studies of Type-II xenoliths from Nógrád-Gömör suggest they crystallized from basaltic melts emplaced within the lithospheric mantle and lower crust, prior to the onset of Plio–Pleistocene volcanic activity. After their consolidation, metasomatic agents reacted with the anhydrous cumulate phases producing amphiboles and micas at the expense of olivine and clinopyroxene. The metasomatic agents appear to have been adakitic rather than basaltic in composition, possibly linked to a retreating arc–forearc system. Large-scale contamination of the lithospheric mantle can therefore be attributed to fluid and melt fractions related to subduction beneath the outer Carpathian arc.  相似文献   
7.
The conventional model of leaching volcanic rocks as a source of metals in a seafloor hydrothermal systems has been tested by examining the behavior of Pb and other trace elements during hydrothermal alteration. ODP Leg 193 drill sites 1188 (Snowcap) and 1189 (Roman Ruins) on Pual Ridge in the eastern Manus Basin offshore eastern Papua New Guinea provide a unique three-dimensional window into an active back-arc hydrothermal system. We investigate by means of a LA-ICP-MS microbeam technique the capacity of Pb to be leached from a host volcanic rock exposed to various types and intensities of alteration. Our results are in general agreement with previous studies that utilized bulk analytical techniques but provide a more detailed explanation of the processes.Fresh representative dacitic lavas from the Pual Ridge have an average whole rock Pb content of 5.2 ppm, an average interstitial glass Pb content of 5.6 ppm and an average plagioclase Pb content of 1.0 ppm. Altered matrix samples have highly variable Pb values ranging from 0 to 52.4 ppm. High Pb values in altered samples are associated with a low temperature chlorite and clay mineral assemblage, in some cases overprinted by a high temperature (up to 350 °C) silica-rich “bleaching” alteration. Only the most highly altered matrix samples have REE patterns that differ from the fresh Pual Ridge dacite. This may represent either different lava histories or alteration characteristics that have affected normally immobile REEs. Altered samples with the highest Pb values have similar REE patterns to those of the local unaltered lavas. They are compositionally similar to typical Pual Ridge dacites indicating a genetic relationship between the main regional volcanic suite and the subseafloor hydrothermally altered, Pb-enriched material.Relative loss/gain for Pb between the analyzed altered samples and a calculated precursor show a maximum relative gain of 901%. Samples with relative Pb gain from both drill sites are associated with lower temperature alteration mineral assemblages characterized by pervasive chloritization. The related lower temperature (220-250 °C) neutral to slightly acidic fluids have been ascribed by others to return circulation of hydrothermal fluids that did not interact with seawater. Because altered samples have a higher Pb content than the fresh precursor, leaching of fresh volcanic rocks cannot be the source of Pb in the hydrothermal systems.  相似文献   
8.
A new approach was developed to measure the water content of silicate glasses using Raman spectroscopy, which is independent of the glass matrix composition and structure. Contrary to previous studies, the compositional range of our studied silicate glasses was not restricted to rhyolites, but included andesitic, basaltic and phonolitic glasses. We used 21 glasses with known water contents for calibration. To reduce the uncertainties caused by the baseline removal and correct for the influence of the glass composition on the spectra, we developed the following strategy: (1) application of a frequency-dependent intensity correction of the Raman spectra; (2) normalization of the water peak using the broad T–O and T–O–T vibration band at 850–1250 cm−1 wavenumbers (instead of the low wavenumber T–O–T broad band, which appeared to be highly sensitive to the FeO content and the degree of polymerization of the melt); (3) normalization of the integrated Si-O band area by the total number of tetrahedral cations and the position of the band maximum. The calibration line shows a ±0.4 wt% uncertainty at one relative standard deviation in the range of 0.8–9.5 wt% water and a wide range of natural melt compositions. This method provides a simple, quick, broadly available and cost-effective way for a quantitative determination of the water content of silicate glasses. Application to silicate melt inclusions yielded data in good agreement with SIMS data.  相似文献   
9.
An unusual quartz-bearing orthopyroxene-rich websterite xenolithhas been found in an alkali basaltic tuff at Szigliget, Bakony–BalatonHighland Volcanic Field (BBHVF), western Hungary. Ortho- andclinopyroxenes are enriched in light rare earth elements (LREE),middle REE and Ni, and depleted in Nb, Ta, Sr and Ti comparedwith ortho- and clinopyroxenes occurring in either peridotiteor lower crustal granulite xenoliths from the BBHVF. Both ortho-and clinopyroxenes in the xenolith contain primary and secondarysilicate melt inclusions, and needle-shaped or rounded quartzinclusions. The melt inclusions are rich in SiO2 and alkalisand poor in MgO, FeO and CaO. They are strongly enriched inLREE and large ion lithophile elements, and display negativeNb, Ta and Sr anomalies, and slightly positive Pb anomalies.The xenolith is interpreted to represent a fragment of an orthopyroxene-richbody that crystallized in the upper mantle from a hybrid meltthat formed by interaction of mantle peridotite with a quartz-saturatedsilicate melt that was released from a subducted oceanic slab.Although the exact composition of the slab melt cannot be determined,model calculations on major and trace elements suggest involvementof a metasedimentary component. KEY WORDS: quartz; mantle; silicate melt inclusion; SiO2-rich melt; subduction; Carpathian-Pannonian Region  相似文献   
10.
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