Elemental composition of concentrated brines in subduction zones and the deep continental crust

It has been well established that fluids played an important part in determining chemical characteristics in many crustal terranes. Studies of fluid inclusions in eclogites have established that brines coexisted with the primary mineral assemblages during their metamorphic crystallization. These brines are currently multiply saturated in halide salts, carbonates, oxides, and sulfides. As a first step in quantitatively bounding the composition of the brines during metamorphism, the equilibrium compositions of the brines at room temperature were computed using the aqueous speciation codes EQ3/6. The results demonstrate that the brines are high density solutions (ca. 1.4 g/cm³) that have ionic strengths of approximately 8 mol, and are approximately 40% dissolved solids, by weight. These are predominately Na- and K-rich brines, with subordinate Ca and Mg. The approximate Na:K:Ca:Mg molar ratios are 4:2:0.5:0.2, but are sensitive to the assumed HCO₃⁻ concentrations. Charge balance is primarily maintained by the very high Cl concentrations. These brines bear resemblance to brines analyzed from fluid inclusions in metamorphic rocks reported by Roedder (Roedder, E., 1972. Composition of fluid inclusions. US Geol. Surv. Prof. Paper 440JJ, p. 164). Although these fluids have the potential of acting as significant metasomatic agents in subduction zones and deep crustal environments, their impact will be mineralogically discernible only if the fluid release and movement is channelized.     

Fluid composition and evolution in coesite-bearing rocks (Dora-Maira massif,Western Alps): implications for element recycling during subduction

Fluid inclusions and F, Cl concentration of hydrous minerals were analysed in the coesite-pyrope quartzite, the interlayered jadeite quartzite and their country-rock gneiss from the Dora-Maira massif using a combination of microthermometry, Raman spectrometry, synchrotron X-ray microfiuorescence and electron microprobe analysis. Three populations of fluid inclusions were recognized texturally and can be related to distinct metamorphic stages. A low-salinity aqueous fluid occurs in the retrogressed country gneiss and as late secondary inclusions in jadeite quartzite and chloritized pyrope. An earlier secondary population is found in matrix quartz of the jadeite- and pyro-pe-quartzites. This population can be related to the early decompression and so to incipient breakdown of garnet into phlogopite-bearing assemblages. The inclusion fluid is highly saline (up to 84 wt% equivalent NaCl) and contains Na, Ca, Fe, Cu and Zn as major cations. In pyrope quartzite, additional K was found in these brines, which locally coexist with CO₂-rich inclusions. The oldest fluid inclusions are preserved in kyanite grains included in fresh pyrope and in pyrope itself. In pyrope, all inclusions have decrepitated and contain magnesite, an Mg-phosphate, sheet-silicate(s), a chloride and an opaque phase, with no fluid preser ved. In contrast, the kyanite inclusions in pyrope preserve primary H₂O-CO₂ low-salinity fluid inclusions, probably owing to the low compressibility of the kyanite inclusions and host garnet. In spite of in-situ re-equilibration, these inclusions can be interpreted as relics of the dehydration fluid that attended pyrope growth. These correlations between textural and chemical fluid inclusion data and metamorphic stages are consistent with the fluid composition calculated from the halogen content of different generations of phlogopite and biotite. The preservation of different fluid compositions, both in time and space, is evidence for local control and possibly origin of the fluids, in agreement with isotopic data. These results, in particular the absence of CO₂ in the jadeite quartzite, are best interpreted in terms of a fluid-melt system evolution. With increasing metamorphism, partitioning of H₂O, Na, Ca, Fe and heavy metals into melt (jadeite quartzite) and Mg, Na/K, F, CO₂ and P(?) into a residual aqueous fluid can account for depletion in Na, Ca and Fe of the pyrope quartzite. During the retrograde path, a _{H 2 O} rose as melt crystallized, generating the two populations of hypersaline and water-rich fluids that were highly reactive to pyrope. The process of fluid-melt interaction envisioned here coupled with models of melt extraction in subduction zones provides an attractive opportunity for the instantaneous ( < 1 Ma) and selective transport of elements between a downgoing slab and the overlying mantle wedge.     

Zircon formation during fluid circulation in eclogites (Monviso, Western Alps): implications for Zr and Hf budget in subduction zones

The zircons from an eclogite and an enclosed eclogite-facies vein from the Monviso ophiolite (Western Alps) display contrasting chemical and morphologic features and document different stages of the evolution of the ophiolite. The zircons from the eclogite show a typical magmatic zoning and are enriched in heavy rare earth elements (HREEs) over middle rare earth elements (MREEs) and have an accentuated negative Eu anomaly, which indicates that the grains co-crystallised with plagioclase. These magmatic zircons document the formation of oceanic crust at 163 ± 2 Ma. In contrast, zircons from the vein contain inclusions of garnet, omphacite, and rutile, which indicate that they crystallised under eclogite-facies conditions. The vein zircons have Th/U ratios < 0.09, lack Eu anomalies, and are only weakly enriched in HREE with respect to MREE. These features are consistent with a garnet-bearing, plagioclase-free, i.e., eclogite-facies paragenesis. Vein zircons yield an age of 45 ± 1 Ma, which is evidence for Eocene subduction-zone metamorphism of the Monviso ophiolite.In the vein, the apparent coexistence of zircon, omphacite, and garnet permits the determination of a set of trace element distribution coefficients among these minerals at high pressure. This set of partitioning can demonstrate chemical equilibrium among these phases in rocks that show less clear evidence of textural equilibrium. In addition, zircon age can now be linked to sensors of metamorphic pressure-temperature conditions. The presence of zircon and rutile in the vein is another example of high field strength element (HFSE) mobility over short distances in aqueous fluids at eclogite-facies conditions. However, the concentrations of Zr and Hf in the aqueous fluid are estimated to be at least a factor of 10 less than primitive mantle values.Mass balance calculations demonstrate that zircon hosts > 95% of the bulk Zr, 90% of Hf, and ∼25% of U in the vein. Zircon is a residual phase in subducted basalts and sediments up to temperatures of at least 800 to 900 °C. Therefore, residual zircon in subducted crust, together with rutile, control the HFSE in liberated subduction zone fluids/melts and might be partly responsible for negative Zr and Hf anomalies in subduction zone magmas.     

Oscillatory zoning in eclogitic garnet and amphibole,Northern Serpentinite Melange,Cuba: a record of tectonic instability during subduction?

Exotic blocks of eclogite from distant localities along the Northern Serpentinite Melange of Cuba have comparable P–T histories that include high‐pressure prograde sections (450–600 °C, >15 kbar) associated with subduction of oceanic lithosphere, and retrograde sections within the albite–epidote amphibolite facies (<500 °C, <10 kbar) related to melange uplift. ⁴⁰Ar/³⁹Ar and Rb/Sr cooling ages (118–103 Ma) of one of the blocks indicate pre‐Aptian subduction and Aptian–Albian uplift. Detailed X‐ray imaging and profiling further reveals that minerals in these eclogite blocks (notably garnet and amphibole) display subtle but well defined oscillatory zoning that developed along the prograde trajectory of the rocks, previous to attainment of peak eclogitic conditions. The chemistry (e.g. coupled changes of Mg# and Mn in garnet, and of Si, Ti, Al and Na in amphibole) and geometry (euhedral to anhedral shapes) of the oscillations can be interpreted in terms of subtle fluctuations in P–T during the general prograde subduction‐related metamorphic path. A (near‐) equilibrium model is presented for the formation of oscillations at near peak conditions by means of recurrent dissolution‐growth reaction processes. This model for near‐peak conditions, and the chemical signatures of earlier oscillations (notably in amphibole), suggest that episodes of retrogression (upward movement?) affected parts of the subducting slab. It is proposed that these retrograde episodes record the tectonic rupture of the subducting slab and, probably, of the upper plate mantle, either due to the intrinsic dynamic behaviour of subduction systems or to the effects of the plate‐tectonic rearrangement of the Caribbean region during the Early Cretaceous.     

Evolving fluid composition during prograde metamorphism in subduction zones: A new approach using carbonate-bearing assemblages in the pelitic system

The changing XCO₂ in fluids during the progressive metamorphism in Sanbagawa belt of the Cretaceous subduction zone, Japan, was estimated by a newly proposed method. The subduction zone meta-sediments are characterized commonly by four-phase assemblages in the CaO–NaAlO₂–KAlO₂–Al₂O₃ system with excess quartz and a CO₂–H₂O binary fluid phase. Using the common assemblage of calcite–albite–muscovite–clinozoisite, XCO₂ of the fluid was estimated to be from about 0.0001–0.0005 (the lowest grade chlorite zone), through 0.004–0.01 (garnet zone), 0.01–0.05 (albite–biotite zone) to 0.06–0.2 (oligoclase–biotite zone).The paragenetic relationship of meta-sediments from the subduction zones was compared in a wide P–T range to cover the stability fields of aragonite and jadeite. As a result, an excellent P–T–XCO₂ relationship was delineated to serve as a quantitative monitor for the evolving fluid composition during the progressive metamorphism in subduction zones.     

Constraints from high-pressure veins in eclogites on the composition of hydrous fluids in subduction zones

Hydrous high-pressure veins formed during dehydration of eclogites in two paleo-subduction zones (Trescolmen locality in the Adula nappe, central Alps and Münchberg Gneiss Massif, Variscan fold belt, Germany) constrain the major and trace element composition of solutes in fluids liberated during dehydration of eclogites. Similar initial isotopic compositions of veins and host eclogites at the time of metamorphism indicate that the fluids were derived predominantly from the host rocks. Quartz, kyanite, paragonite, phengite, zoisite and omphacite are the dominant minerals in the veins. The major element compositions of the veins are in agreement with experimental evidence indicating that the composition of solutes in such fluids is dominated by SiO₂ and Al₂O₃. Relative to N-MORB, the veins show enrichments of Cs, Rb, Ba, Pb, and K, comparable or slightly lower abundances of Sr, U, and Th, and very low abundances of Nd, Sm, Zr, Nb, Ti and Y. The differential fractionation of highly incompatible elements such as K, U and Th in the veins, as well as the presence of hydrous minerals in the eclogites rule out partial melting as a cause for vein formation. These results confirm previous suggestions that fluids derived from subducted basalt may have low abundances of high field strength elements, rare earth elements and Y. Variable vein-eclogite enrichment factors of incompatible alkalis and to a lesser extent Pb appear to reflect mineralogical controls (phengite, epidote-group minerals) on partitioning of these elements during dehydration of eclogite in subduction zones. However, abundance variations of incompatible elements in minerals from eclogites suggest that the composition of fluids released from eclogites at temperatures <700°C may not reflect true equilibrium partitioning during dehydration. Simple models for the trace elements U and Th indicate the relative importance of the basaltic and sedimentary portions of subducted oceanic crust in producing the characteristic chemical signatures of these elements in convergent plate margin volcanism.     

Partitioning of halogens between mantle minerals and aqueous fluids: implications for the fluid flow regime in subduction zones

We have performed phase equilibrium experiments in the system forsterite–enstatite–pyrope-H₂O with MgCl₂ or MgF₂ at 1,100 °C and 2.6 GPa to constrain the solubility of halogens in the peridotite mineral assemblage and the fluid–mineral partition coefficients. The chlorine solubility in forsterite, enstatite and in pyrope is very low, 2.1–3.9 and 4.0–11.4 ppm, respectively, and it is independent of the fluid salinity (0.3–30 wt% Cl), suggesting that some intrinsic saturation limit in the crystal is reached already at very low chlorine concentrations. Chlorine is therefore exceedingly incompatible in upper-mantle minerals. The fluorine solubility is 170–336 ppm in enstatite and 510–1,110 ppm in pyrope, again independent of fluid salinity. Forsterite dissolves 1,750–1,900 ppm up to a fluid salinity of 1.6 wt% F. At higher fluorine contents in the system, forsterite is replaced by the minerals of the humite group. The lower solubility of chlorine by three orders of magnitude when compared to fluorine is consistent with increasing lattice strain. Fluid–mineral partition coefficients are 10⁰–10² for fluorine and 10³–10⁵ for chlorine. Since the latter values are orders of magnitude higher than those for hydroxyl partitioning, fluid flow from the subducting slab through the mantle wedge will lead to an efficient sequestration of H₂O into the nominally anhydrous minerals in the wedge, whereas chlorine becomes enriched in the residual fluid. Simple mass balance calculations reveal that rock–fluid ratios of up to >3,000 are required to produce the elevated Cl/H₂O ratios observed in some primitive arc magmas. Accordingly, fluid flow from the subducted slab into the zone of melting in the mantle wedge does not only occur rapidly in narrow channels, but at least in some subduction zones, fluid pervasively infiltrates the mantle peridotite and interacts with a large volume of the mantle wedge. Together with the Cl/H₂O ratios of primitive arc magmas, our data therefore constrain the fluid flow regime below volcanic arcs.     

Change in carbonate budget and composition during subduction below metal saturation boundary

It is generally accepted that carbonates can be subducted to the mantle depths, where they are reduced with iron metal to produce a diamond. In this work, we found that this is not always the case. The mantle carbonates from inclusions in diamonds show a wide range of cation compositions (Mg, Fe, Ca, Na, and K). Here we studied the reaction kinetics of these carbonates with iron metal at 6–6.5 GPa and 1000–1500 °C. We found that the reduction of carbonate with Fe produces C-bearing species (Fe, Fe-C melt, Fe₃C, Fe₇C₃, C) and wüstite containing Na₂O, CaO, and MgO. The reaction rate constants (k = Δx²/2t) are log-linear relative to 1/T and their temperature dependences are determined to bek_MgCO3 (m²/s) = 4.37 × 10^?3 exp [?251 (kJ/mol)/RT]k_CaMg(CO3)2 (m²/s) = 1.48 × 10^?3 exp [?264 (kJ/mol)/RT]k_CaCO3 (m²/s) = 3.06 × 10^?5 exp [?245 (kJ/mol)/RT] andk_Na2CO3 (m²/s) = 1.88 × 10^?10 exp [?155 (kJ/mol)/RT].According to obtained results at least, 45–70 vol% of carbonates preserve during subduction down to the 660-km discontinuity if no melting occurs. The slab stagnation and warming, subsequent carbonate melting, and infiltration into the mantle saturated with iron metal are accompanied by a reduction of carbonate melt with Fe. The established sequence of reactivity of carbonates: FeCO₃ ≥ MgCO₃ > CaMg(CO₃)₂ > CaCO₃ ? Na₂CO₃, where K₂CO₃ does not react at all with iron metal, implies that during reduction carbonate melt with Fe evolves toward alkali-rich. The above conclusions are consistent with the findings of carbonates in inclusions in diamonds from the lower mantle and high concentrations of alkalis, particularly K, in mantle carbonatite melts entrapped by diamonds from kimberlites and placers worldwide.     

西天山高压脉及主岩的氧同位素研究——古俯冲带深部流体及俯冲特征的启示

位于中国南天山的西天山高压变质带代表了伊犁-中天山与塔里木两个板块间古生代南天山洋的古俯冲混杂岩带.高压变质带内广泛发育高压脉.为探讨古俯冲深部流体来源及运移特点及板块俯冲特征,对高压脉和主岩的全岩及主要的高压变质矿物的氧同位素进行了分析.高压脉的δ18O值变化于+8.28‰与+10.70‰之间,多数在+9.50‰±1范围内.基性变质岩的主岩与高压脉具相似的氧同位素组成,变化于+9.25‰～+10.10‰之间.高压脉和主岩的全岩δ18O值变化不大.高压脉与相邻主岩间、同一高压脉中间与边部间氧同位素组成的变化没有明显的规律,一般变化不大,对于大多数脉-主岩对,变化小于1‰.与全岩完全不同的是,单矿物氧同位素组成显示出很大的变化范围,石英、石榴石、绿辉石的δ18O值分别为+11.40‰～+15.20‰,+3.59‰～+11.60‰和+8.30‰～+13.05‰,多硅白云母和蓝闪石δ18O的变化较小,分别为+10.00‰～+11.10‰和+9.26‰～+9.94‰.榴辉质岩石中高压变质矿物间氧同位素分馏广泛不平衡.全岩氧同位素组成特征表明,俯冲带深部流体主体来自邻近主岩,外来流体对氧同位素贡献有限.单矿物氧同位素广泛不平衡特征可能指示古俯冲带俯冲板片的快速俯冲和折返以及部分外来流体的参与.     

Isotopic composition of oil-field brines from Kettleman North Dome,California, and their geologic implications

Deuterium and O¹⁸ analyses were made on 25 formation-water samples from Miocene (Temblor Formation) and Eocene (McAdams Formation) reservoir rocks at Kettleman North Dome oil field, California, and on three surface water samples from Reef Ridge located about three miles to the west of the field. The δO¹⁸ values obtained generally increase with depth and most probably are due to temperature controlled exchange reactions with carbonate cement and dissolved carbonate species. The δD values obtained seem to be controlled primarily by the membrane behavior of shales modifying the assumed original values. The contribution of isotopic exchange between water and clays cannot be evaluated at present.The isotopic data support the conclusions based on a detailed study of geology, hydrodynamics, and formation water geochemistry (Kharaka, 1971) which indicate that:1. The Temblor Formation waters are probably meteoric in origin concentrated chemically and isotopically by shale membranes, and 2. The McAdams Formation waters were most probably obtained by squeezing the original interstitial marine connate waters of deposition from the underlying Mesozoic sediments.     

F,Cl and S input via serpentinite in subduction zones: implications for the nature of the fluid released at depth

The abundances of F, Cl and S in arc magmas are systematically higher than in other mantle‐derived magmas, suggesting that these elements are added from the slab along with H₂O. We present ion probe microanalyses of F, Cl and S in serpentine minerals that represent the P–T evolution of the oceanic lithosphere, from its serpentinization at the ridge, to its dehydration at around 100 km depth during subduction. F, Cl and S are incorporated early into serpentine during its formation at mid‐ocean ridges, and serpentinized lithosphere then carries these elements to subduction zones. More than 50% of the F, Cl and S are removed from serpentine during the prograde metamorphic lizardite/antigorite transition. Due to the low solubility of F in water, and to the low amount of water released during this phase transition, the fluids mobilizing these elements must be dominated by SO_X rather than H₂O.     

Ordering in double carbonates and implications for processes at subduction zones

We have studied cation ordering in dolomite in situ as a function of pressure, temperature, and experimental time using the multi-anvil apparatus and synchrotron radiation. Starting with ordered dolomite, we observe the onset of disordering taking place at 950°C, while complete disordering is achieved at 1,070 (±20)°C, for pressures ranging between 3.37 and 4.05 GPa. Pressure does not appear to have significant effect on the order/disorder transition over the investigated range. We find that dolomite can reach its equilibrium ordering state above 900°C within duration of laboratory experiment (few hours), both from disordered state and from ordered state. In addition, we have reversed the dolomite breakdown reaction [magnesite + aragonite = dolomite] between 4.5 and 5.5 GPa, by monitoring diffraction peak intensity. We also have determined that dolomite is stable up to 7.4 GPa at 1,100°C. We confirm some earlier studies where a change in slope (dP/dT) has been observed, but we find a non-zero slope in the low pressure range. Combining the values of entropy obtained from dolomite degree of ordering with enthalpy values deduced from our bracketing of [magnesite + aragonite = dolomite] equilibrium, we model the location of dolomite breakdown in the P–T space as a function of cation ordering. By comparing previous conflicting studies, we show that, although kinetics of order/disorder is fast, disequilibrium dolomite breakdown is possible. Our modeling shows that subducted disordered dolomite present in carbonated sediments could be decomposed to [magnesite + aragonite] at lower pressure (3.5 GPa) than usually considered (>5 GPa). This 2-GPa (60 km) difference is valid on a fast subduction path and is possible if disorder inherited from sedimentation is preserved. On a slow subduction path, however, dolomite breakdown is encountered at about 250 km depth, which is 100 km deeper than currently considered.     

Mobilization of Ti-Nb-Ta during subduction: Evidence from rutile-bearing dehydration segregations and veins hosted in eclogite, Tianshan, NW China

Field evidence from the western Tianshan subduction complex in northwestern China indicates that the high field strength elements Ti, Nb, and Ta were mobilized and thereby fractionated from Zr and Hf during the dehydration process that transformed blueschist into eclogite. Both a segregation with a depletion halo, thought to represent initial mobilization during dehydration, and a transport vein, indicative of the long distance transport were investigated. In each case, centimeter-sized rutile grains grew as needle-like crystals in the segregation and as prismatic crystals in the vein. Within the host rock of the segregation, the Ti contents of garnet and omphacite, the modal abundances of rutile and titanite and the bulk rock Ti, Nb, and Ta contents decrease towards the segregation. These observations are consistent with transport of Ti, Nb, and Ta from the host rock into the segregation. Textural and geochemical data for the eclogite-facies vein minerals indicate that Ti-Nb-Ta-rich fluids were transported over long-distances (at minimum meter-scale) during fracture-controlled fluid flow. Complex forming ligands (e.g., Na-Si-Al polymers and F⁻) may have enhanced the solubility of Ti, Nb, and Ta in the fluid. Changes in fluid composition (e.g., X_CO2) may both precipitate rutile and fractionate Ti, Nb, and Ta from LILE and REE.     

Oxygen and nitrogen isotopes as tracers of fluid activities in serpentinites and metasediments during subduction

Summary N and O isotope systematics of a suite of high-pressure (HP) and ultrahigh-pressure (UHP) metasediments of the Schistes Lustrés nappe and metaperidotites of the Erro Tobbio Massif from the Alpine-Appennine system are compared with their unmetamorphosed or hydrothermally-altered equivalent from the same localities and from the South West Indian Ridge (SWIR). The HP and UHP rocks studied represent a sequence of pelagic sediments and altered ultramafic rocks subducted to different depths of down to 90 km along a cold geothermal gradient (8 °C/km). Unmetamorphosed and HP metasediments show the same range in δ¹⁵N values irrespective of their metamorphic grade and bulk nitrogen concentrations. Together with several other geochemical features (K, Rb and Cs contents, δD), this indicates that δ¹⁵N values were unaffected by metamorphism and N was not released during subduction. N isotope analysis of serpentinites coupled with δ¹⁸O systematics suggests the involvement of a mafic (crustal) component during partial deserpentinization of the subducted oceanic mantle at the depth locus of island arc magmatism. This does not imply large-scale fluxes as the metagabbros are spatially associated with the analyzed serpentinites. It rather indicates preservation of presubduction chemical and isotopic heterogeneities on a local scale as documented for the metasediments.     

Chalk–fluid interactions with glycol and brines

Mechanical properties of high porosity chalks are strongly dependent on the type of fluid in the pores. Dry chalk is considerably stronger than water-saturated chalk, and this phenomenon is often referred to as the water-weakening effect. To address the problem of chalk–fluid interactions, several series of tests have been performed with glycol and high concentration brines as saturating fluids. Glycol is a fluid that in many aspects resembles oil, except that glycol is miscible with water. Glycol-saturated chalk turns out to have properties very similar to oil-saturated chalk. Compared to dry chalk, both oil and glycol make the chalk somewhat weaker, but this weakening effect is much less than with water. Several series of tests with brines with high concentrations of calcium chloride or sodium chloride show that the water-weakening effect is considerably reduced in high ionic strength solutions. Most tests were performed as quasi-hydrostatic tests, with a constant stress ratio of 0.9. In such tests, the yield point marks the onset of accelerated pore collapse, and the yield value is close to the hydrostatic yield stress. In addition to these compressive tests, a series of Brazilian tests were performed, revealing the same trend. The variations in mechanical strength have been correlated with the activity of water in the brines. Within the experimental accuracy of the compressive tests, there is a linear trend between reduction of water activity and the corresponding increase in strength. This leads to the hypothesis that the water activity may be a key parameter in the water-weakening mechanism. But this conclusion also indicates that water weakening may be a special case of general chalk–fluid interactions where the degree of weakening depends on the strength of adsorption of the fluid molecules to the calcite surfaces.     

Andalusite-bearing veins at Vedrette di Ries (eastern Alps, Italy): fluid phase composition based on fluid inclusions

Abstract Andalusite-bearing veins formed during contact metamorphism in the aureole of the Vedrette di Ries tonalite. In the veins, quartz crystals that are completely armoured by andalusite or that occur in strain shadow areas contain three generations of fluid inclusions: low-salinity H₂O-CO₂-CH₄ mixtures with CH₄/(CO₂+ CH₄) ± 0.35 (type A); low-salinity aqueous fluids (type B); H₂O-free, CO₂-CH₄ fluids with the same carbonic speciation as A (type C). Carbonic types A and C typically have a dark appearance, which is attributed to graphite coatings on inclusion walls. Microstructural analysis of the host quartz and calculated densities indicate that type A inclusions were likely trapped during vein formation. These inclusions underwent strain-assisted re-equilibration during cooling that resulted in density increases without change of composition. After the rocks had cooled below about 350 ° C, type C inclusions appear to have formed from one of the immiscible fractions after unmixing of the H₂O-CO₂-CH₄ fluid mixtures. Aqueous type B inclusions, apparently trapped between 225 and 350 ° C, could represent an independent fluid, or could be the H₂O-rich fraction of unmixed type A fluids. Taking account of the uncertainties, the composition and density of the complex type A inclusion fluids are in good agreement with the properties of primary fluids calculated from the petrological data. The fluid inclusion data support the model of vein formation by hydrofracturing as a result of dehydration of graphitic metapelites. These new results also demonstrate the importance of considering strain in the interpretation of metamorphic fluid inclusions.     

TC/EA-MS online determination of hydrogen isotope composition and water concentration in eclogitic garnet

A continuous flow method, by a combination of thermal conversion elemental analyzer (TC/EA) with isotope ratio mass spectrometry (MS), is presented for determination of both H isotope composition and H₂O concentration of garnet from eclogite. Together with biotite NBS-30, the garnet was tested by preheating mineral grains at different temperatures. Preheating at 90°C for 12 h was found to be capable of eliminating adsorption water on sample surface. This results in constant δD values and total H₂O contents for the garnet, with weighted means of −93 ± 2‰ and 522 ± 11 ppm (wt), respectively. The garnet that was preheated at 350°C for 4 h also gave constant δD values of −86 ± 6‰ and H₂O contents of 281 ± 13 ppm (wt). The latter result for the H₂O contents agrees with the H₂O contents 271 ± 58 ppm (wt) measured by Fourier transform infrared spectroscopy for quantitative analysis of structural hydroxyl in the same garnet. Stepwise-heating TC/EA-MS analyses for the garnet show that the molecular H₂O are depleted in D relative to the structural OH and has higher mobility than the structural OH. Therefore, the TC/EA-MS method can be used not only for quantitative determination of both H isotope composition and H₂O concentration of hydrous and anhydrous minerals, but also for the concentration of structural hydroxyl after high-T dehydration.     

蛇纹石化和俯冲带蛇纹岩变质脱水过程中流体活动性元素的行为

蛇纹石是大洋岩石圈和俯冲带内水和流体活动性元素最重要的载体之一。研究蛇纹石化和蛇纹岩变质脱水过程中流体活动性元素的行为是认识俯冲带元素地球化学循环的关键。蛇纹岩是指主要由蛇纹石类矿物构成的岩石,包括利蛇纹石、纤蛇纹石和叶蛇纹石。蛇纹石化过程中会造成流体活动性元素(B、Li、As、Sb、Pb、Cs、U、Sr和Ba等)的显著富集,并且由于原岩性质、流体成分和氧逸度等条件的不同,大洋岩石圈蛇纹岩和弧前蛇纹岩的特征也略有不同。例如,弧前蛇纹岩具有相对高的As、Sb、B和相对低的U,这反映了俯冲沉积物来源流体的贡献。在俯冲带蛇纹岩的变质脱水过程中,利蛇纹石向叶蛇纹石的转变伴随着矿物内超过50%F和Cl的释放,以及一些流体活动性元素(如B和Li)的迁出;此外,蛇纹石分解形成的变质橄榄石中的流体包裹体指示,蛇纹石脱水分解所产生的流体具有高于原始地幔几个数量级的Cl、Cs、Pb、As、Sb、Ba、Rb、B、Sr、Li和U含量。由于利蛇纹石中的Fe~(3+)含量较叶蛇纹石高,这种矿物相转变过程中也伴随着俯冲通道内的一系列氧化还原过程,从而影响流体性质和新形成的叶蛇纹石的成分。蛇纹岩与岛弧岩浆在流体活动性元素富集规律上的相似性说明蛇纹岩在俯冲带元素循环中扮演着重要的角色。此外,蛇纹石矿物相转变过程中F、Cl、B等元素的释放,可能对于斑岩型金矿、蛇绿岩中的金矿和某些蛇纹岩作为赋矿围岩的硼矿的形成起到重要的作用。     

Oxygen bulk diffusion measurements and TEM characterization of a natural ultramylonite: implications for fluid transport in mica-bearing rocks

Oxygen bulk diffusion rates were experimentally determined in a natural ultramylonite sample ( c . 5   μ m grain size; 15–20% biotite, 20% quartz, 60–65% feldspars, and minor Fe-oxides) from the Gerrish Island shear zone, SE Maine, USA. The diffusion experiments were performed at 250–550  °C and 100  MPa water pressure. Oxygen bulk diffusion rates were determined both parallel and perpendicular to the strong foliation of the sample. The Arrhenius parameters for transport parallel to the foliation are: D _bulk0=2.0×10⁻¹¹ m² s⁻¹ and Q =30±6 kJ mol⁻¹. The bulk diffusivity perpendicular to the foliation is about a factor of 3.5 less than that parallel to the foliation with the same activation energy. The values of bulk diffusivity and activation energy obtained are consistent with ionic diffusion through a static aqueous fluid, suggesting that an interconnected fluid exists in the ultramylonite even under hydrostatic conditions. The microstructure of the ultramylonite was characterized using transmission electron microscopy (TEM). The nature and distribution of the interconnected fluid cannot be completely resolved from the TEM analysis; however, the low percentage of three-grain channels and open grain/interphase boundaries suggests that the fluid resides as a thin film on the grain surfaces. The results of this study have direct applications in many important geological settings and provide valuable insights into the observed rapid diffusion rates, strong lithological control and pervasive nature of fluid transport in mica-bearing rocks.     

Fluid variability in 2 GPa eclogites as an indicator of fluid behavior during subduction

Fluid activity ratios calculated between millimeter- to centimeter-scale layers in banded mafic eclogites from the Tauern Window, Austria, indicate that variations in a _{H 2 O} existed between layers during equilibration at P approximately equal to 2GPa and T approximately equal to 625°C, whereas a _{CO 2} was nearly constant between the same layers. Model calculations in the system H₂O–CO₂–NaCl show that these results are consistent with the existence of different saturated saline brines, carbonic fluids, or immiscible pairs of both in different layers. The data cannot be explained by the exisience of water-rich fluids in all layers. The model fluid compositions agree with fluid inclusion compositions from eclogite-stage veins and segregations that contain (1) saline brines (up to 39 equivalent wt. % NaCl) with up to six silicate, oxide, and carbonate daughter phases, and (2) carbonic fluids. The formation of crystalline segregations from fluid-filled pockets or hydrofractures indicates high fluid pressures at 2 GPa; the record of fluid variability in the banded eclogite host rocks, however, implies that fluid transport was limited to local flow along individual layers and that there was no large-scale mixing of fluids during devolatilization at depths of 60–70 km. The lack of evidence for fluid mixing may, in part, reflect variations in wetting behavior of fluids of different composition; nonwetting fluids (water-rich or carbonic) would be confined to intergranular pore spaces and would be essentially immobile, whereas wetting fluids (saline brines) could migrate more easily along an interconnected fluid network. The heterogeneous distribution of chemically distinct fluids may influence chemical transport processes during subduction by affecting mineral-fluid element partitioning and by altering the migration properties of the fluid phase(s) in the downgoing slab.