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1.
Garnet and omphacite from ultrahigh-pressure eclogites from the Dabie orogen, eastern China were investigated by Micro-FTIR. The results show that all garnet and omphacite grains contain structural water occurring as hydroxyl (OH), with H2O contents varying from 14 to 1915 ppm (H2O wt) and from 105 to 695 ppm, respectively. Within the same sample, the water contents are either homogeneous at the grain scale or vary systematically from higher in the core to lower in the rim. Low water contents at crystal rims possibly result from hydroxyl exsolution after pressure decrease upon rock exhumation. The δD values of omphacites are between −108.4‰ and −114.2‰, and independent of water contents. Heterogeneous water contents of garnet occur at the centimeter scale and fluid mobility during UHP metamorphism was very limited. The estimated whole-rock water content based on mineral H2O contents is between 260 and 750 ppm, thereby implying that eclogitic rocks formed during continental subduction have the potential to recycle (at least) several hundreds ppm water to mantle depths. The preserved chemical differences likely indicate that the eclogitic rocks resided at mantle conditions for a limited time span, and imply that they were exhumed shortly after subduction. The water released during decompression might represent the early-stage retrograde fluid.  相似文献   

2.
By taking advantage of having depth profiles between contrasting lithologies from core samples of the Chinese Continental Scientific Drilling (CCSD) project, a combined study was carried out to examine changes in mineral H isotope, total water and hydroxyl contents in garnet and omphacite across the contacts between ultrahigh-pressure (UHP) eclogite and gneiss in the Sulu orogen, east-central China. The samples of interest were from two continuous core segments from the CCSD main hole at depths of 734.21-737.16 and 929.67-932.86 m, respectively. The results show δD values of −116‰ to  − 64‰ for garnet and −104‰ to −82‰ for omphacite, consistent with incorporation of meteoric water into protoliths of UHP metamorphic rocks by high-T alteration. Both equilibrium and disequilibrium H isotope fractionations were observed between garnet and omphacite, suggesting fluid-assisted H isotope exchange at local scales during amphibolite-facies retrogression. While bulk water analysis gave total H2O concentrations of 522-1584 ppm for garnet and 1170-20745 ppm for omphacite, structural hydroxyl analysis yielded H2O contents of 80-413 ppm for garnet and 228-412 ppm for omphacite. It appears that significant amounts of molecular H2O are present in the minerals, pointing to enhanced capacity of water storage in the UHP eclogite minerals. Hydrogen isotope variations in the transition between eclogite and gneiss show correlations with variations in their water contents. Petrographically, the degree of retrograde metamorphism generally increases with decreasing distance from the eclogite-gneiss boundary. Thus, retrograde metamorphism results in mineral reactions and H isotope variation. Because hydroxyl solubility in nominally anhydrous minerals decreases with dropping pressure, significant amounts of water are expected to be released from the minerals during decompression exhumation. Decompression exsolution of structural hydroxyl from 1 m3 volume of eclogite composed of only garnet and omphacite results in release of a quantitative estimate of 3.07-3.44 kg water that can form 140-156 kg amphibole during exhumation. Therefore, it is concluded that fluid for retrogression of the eclogites away from the eclogite-gneiss boundary was derived from the decompression exsolution of structural hydroxyl and molecular H2O in nominally anhydrous minerals. For the eclogites adjacent to gneiss, in contrast, the retrograde metamorphism was principally caused by aqueous fluid from the gneiss which is relatively rich in water. Consequently, both the origin and availability of metamorphic fluid during exhumation of deeply subducted continental crust are deciphered by this combined study focusing on the transitions and the retrograde processes between the felsic and mafic UHP rocks.  相似文献   

3.
Little is known about water in nominally anhydrous minerals of orogenic garnet peridotite and enclosed metabasic rocks. This study is focused on peridotite-hosted eclogite and garnetite (metarodingite) from the Erzgebirge (EG), Germany, and the Lepontine Alps (LA), Switzerland. Newly discovered, peridotite-hosted eclogite in the Erzgebirge occurs in the same ultra-high pressure (UHP) unit as gneiss-hosted coesite eclogite, from which it is petrologically indistinguishable. Garnet is present in all mafic and ultramafic high pressure (HP) rocks providing for an ideal proxy to compare the H2O content of the different rock types. Garnet composition is very similar in EG and LA samples and depends on the rock type. Garnet from garnetite, compared to eclogite, contains more CaO (garnetite: 10.5–16.5 wt%; eclogite: 5–11 wt%) and is also characterized by an anomalous REE distribution. In contrast, the infrared (IR) spectra of garnet from both rock types reveal the same OH absorption bands that are also identical to those of previously studied peridotitic garnet from the same locations. Two groups of IR bands, SW I (3,650 ± 10 cm−1) and SW II (3,570–3,630 cm−1) are ascribed to structural hydroxyl (colloquially ‘water’). A third, broad band is present in about half of the analysed garnet domains and related to molecular water (MW) in submicroscopic fluid inclusions. The primary content of structural H2O, preserved in garnet domains without fluid inclusions (and MW bands), varies systematically—depending on both the location and the rock type. Garnet from EG rocks contains more water compared to LA samples, and garnet from garnetite (EG: 121–241 wt.ppm H2O; LA: 23–46 wt.ppm) hosts more water than eclogitic garnet (EG: 84 wt.ppm; LA: 4–11 wt.ppm). Higher contents of structural water (SW) are observed in domains with molecular water, in which the SW II band (being not restricted to HP conditions) is simultaneously enhanced. This implies that fluid influx during decompression not only led to fluid inclusions but also favoured the uptake of secondary SW. The results signify that garnet from all EG and LA samples was originally H2O-undersaturated. Combining the data from eclogite, garnetite and previously studied peridotite, H2O and CaO are positively correlated, pointing to the same degree of H2O-undersaturation at peak metamorphism in all rock types. This ubiquitous water-deficiency cannot be reconciled with the derivation of any of these rocks from the lowermost part of the mantle wedge that was in contact with the subducting plate. This agrees with the previously inferred abyssal origin for part of the rocks from the LA (Cima di Gagnone). A similar origin has to be invoked for the Erzgebirge UHP unit. We suggest that all mafic and ultramafic rocks of this unit not only shared the same metamorphic evolution but also a common protolith origin, most probably on the ocean floor. This inference is supported by the presence of peridotite-hosted garnetite, representing metamorphosed rodingite.  相似文献   

4.
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.  相似文献   

5.
We studied the systematics of Cl, F and H2O in Izu arc front volcanic rocks using basaltic through rhyolitic glass shards and melt inclusions (Izu glasses) from Oligocene to Quaternary distal fallout tephra. These glasses are low-K basalts to rhyolites that are equivalent to the Quaternary lavas of the Izu arc front (Izu VF). Most of the Izu glasses have Cl ∼400-4000 ppm and F ∼70-400 ppm (normal-group glasses). Rare andesitic melt inclusions (halogen-rich andesites; HRA) have very high abundances of Cl (∼6600-8600 ppm) and F (∼780-910 ppm), but their contents of incompatible large ion lithophile elements (LILE) are similar to the normal-group glasses. The preeruptive H2O of basalt to andesite melt inclusions in plagioclase is estimated to range from ∼2 to ∼10 wt% H2O. The Izu magmas should be undersaturated in H2O and the halogens at their preferred levels of crystallization in the middle to lower crust (∼3 to ∼11 kbar, ∼820° to ∼1200°C). A substantial portion of the original H2O is lost due to degassing during the final ascent to surface. By contrast, halogen loss is minor, except for loss of Cl from siliceous dacitic and rhyolitic compositions. The behavior of Cl, F and H2O in undegassed melts resembles the fluid mobile LILE (e.g.; K, Rb, Cs, Ba, U, Pb, Li). Most of the Cl (>99%), H2O (>95%) and F (>53%) in the Izu VF melts appear to originate from the subducting slab. At arc front depths, the slab fluid contains Cl = 0.94 ± 0.25 wt%, F = 990 ± 270 ppm and H2O = 25 ± 7 wt%. If the subducting sediment and the altered basaltic crust were the only slab sources, then the subducted Cl appears to be almost entirely recycled at the Izu arc (∼77-129%). Conversely, H2O (∼13-22% recycled at arc) and F (∼4-6% recycled) must be either lost during shallow subduction or retained in the slab to greater depths. If a seawater-impregnated serpentinite layer below the basaltic crust were an additional source of Cl and H2O, the calculated percentage of Cl and H2O recycled at arc would be lower. Extrapolating the Izu data to the total length of global arcs (∼37,000 km), the global arc outflux of fluid-recycled Cl and H2O at subduction zones amounts to Cl ∼2.9-3.8 × 1012 g/yr and H2O ∼0.7-1.0 × 1014 g/yr, respectively—comparable to previous estimates. Further, we obtain a first estimate of global arc outflux of fluid-recycled F of ∼0.3-0.4 × 1012g/yr. Despite the inherent uncertainties, our results support models suggesting that the slab becomes strongly depleted in Cl and H2O in subduction zones. In contrast, much of the subducted F appears to be returned to the deep mantle, implying efficient fractionation of Cl and H2O from F during the subduction process. However, if slab devolatilization produces slab fluids with high Cl/F (∼9.5), slab melting will still produce components with low Cl/F ratios (∼0.9), similar to those characteristic of the upper continental crust (Cl/F ∼0.3-0.9).  相似文献   

6.
Distribution of water among the main rock-forming nominally anhydrous minerals of mantle xenoliths of peridotitic and eclogitic parageneses from the Udachnaya kimberlite pipe, Yakutia, has been studied by IR spectroscopy. The spectra of all minerals exhibit vibrations attributed to hydroxyl structural defects. The content of H2O (ppm) in minerals of peridotites is as follows: 23–75 in olivine, 52–317 in orthopyroxene, 29–126 in clinopyroxene, and 0–95 in garnet. In eclogites, garnet contains up to 833 ppm H2O, and clinopyroxene, up to 1898 ppm (~ 0.19 wt.%). The obtained data and the results of previous studies of minerals of mantle xenoliths show wide variations in H2O contents both within different kimberlite provinces and within the Udachnaya kimberlite pipe. Judging from the volume ratios of mineral phases in the studied xenoliths, the water content varies over narrow ranges of values, 38–126 ppm. At the same time, the water content in the studied eclogite xenoliths is much higher and varies widely, 391–1112 ppm.  相似文献   

7.
Coesite is typically found as inclusions in rock‐forming or accessory minerals in ultrahigh‐pressure (UHP) metamorphic rocks. Thus, the survival of intergranular coesite in UHP eclogite at Yangkou Bay (Sulu belt, eastern China) is surprising and implies locally “dry” conditions throughout exhumation. The dominant structures in the eclogites at Yangkou are a strong D2 foliation associated with tight‐to‐isoclinal F2 folds that are overprinted by close‐to‐tight F3 folds. The coesite‐bearing eclogites occur as rootless intrafolial isoclinal F1 fold noses wrapped by a composite S1–S2 foliation in interlayered phengite‐bearing quartz‐rich schists. To evaluate controls on the survival of intergranular coesite, we determined the number density of intergranular coesite grains per cm2 in thin section in two samples of coesite eclogite (phengite absent) and three samples of phengite‐bearing coesite eclogite (2–3 vol.% phengite), and measured the amount of water in garnet and omphacite in these samples, and also in two samples of phengite‐bearing quartz eclogite (6–7 vol.% phengite, coesite absent). As coesite decreases in the mode, the amount of primary structural water stored in the whole rock, based on the nominally anhydrous minerals (NAMs), increases from 107/197 ppm H2O in the coesite eclogite to 157–253 ppm H2O in the phengite‐bearing coesite eclogite to 391/444 ppm H2O in the quartz eclogite. In addition, there is molecular water in the NAMs and modal water in phengite. If the primary concentrations reflect differences in water sequestered during the late prograde evolution, the amount of fluid stored in the NAMs at the metamorphic peak was higher outside of the F1 fold noses. During exhumation from UHP conditions, where NAMs became H2O saturated, dehydroxylation would have generated a free fluid phase. Interstitial fluid in a garnet–clinopyroxene matrix at UHP conditions has dihedral angles >60°, so at equilibrium fluid will be trapped in isolated pores. However, outside the F1 fold noses strong D2 deformation likely promoted interconnection of fluid and migration along the developing S2 foliation, enabling conversion of some or all of the intergranular coesite into quartz. By contrast, the eclogite forming the F1 fold noses behaved as independent rigid bodies within the composite S1–S2 foliation of the surrounding phengite‐bearing quartz‐rich schists. Primary structural water concentrations in the coesite eclogite are so low that H2O saturation of the NAMs is unlikely to have occurred. This inherited drier environment in the F1 fold noses was maintained during exhumation by deformation partitioning and strain localization in the schists, and the fold noses remained immune to grain‐scale fluid infiltration from outside allowing coesite to survive. The amount of inherited primary structural water and the effects of strain partitioning are important variables in the survival of coesite during exhumation of deeply subducted continental crust. Evidence of UHP metamorphism may be preserved in similar isolated structural settings in other collisional orogens.  相似文献   

8.
Fluid inclusions and clusters of water molecules at nanometer-to submicron-scale in size have been investigated using transmission electron microscopy (TEM) and Fourier transform infrared spectroscopy (FTIR) in jadeite, quartz and symplectite aegirine–augite, albite, taramite and magnetite corona minerals from ultrahigh-pressure (UHP) jadeite–quartzite at Shuanghe, the Dabie Mountains, China. Fluid inclusions from 0.003 μm to 0.78 μm in size occur in jadeite and quartz crystals, and a small number of fluid inclusions from 0.001 μm to 0.25 μm have also been detected in symplectite-forming minerals. Most of the fluid inclusions have round or negative crystal morphology and contain aqueous fluids, but some contain CO2-rich fluids. They are usually connected to dislocations undetectable at an optical scale. The dislocations represent favorable paths for fluid leakage, accounting for non-decrepitation of most fluid inclusions when external pressure decreased at later stages, although there was partial decrepitation of some fluid inclusions unconnected to defect microstructures resulting from internal overpressure. Non-decrepitation and partial decrepitation of fluid inclusions resulted in changes of original composition and/or density. It is clear that identification of hidden re-equilibration features has significant implications for the petrological interpretation of post-peak metamorphic processes. Micro-FTIR results show that all jadeite and quartz samples contain structural water occurring as hydroxyl ions (OH−) and free water (H2O) in the form of clusters of water molecules. The H2O transformed from OH− during exhumation and could have triggered and enhanced early retrograde metamorphism of the host rocks and facilitated plastic deformation of jadeite and quartz grains by dislocation movement, and thus the H2O released during decompression might represent early-stage retrograde metamorphic fluid. The nominally anhydrous mineral (NAM) jadeite is able to transport aqueous fluids in concentrations of at least several hundred ppm water along a subduction zone to mantle depths in the form of clusters of water molecules and hydroxyl ions within crystals.  相似文献   

9.
Mineral water contents, together with the elements and isotopes of minerals and whole‐rock, were determined for garnet pyroxenites enclosed by ultrahigh‐pressure (UHP) metamorphic gneiss at Hujialin in the Sulu orogen. The results suggest that the garnet pyroxenites were generated in the Triassic by metasomatic reaction of the mantle wedge peridotite with hydrous felsic melts derived from partial melting of the deeply subducted continental crust. Measured water contents vary from 523 to 1213 ppm for clinopyroxene, and 55 to 1476 ppm for garnet. These mineral water contents are not only correlated with mineral major and trace element abundances but also relatively homogenous within single mineral grains. Such features preclude significant disturbance of the mineral water contents during pyroxenite exhumation from the mantle depth to the surface and thus indicate preservation of the primary water contents for the UHP metasomatites. The garnet pyroxenites are estimated to have bulk water contents of 424–660 ppm, which are higher than those for the MORB source, similar to or higher than those for the OIB sources and close to the lower limit for the arc magma source. The relationships between contents of mineral water and some elements suggest that the high water contents of garnet pyroxenites are primarily determined by the abundance of water‐rich clinopyroxene. Calculated whole‐rock H2O/Ce ratios are 63–145, higher than those for Hawaiian garnet pyroxenites and SWIR abyssal pyroxenites. These observations suggest that metasomatic pyroxene‐rich lithologies have the capacity to contribute high H2O concentrations and variable H2O/Ce ratios to the mantle. This lends support to the interpretation that the source of some intraplate basalts may be a heterogeneous mixture of peridotite and pyroxenite. On the other hand, the high water contents of garnet pyroxenites suggest that the ultramafic metasomatites are an important water reservoir in the mantle wedge.  相似文献   

10.
Liquidus phase relationships have been determined for a high-MgO basalt (STV301: MgO=12.5 wt%, Ni=250 ppm, Cr=728 ppm) from Black Point, St Vincent (Lesser Antilles arc). Piston-cylinder experiments were conducted between 7.5 and 20 kbar under both hydrous and oxidizing conditions. AuPd capsules were used as containers. Compositions of supraliquidus glasses and mass-balance calculations show that Fe loss is < 10% in the majority of experiments. Two series of water concentrations in melt were investigated: (i) 1.5 wt% and (ii) 4.5 wt% H2O, as determined by SIMS analyses on quenched glasses and with the by difference technique. The Fe3+/Fe2+ partitioning between Cr-Al spinel and melt and olivine-spinel equilibria show that oxidizing fO2 were imposed (NNO + 1.5 for the 1.5 wt% H2O series, NNO + 2.3 for the 4.5 wt% H2O series). For both series of water concentrations, the liquid is multiply-saturated with a spinel lherzolite phase assemblage on its liquidus, at 1235°C, 11.5 kbar (1.5 wt% H2O) and 1185°C, 16 kbar (4.5 wt% H2O). Liquidus phases are homogeneous and comparable to typical mantle compositions. Mineral-melt partition coefficients are generally identical to values under anhydrous conditions. The modal proportion cpx/opx on the liquidus decreases from the 1.5 wt% to the 4.5 wt% H2O series. The experimental data are consistent with STV301 being a product of partial melting of lherzolitic mantle. Conditions of multiple saturation progressively evolve toward lower temperatures and higher pressures with increasing melt H2O concentration. Phase equilibria constraints, i.e., the necessity of preserving the mantle signature seen in high-MgO and picritic arc basalts, and glass inclusion data suggest that STV301 was extracted relatively dry (∼ 2 wt% H2O) from its mantle source. However, not all primary arc basalts are extracted under similarly dry conditions because more hydrous melts will crystallize during ascent and will not be present unmodified at the surface. From degrees of melting calculated from experiments on KLB-1, extraction of a 12.5 wt% MgO melt with ∼ 2 wt% H2O would require a H2O concentration of 0.3 wt% in the sub-arc mantle. For mantle sources fluxed with a slab-derived hydrous component, extracted melts may contain up to ∼ 5.5 wt% H2O.  相似文献   

11.
New volatile data (CO2, H2O, He, Ne, and Ar) are presented for 24 submarine basaltic glasses from the Kolbeinsey Ridge, Tjörnes Fracture Zone and Mohns Ridge, North Atlantic. Low CO2 and He contents indicate that magmas were strongly outgassed with the extent of degassing increasing toward the south, as expected from shallower ridge depths. Ne and Ar are significantly more abundant in the southernmost glasses than predicted for degassed melt. The strong atmospheric isotopic signal associated with this excess Ne and Ar suggests syn- or posteruptive contamination by air. Degassing, by itself, cannot generate the large variations in δ13C values of dissolved CO2 or coupled CO2-Ar variations. This suggests that δ13C values were also affected by some other processes, most probably melt-crust interaction. Modelling indicates that degassing had a negligible influence on water owing to its higher solubility in basaltic melt than the other volatiles. Low H2O contents in the glasses reflect melting of a mantle source that is not water-rich relative to the source of N-MORB.Before eruption, Kolbeinsey Ridge melts contained ∼400 ppm CO2 with δ13C of −6‰, 0.1 to 0.35 wt.% H2O, 3He/4He ∼11 RA, and CO2/3He of ∼2 × 109. We model restored volatile characteristics and find homogeneous compositions in the source of Kolbeinsey Ridge magmas. Relative to the MORB-source, He and Ne are mildly fractionated while the 40Ar/36Ar may be low. The 3He/4He ratios in Tjörnes Fracture Zone glasses are slightly higher (13.6 RA) than on Kolbeinsey Ridge, suggesting a greater contribution of Icelandic mantle from the south, but the lack of 3He/4He variation along the Kolbeinsey Ridge is inconsistent with active dispersal of Icelandic mantle beyond the Tjörnes Fracture Zone.  相似文献   

12.
F, Cl, S and P were determined, using electron microprobe, in magmatic inclusions trapped within minerals and glass mesostasis from Wudalianchi volcanic rocks. The initial volcanic magma from Wudalianchi corresponds to the basanitic magma crystallized near the surface ( pressure < 91 Mpa ). The potential H2O content of this magma is in the range 2 — 4 wt. %. The initial composition of volcanic magmas varies regularly from early to late volcanic events. From the Middle Pleistocene to the recent eruptions (1719 – 1721 yr.), the basicity of volcanic magma tends to increase, as reflected by an increase in MgO and CaO contents and by a progressive decrease in SiO2 and K2O contents. Meanwhile. from early (Q2 ) to late (Q3) episodic eruptions of the Middle Pleistocene, the initial concentrations of chlorine in volcanic magmas range from 1430 – 1930 ppm to 1700 ppm and decrease to 700 — 970 ppm for the first episodic eruption during the Holocene (Q 4 1 ). The chlorine concentrations of volcanic magmas of recent eruption (Q 4 2 ) are increased again to 2600 – 2870 ppm. A parallel evolution trend for phosphorus and chlorine concentrations in magmas has been certified: 1500 – 5970 ppm (Q2)→ 3500 – 4210 ppm (Q3)→ 1100– 3500 ppm (Q 4 1 )→ 6800– 7900 ppm (Q 4 2 ). The fluorine contents of volcanic magmas, from early to late volcanic events, show the same trend: 770 – 2470 ppm → 200–700 ppm → 700 – 800 ppm. During the crystallization-evolution of volcanic magmas, fluorine and phosphorus tend to be enriched in residual magmas as a result of crystal-melt differentiation. for example. the fluorine contents reach 5000– 6800 ppm and the phosphorus contents, 2.93wt.% in residual magmas. An appreciable amount of chlorine may be lost from water rich volcanic magmas prior to eruption as a result of degassing. Apparently, water serves as a gas carrier for the chlorine. The chlorine contents of residual magmas may decrease to 100 – 300 ppm. The volcanic magmas from Wudalianchi are poor in sulfur, normally ranging from 200 to 400ppm. On account of the behavior of sulfur in magmas and the strontium and oxygen isotopic analyses ((87Sr /86Sr)i=0.70503– 0.70589; δ18O = + 5.50 – + 6.89 ‰ ), it can be considered that the basanitic magmas in the Wudalianchi volcanic area came from the upper mantle and have not yet been contaminated probably by continental crust materials.  相似文献   

13.
 The solubility of hydroxyl in the α, β and γ phases of (Mg,Fe)2SiO4 was investigated by hydrothermally annealing single crystals of San Carlos olivine. Experiments were performed at a temperature of 1000° or 1100 °C under a confining pressure of 2.5 to 19.5 GPa in a multianvil apparatus with the oxygen fugacity buffered by the Ni:NiO solid-state reaction. Hydroxyl solubilities were determined from infrared spectra obtained of polished thin sections in crack-free regions ≤100 μm in diameter. In the α-stability field, hydroxyl solubility increases systematically with increasing confining pressure, reaching a value of ∼20,000 H/106Si (1200 wt ppm H2O) at the α-β phase boundary near 13 GPa and 1100 °C. In the β field, the hydroxyl content is ∼400,000 H/106Si (24,000 wt ppm H2O) at 14–15 GPa and 1100 °C. In the γ field, the solubility is ∼450,000 H/106Si (27,000 wt ppm H2O) at 19.5 GPa and 1100 °C. The observed dependence of hydroxyl solubility with increasing confining pressure in the α phase reflects an increase in water fugacity with increasing pressure moderated by a molar volume term associated with the incorporation of hydroxyl ions into the olivine structure. Combined with published results on the dependence of hydroxyl solubility on water fugacity, the present results for the α phase can be summarized by the relation C OH = A(T)f nH2Oexp(−PΔV/RT), where A(T) = 1.1 H/106Si/MPa at 1100 °C, n = 1, and ΔV = 10.6×10–6 m3/mol. These data demonstrate that the entire present-day water content of the upper mantle could be incorporated in the mineral olivine alone; therefore, a free hydrous fluid phase cannot be stable in those regions of the upper mantle with a normal concentration of hydrogen. Free hydrous fluids are restricted to special tectonic environments, such as the mantle wedge above a subduction zone. Received: 10 February 1995 / Accepted: 23 October 1995  相似文献   

14.
The present study illustrates the interest of using the elastic recoil detection analysis (ERDA) method to characterize any geological sample matrix with respect to hydrogen. ERDA is combined with Rutherford back scattering (RBS) and particle induced X-ray emission (PIXE), allowing the simultaneous characterization of the matrix with respect to major and trace elements (Z > 15). Analyses are performed by mapping of a 4 × 16 μm2 incident beam of 4He+ on large areas (50 × 200 μm2). The method is almost not destructive and requires no calibration with respect to well known hydrous samples. Hydrous and nominally anhydrous phases in contact with each other in the same sample may both be characterized. The depth of the analyses is limited to several μm beneath the surface, allowing tiny samples to be investigated, provided their sizes are larger than the incident beam. Our setup has been improved in order to allow H determination on a micrometric scale with a 5-15% relative uncertainty and a detection limit of 94 wt ppm H2O. We present multi-elemental mappings on a large panel of samples: (1) natural and analogue synthetic glasses from Stromboli volcano (0.44-4.59 wt% H2O), natural rhyolitic glasses (1466-1616 wt ppm H2O); (2) magmatic rhyolitic melt inclusions from Guadeloupe Island (4.37-5.47 wt% H2O) and their quartz host crystal (2020 ± 230 wt ppm H2O); (3) nominally anhydrous natural (82-260 wt ppm H2O) and experimentally hydrated (240-790 wt ppm H2O) olivines; natural clinopyroxenes (159-716 wt ppm H2O); natural orthopyroxenes (201-452 wt ppm H2O); a natural garnet (90 wt ppm H2O). Results show that ERDA is a strong and accurate reference method that can be used to characterize geological sample from various matrix compositions from high to low water contents. It can be used to calibrate other methods of microanalysis such as Fourier Transform Infrared Spectroscopy (FTIR) or secondary ion mass spectrometry (SIMS).  相似文献   

15.
Water partitioning between mantle minerals from peridotite xenoliths   总被引：1，自引：1，他引：1  
The speciation and amount of water dissolved in nominally anhydrous silicates comprising eight different mantle xenoliths has been quantified using synchrotron micro-FTIR spectroscopy. Samples studied are from six geographic localities and represent a cross-section of the major upper mantle lithologies from a variety of tectonic settings. Clinopyroxene contains between 342 and 413 ppm H2O. Orthopyroxene, olivine and garnet contain 169–201, 3–54 and 0 to <3 ppm H2O, respectively. Pyroxenes water contents and the distribution of water between ortho- and clinopyroxene is identical regardless of sample mineralogy (D watercpx/opx = 2.1 ± 0.1). The total water contents of each xenolith are remarkably similar (113 ± 14 ppm H2O). High-resolution spectroscopic traverses show that the concentration and speciation of hydrous defects dissolved in each phase are spatially homogeneous within individual crystals and identical in different crystals interspersed throughout the xenolith. These results suggest that the amount of water dissolved in the silicate phases is in partial equilibrium with the transporting melt. Other features indicate that xenoliths have also preserved OH signatures of equilibrium with the mantle source region: Hydroxyl stretching modes in clinopyroxene show that garnet lherzolites re-equilibrated under more reducing conditions than spinel lherzolites. The distribution of water between pyroxenes and olivine differs according to xenolith mineralogy. The distribution of water between clinopyroxene and olivine from garnet peridotites (D watercpx/oliv(gnt) = 22.2 ± 24.1) is a factor of four greater than mineral pairs from spinel-bearing xenoliths (D watercpx/oliv(sp) = 88.1 ± 47.8). Such an increase in olivine water contents at the spinel to garnet transition is likely a global phenomenon and this discontinuity could lead to a reduction of the upper mantle viscosity by 0.2–0.7 log units and a reduction of its electrical resistivity by a factor of 0.5–0.8 log units.  相似文献   

16.
Major and trace elements and water contents were analyzed in 16 peridotite xenoliths embedded by the Cenozoic basalts in Pingnan (southeastern Guangxi Province), to constrain the chemical composition and evolution of the lithospheric mantle located in the central part of the South China Block (SCB). The peridotites are mainly moderately refractory harzburgites and lherzolites (Mg#-Ol?=?90.3–91.7) and minor fertile lherzolites (Mg#-Ol?=?88.9–89.9). Clinopyroxenes in the peridotites show LREE-depleted pattern, and commonly exhibit negative anomalies in Nb and Ti, suggesting the peridotites probably represent residues after 1–10% of partial melting without significant mantle metasomatism. Water contents range from 146 to 237 ppm wt. H2O in clinopyroxene, and from 65 to 112 ppm wt. H2O, in orthopyroxene but are below detection limit (2 ppm wt. H2O) in olivine. Calculated bulk water contents, based on the mineral modes and partition coefficient, range from 14 to 83 ppm wt. H2O (average 59 ppm wt. H2O). There is a correlation between melting indices (such as Mg#-Ol, Ybn in clinopyroxene) and water contents in clinopyroxene and orthopyroxene, but no correlation is observed between the whole-rock water contents and the redox state (Fe3+/∑Fe ratios in spinel), suggesting that water contents in the peridotites are mainly controlled by the degree of partial melting rather than by oxygen fugacity. The lithospheric mantle beneath the interior of the SCB may not be compositionally stratified; fertile and moderately refractory mantle coexist at the similar depths. Geochemical data and water contents of the studied peridotites are similar to the proposed MORB source and indicate that the ancient refractory lithospheric mantle was irregularly eroded or reacted by the upwelling asthenosphere, and eventually replaced by juvenile fertile accreted mantle through the cooling of the asthenosphere.  相似文献   

17.
Chlorine-35 magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectra were collected at 14.1 and 18.8 Tesla fields to determine the atomic scale structural environments of the chloride ions in anhydrous and hydrous silicate and aluminosilicate glasses containing 0.2 to 0.7 wt% Cl. NMR peaks are broad and featureless, but are much narrower than the total chemical shift range for the nuclide in inorganic chlorides. Peak widths are primarily due to quadrupole interactions and to a lesser extent to chemical shift distributions. Peak positions are quite different for the Na- and Ca-containing glasses, suggesting that most Cl− coordination environments contain network modifier cations. Comparison of peak positions and shapes for silicate and aluminosilicate glasses containing either Na or Ca suggests that there is no obvious contribution from Cl− bonded to Al, and relative quantitation of peak areas indicates that there is no systematic undercounting of 35Cl spins in the aluminous vs. the Al-free samples. In Ca-Na silicate glasses with varying Ca/(Ca + Na), the mixed-cation glasses have intermediate chemical shifts between those of the end members, implying that there is not a strong preference of either Ca2+ or of Na+ around Cl−. Hydrous Na-aluminosilicate glasses with H2O contents up to 5.9 wt% show a shift to higher frequency NMR signal with increasing H2O content, while the quadrupole coupling constant (CQ) remains constant at ∼3.3 MHz. However, the change in frequency is much smaller than that expected if H2O systematically replaced Na+ in the first-neighbor coordination shell around Cl−. A series of hydrous Ca-aluminosilicate glasses with H2O contents up to 5.5 wt% show no shift in NMR signal with increasing H2O content. The CQ remains constant at ∼4.4 MHz, again suggesting no direct interaction between Cl− and H2O in these samples.  相似文献   

18.
Raman spectroscopy was used to analyze quantitatively water in silicate glasses and melt inclusions and to monitor H2O–OH speciation. Calibration is based on synthetic glasses with various water contents (0.02–7.67% H2O); water determination and OH–H2O differentiation on the area of the Si–O broad band at 468 cm–1 and the asymmetric O–H band at 3,550 cm–1. Each Raman spectrum has been decomposed into four Gaussian + Lorentzian components centered at 3,330, 3,458, 3,560, and 3,626 cm–1 using the Levenberg–Marquardt algorithm. These components are interpreted to be two different types of H2O molecule sites. The influence of the temperature on the loss of water is more important for molecular water than for the hydroxyl groups. The H2O–OH partition confirms the typical evolution of water speciation in rhyolitic glasses as a function of the bulk water content. Method limitations have been studied for the application to natural melt inclusions.Editorial responsibility: T.L Grove  相似文献   

19.
Hydrous species and the amount of water (OH? ions and crystal hydrate H2O) in structures of nominally anhydrous rock-forming minerals (olivine, ortho- and clinopyroxenes) were studied with Fourier spectroscopy in peridotite nodules (19 samples) from Cenozoic alkali basalts of the Baikal-Mongolia region (Dariganga Plateau, Taryat Depression, and Vitim Plateau). Single-crystal samples oriented relative to the crystallographic axes of minerals were examined with an FTIR spectrometer equipped with an IR microscope at the points of platelets free from fluid inclusions. FTIR spectra were measured in regions of stretching vibrations of OH? and H2O (3800–3000 cm?1) and deformation vibrations of H2O (1850–1450 cm?1). The water content in mineral structures was determined from integral intensities. To estimate the conditions of entrapment and loss of structural water in minerals, their chemical composition, including Fe2+ and Fe3+ contents, was determined with an electron microprobe analysis and Mössbauer spectroscopy. The bulk chemical composition of some nodules was determined with XRF and ICP MS. The total water content (OH? + H2O) varies from 150 to 1140 ppm in olivines, from 45 to 870 ppm in clinopyroxenes, and from 40 to 1100 ppm in orthopyroxenes. Both water species in the mineral structures are retained down to a depth of 150–160 km in wide temperature and pressure ranges (1100–1500 °C, 32–47 kbar) at the oxygen fugacity of ?1.4 to ?0.1 log units relative to that of the quartz-fayalite-magnetite buffer.  相似文献   

20.
Although, the kinetic reactivity of a mineral surface is determined, in part, by the rates of exchange of surface-bound oxygens and protons with bulk solution, there are no elementary rate data for minerals. However, such kinetic measurements can be made on dissolved polynuclear clusters, and here we report lifetimes for protons bound to three oxygen sites on the AlO4Al12(OH)24(H2O)127+ (Al13) molecule, which is a model for aluminum-hydroxide solids in water. Proton lifetimes were measured using 1H NMR at pH ∼ 5 in both aqueous and mixed solvents. The 1H NMR peak for protons on bound waters (η-H2O) lies near 8 ppm in a 2.5:1 mixture of H2O/acetone-d6 and broadens over the temperature range −20 to −5 °C. Extrapolated to 298 K, the lifetime of a proton on a η-H2O is τ298 ∼ 0.0002 s, which is surprisingly close to the lifetime of an oxygen in the η-H2O (∼0.0009 s), but in the same general range as lifetimes for protons on fully protonated monomer ions of trivalent metals (e.g., Al(H2O)63+). The lifetime is reduced somewhat by acid addition, indicating that there is a contribution from the partly deprotonated Al13 molecule in addition to the fully protonated Al13 at self-buffered pH conditions. Proton lifetimes on the two distinct sets of hydroxyls bridging two Al(III) (μ2-OH) differ substantially and are much shorter than the lifetime of an oxygen at these sites. The average lifetimes for hydroxyl protons were measured in a 2:1 mixture of H2O/dmso-d6 over the temperature range 3.7-95.2 °C. The lifetime of a hydrogen on one of the μ2-OH was also measured in D2O. The τ298 values are ∼0.013 and ∼0.2 s in the H2O/dmso-d6 solution and the τ298 value for the μ2-OH detectable in D2O is τ298 ∼ 0.013 s. The 1H NMR peak for the more reactive μ2-OH broadens slightly with acid addition, indicating a contribution from an exchange pathway that involves a proton or hydronium ion. These data indicate that surface protons on minerals will equilibrate with near-surface waters on the diffusional time scale.  相似文献   

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