water solubility in pyrope to 100 kbar the solubility and incorporation mechanism of water in natural almost pure pyrope from dora maira western alps was investigated the infrared spectrum of the natural untreated sample 58 ppm water shows several exceptionally sharp bands in the oh stretching region including a single band at 3601 9 cm 1 and a band system with main components at 3640 5 3650 8 and 3660 6 cm 1 high temperature and high pressure infrared spectra suggest that the two absorption features arise from almost free oh groups in sites with different compressibility and thermal expansivity with the site causing the 3601 9 cm 1 band being much stiffer pyrope samples were annealed in a piston cylinder or multi anvil apparatus for several days in the presence of excess water excess sio2 and excess al2sio5 to determine the equilibrium solubility of water in pyrope to 100 kbar total solubility increases with pressure however this is exclusively due to the high frequency band system while the intensity of the low frequency band decreases with pressure at 1000 c and the oxygen fugacity of the ni nio buffer the bulk solubility can be described by the equation c oh af h2o 0 5exp p v rt with a 0 679 ppm bar0 5 and v 5 71 cm3 mol this equation implies the incorporation of water in the crystal as isolated oh groups with increasing temperature solubility appears to decrease with h 14 kj mol at fe feo buffer conditions solubility is 30 to 50 lower than with the ni nio buffer suggesting that the incorporation of oh is not coupled to the reduction of fe3 possibly the 3601 9 cm 1 band is associated with the tetrahedral oh b defect and the high frequency system with the dodecahedral oh li defect based on the experimentally established solubility model it is estimated that garnet in a hot subducted slab will transport 170 ppm of water into the mantle beyond the breakdown limit of amphibole in a cold slab 470 ppm of water can be incorporated into garnet at the breakdown limit of phengite these numbers imply that a significant fraction of the total water in the hydrosphere has been recycled into the mantle since the proterozoic

monitoring volcano slope instability with synthetic aperture radar a review and new data from pacaya guatemala and stromboli italy volcanoes abstract volcano slope instability manifests in many forms ranging from steady state to punctuated movement or shallow erosion to deep seated spreading the interplay of gravity magmatic or hydrothermal fluids and often active tectonics on a volcanic edifice results in complex spatial and temporal variations in deformation kinematics while this makes the recognition assessment and monitoring of volcano slope instability challenging advancements in synthetic aperture radar sar technology have significantly accelerated our knowledge of instability phenomena and our ability to assess their hazards this review discusses the applications and challenges of sar imagery to various slope instabilities at volcanoes around the world sar amplitude images are powerful tools for mapping areas of geomorphological changes these snapshots can be combined using interferometric sar insar to create multi temporal deformation maps that provide unique information on the evolution of slope failures space borne insar has become an economic way to detect changes at volcanoes at very high resolution ground based insar gbinsar can produce frequent sar images on the order of seconds to minutes propelling insar from monitoring to surveillance and early warning applications however interpreting insar derived ground deformation signals related to volcano slope instability is still challenging deformation from magma rise or variations in hydrothermal systems may be inseparable from persistent deep seated flank motion similarly shallow or localized ground motion may occur in overlap with thermal contraction or subsidence of newly emplaced lava or tephra deposits if triggered to failure landslides can vary over several magnitudes from small volume rock falls that pose only a localized hazard to large volume debris avalanches capable of travelling tens of kilometers away from the source these collapses can have cascading hazards if accompanied by directed blasts or tsunamis emphasizing the need for continued advancement of our understanding of these events and their consequences to highlight the utility of sar for measuring and monitoring mass movement two case studies of stromboli italy and pacaya guatemala volcanoes are discussed in detail where recent instability events persistent volcanic activity and ground truth constraints have resulted in excellent case histories in applying sar imagery to understand these potentially hazardous slope instabilities

fluid evolution during hp and uhp metamorphism in dabie shan china constraints from mineral chemistry fluid inclusions and stable isotopes the dabie shan ultrahigh pressure uhp metamorphic terrane is introduction located in the eastern part of the east west striking qinling dabie the discovery of coesite and micro diamond as phases orogenic belt in china a major mylonitized contact zone of produced by deep metamorphism of continental crust 200 300 m width divides dabie shan into the south dabie revolutionized our understanding of continental collision terrane sdt and the north dabie complex ndc combined zones and mantle dynamics attending subduction of investigation of major and trace element geochemistry fluid inclusions continental lithosphere in general we define metaand oxygen and hydrogen isotopes constrains the fluid history during morphic rocks with coesite and micro diamond as ultrathe metamorphic evolution of the two metamorphic belts which high pressure uhp rocks which have been increasingly differ in their fluid and metamorphic evolution fluid inclusions in recognized so far more than a dozen uhp terranes rocks from the sdt are mainly aqueous with varying salinities have been documented within the major continental whereas those from the ndc are dominated by co2 low o collision belts in the eurasian plate values in the sdt rocks 2 8 to 8 6 indicate meteoric the dabie sulu belt in east central china is the water rock interactions before uhp metamorphism whereas rocks largest among the uhp metamorphic terranes found from the ndc show normal o values 6 7 9 0 with no worldwide research activities over the past decade have obvious meteoric water rock signature whole rock rare earth element documented a number of characteristic features of this ree contents correlate with oxygen isotope compositions samples area including rapid subduction followed by rapid initial from the sdt have higher ree contents and lower o values uplift e g li et al 1993 xiao li 1993 eide et al whereas samples from the ndc have lower ree contents and 1994 the abundance of hydroxyl bearing uhp mineral higher o values during retrograde metamorphism fluids with phases okay 1994 zhang et al 1995 very low o different hydrogen isotope compositions interacted with the rocks from values ranging from 15 to 10 yui et al 1995 1997 the sdt zheng et al 1996 1998 1999 xiao et al 1997 rumble yui 1998 and the world record highest nd 0 values ever measured for eclogite jahn et al 1996 the nature and mobility of fluids in high pressure hp

hydroxide in pyroxene variations in the natural environment a suite of 51 pyroxenes from a wide range of geological environments was examined with infrared spectroscopy small amounts of oh occur in nearly all the samples suggesting that oh groups are a minor component of most pyroxenes the oh concentrations vary 0 002 0 12 wt oh as a function of geological setting with the greatest amounts occurring in mantle derived samples the intensities of certain oh absorption bands are somewhat correlated with pyroxene composition in particular with the presence of trivalent cations this suggests that crystal chemical or compositional factors also control the oh incorporation the oh incorporated in the pyroxene structure is easily distinguishable from oh owing to amphibole lamellae which usually occur in diopsides and often in orthopyroxenes oh in pyroxene is probably a function of the activity of hydrous components during crystallization but may also depend on postcrystallization changes in the geological environment

water content in natural eclogite and implication for water transport into the deep upper mantle abstract infrared spectroscopy and ion micro probe measurements showed that the major constituent minerals of eclogites from the kokchetav massif which have been subducted to 180 km depths contain significant amounts of water up to 870 ppm h 2 o by weight in omphacite 130 ppm h 2 o in garnet and 740 ppm h 2 o in rutile omphacite shows three hydroxyl absorption bands at 3440 3460 3500 3530 and 3600 3625 cm 1 garnet has a single band at 3580 3630 cm 1 and rutile has a single sharp band at 3280 cm 1 the hydroxyl absorbance at these wavenumbers changes with the crystal orientation in polarized infrared radiation indicating that the water is structurally incorporated in these minerals the water contents in omphacite and garnet increase systematically with the metamorphic pressure of the host eclogites the partitioning coefficient of the water content between coexisting garnet and omphacite is similar in different eclogites d grt omp 0 1 0 2 but decreases slightly at high pressure based on the mineral proportions of the eclogites we estimate bulk rock water content in the eclogites ranging from 3070 to 300 ppm h 2 o by weight although hydrous minerals are absent in the diamond grade eclogite 60 kbar and 1000 c trace amounts of water are incorporated in the nominally anhydrous minerals such as omphacite and garnet the presence of significant water in these minerals implies that the subducting oceanic crust can transport considerable amounts of water into the deep upper mantle beyond the stability of hydrous minerals such water may be stored in the deep upper mantle and have an important influence on dynamics in the earth s interior

low δ18o zircons u pb dating and the age of the qinglongshan oxygen and hydrogen isotope anomaly near donghai in jiangsu province china zircons from metamorphosed granites exposed near qinglongshan have 18ovsmow values of 7 to 0 in both grain rims and cores the concordant 238u 206pb ages of zircon cores are 684 to 754 ma with rims at 221 ma discordant 238u 206pb ages range from 242 to 632 ma results demonstrate a neoproterozoic age for the origin of the qinglongshan oxygen and hydrogen isotope anomaly the low 18o values were imprinted on the rocks by a hydrothermal system charged with meteoric water from a cold climate groundwater circulation was driven by heat from cooling granitic magma the geologic age of the hydrothermal system correlates with that of the nantuo tillite in the sinian strata of the south china block suggesting that qinglongshan s cold climate may be a manifestation of neoproterozoic snowball earth

sm nd and rb sr dating of pyroxene garnetite from north dabie in east central china problem of isotope disequilibrium due to retrograde metamorphism abstract oxygen isotopes may serve as a guide to evaluate whether equilibria are preserved in the sm nd and or rb sr systems in eclogites that experience retrograde metamorphism this study demonstrates that sm nd rb sr and o isotopes for minerals from two portions of a clinopyroxene garnetite from north dabie in east central china record both equilibrium peak metamorphic conditions and disequilibrium conditions resulting from anhydrous retrograde metamorphism the minerals are homogeneous in terms of major elements and show no variation across the sample but clinopyroxene shows variable degrees of alteration pure primary mineral separates that are in o isotope equilibrium yield triassic sm nd isochron ages of 219 11 and 229 13 ma that match previously published zircon u pb ages for peak metamorphism thus the sm nd system in these minerals equilibrated during peak metamorphism and remained unaffected by retrograde metamorphism in contrast altered and impure clinopyroxenes that display oxygen isotope disequilibria fall off the sm nd isochron defined by the pure minerals implying that like oxygen the sm nd systems in these clinopyroxene were disturbed during retrogression no meaningful isochrons are found from the rb sr dating even in the pure primary minerals implying that these systems were disturbed during retrograde metamorphism and the diffusion rate of sr is faster than those of sm nd and o in mafic minerals our results suggest that the oxygen isotopes in metamorphic minerals can be used to evaluate the validity of sm nd mineral isochrons in dating peak metamorphic events in addition variations in the sm nd concentration and isotopic compositions of altered and impure clinopyroxenes from the two portions suggest heterogeneous effects on the minerals from external and internal fluids

multiphase solid inclusions in uhp rocks su lu china remnants of supercritical silicate rich aqueous fluids released during continental subduction abstract primary multiphase solid ms inclusions without preserved fluid are found within peak minerals in kyanite quartzite topaz and kyanite phengite epidote eclogite from donghai area su lu terrane typical mineral association in inclusions is paragonite muscovite anhydrite corundum alunite type sulphate zircon calcite chlorite sio 2 barite pyrite apatite in quartzites and paragonite rutile apatite amphibole zn staurolite magnetite plagioclase zircon pyrite alunite type sulphate zn mg fe al ti spinel in eclogites on the basis of the fluid inclusion textures and of the daughter phase assemblage calculated fluid composition is as follows in quartzites 24 wt sio 2 30 wt al 2 o 3 9 wt cao 5 wt k 2 o 3 wt na 2 o 11 wt so 3 18 wt h 2 o with traces of tio 2 fe 2 o 3 feo mgo bao p 2 o 5 cl f and co 3 2 and in eclogites 26 wt sio 2 21 wt tio 2 20 wt al 2 o 3 2 wt mgo 4 wt feo 6 wt fe 2 o 3 7 wt cao 3 wt na 2 o 3 wt p 2 o 5 7 wt h 2 o 1 wt cl and traces of zno mno k 2 o so 3 and f originally trapped chloride poor aqueous fluids contained very high amounts in the order of tens of wt of si 4 al 3 and ti 4 solute species reflect the chemical composition of the host rocks mg 2 fe 2 ti 4 p 5 and na are abundant in the fluids present in eclogites while fluids are enriched in al 3 k na so 4 2 co 3 2 in quartzites we propose that multiphase solid inclusions represent remnants of high density supercritical silicate rich aqueous fluids that were in equilibrium with peak minerals at uhp conditions these fluids show characters which are transitional between aqueous fluids and silicate melts and were probably produced by dehydration reactions of the host rocks during the latest stages of subduction

talc magnesite and ti clinohumite bearing ultrahigh pressure meta mafic and ultramafic complex in the dabie mountains china

an experimental investigation of hydroxyl solubility in jadeite and na rich clinopyroxenes the solubility and incorporation mechanisms of water in synthetic water saturated jadeite and na rich clinopyroxenes have been experimentally investigated infrared spectra for water saturated jadeite synthesised from 2 0 to 10 gpa show two prominent sharp peaks at 3 373 and 3 613 cm 1 together with several weaker features in the oh stretching region indicating that there are at least 5 distinct modes of hydrogen incorporation in the structure water solubility in pure jadeite reaches a maximum of about 450 ppm by weight at 2 gpa and slowly decreases with increasing pressure to about 100 ppm at 10 gpa solubility can be described by the function coh a fh2o0 5 exp p vsolid rt where coh is water solubility in ppm h2o by weight a is 7 144 ppm bar0 5 fh2o is water fugacity and vsolid 8 019 cm3 mol is the volume change of the clinopyroxene upon incorporation of oh jadeite provides a good model for understanding hydrogen incorporation mechanisms in more complex omphacite compositions assignment of absorption bands in ir spectra verifies the importance of cation vacancies on the m2 site in providing mechanisms for hydrogen incorporation however results also suggest that substitution of lower valency cations onto the m1 site may also be important solid solution of jadeite with diopside and in particular with ca eskola component leads to a drastic increase of water solubility and the bulk composition has a more important effect on the capacity of omphacite to store water than pressure and temperature omphacite is expected to be the major carrier of water in a subducted eclogite after the breakdown of hydrous minerals

archean mantle heterogeneity and the origin of diamondiferous eclogites siberia evidence from stable isotopes and hydroxyl in garnet data are presented for the o isotopic composition of clinopyroxene and garnet the c isotopic composition of diamond and the oh content of garnet from eclogite xenoliths brought to the surface by the udachnaya kimberlite pipe yakutia siberia radiogenic isotopic data suggest that the eclogites could have been derived from an ultradepleted mantle at approximately 2 9 ga pearson et al 1995 snyder et al in preparation o isotopic compositions generally show equilibration between the eclogitic minerals cpx grt 0 11 0 41 and have 18 o smow for both garnet and clinopyroxene that lie near the range of accepted mantle values of 5 7 0 7 however several eclogites indicate significant deviations from this range at higher values of 6 8 7 0 also two eclogites lie at the lower end of the mantle range at values of 4 8 and 5 0 all in clinopyroxene c isotopic compositions of diamonds all have 13 c pdb in the range of 1 to 7 and are centered at approximately 5 also within the range of accepted mantle values the oh contents of the garnet are generally between 0 and 22 ppm as h 2 0 although two samples exceed 70 ppm this range of oh is similar to eclogitic garnet from the kaapvaal craton of southern africa the mantle c isotopic values of associated diamonds the majority of o isotopic data and the low oh content of the minerals although suggesting a general lack of crustal participation in the formation of the udachnaya eclogites do not rule out the participation of some ancient crustal material that these eclogites include both 18 o enriched and 18 o depleted types suggests that the protoliths may have been overprinted by both low and high temperature hydrothermal events cf jacob et ai 1994 a positive correlation between 18 o and 87 sr 86 sr allows the interpretation of these eclogites as representing a cross section of an archean ophiolite however the lack of a single coherent grouping on a plot of 18 o vs 87 sr 86 sr suggests that if the udachnaya eclogites were derived from oceanic crust they cannot be cogenetic and must represent at least two separate ophiolite sequences conversely if the eclogites are found to be cogenetic then a totally different process affected their formation and a probable metasomatic mechanism was operative because of the total lack of correlation of 18 o with other geochemical parameters we find no compelling evidence that all eclogites are derived ultimately from oceanic crust

the influence of water on the petrogenesis of subductionrelated igneous rocks the presence of dissolved water can significantly change the sequence in which different minerals crystallize from a silicate magma1 3 this will alter the compositional path followed by residual liquids the liquid line of descent and modify the types and compositions of crystals that accumulate at the site of cooling the sharp decrease in the solubility of water in silicate melts with decreasing pressure makes direct measurements of pre eruptive concentrations in magmas difficult because much of the dissolved water boils off before eruption here we report experimental results on the crystallization of basalts that contain substantial dissolved water up to 6 wt and show how the results can be used to infer the amount of dissolved h2o involved in the petrogenesis of lavas that preserve a record of their liquid lines of descent or the accumulated minerals left behind after solidification the presence of abundant magmatic water is a signature of subduction zone volcanism4 and can be used to associate a suite of magmas or igneous cumulates with a convergent margin back arc or interarc tectonic setting

the high pressure stability of hydrous phases in orogenic belts an experimental approach on eclogite forming processes abstract metamorphic evolution of orogenic belts is characterized by reactions involving hydrous phases stability relations of hydrous phases depend on h 2 o activity availability during metamorphism however hydrous phases do occur in synthetic and natural systems also at water undersaturated conditions h 2 o undersaturated experiments in the cao al 2 o 3 sio 2 h 2 o model system were performed in order to predict the role of hydrous phases in h 2 o undersaturated compositions at constant pressure and temperature these experiments yielded different assemblages of hydrous anhydrous phases depending on the experimental bulk h 2 o content in natural eclogites of mafic to intermediate bulk composition common hydrous phases include amphibole lawsonite zoisite mg chloritoid paragonite and talc complex continuous reactions delimit the stability fields of the different assemblages involving these hydrous phases such continuous reactions can be used as powerful petrogenetic tools to derive p t conditions of natural eclogites derivation of h 2 o undersaturated phase relationships for natural and synthetic systems show that hydrous phases also occur in h 2 o undersaturated bulk compositions at eclogite facies conditions comparison of experimentally determined phase relationships in mafic rocks with pressure temperature evolution of orogenic terrains demonstrates that at subsolidus conditions a trend toward h 2 o saturation is necessarily maintained during prograde p t paths in orogenic belts as far as dehydration reactions occur any prograde p t path necessarily leads to a maximized occurrence of hydrous phases and thus a maximized h 2 o preservation is achieved during metamorphism

the isotopic composition of hydrogen in nominally anhydrous mantle minerals the common nominally anhydrous minerals of the earth s mantle are an important reservoir for hydrogen in the earth s interior due to their ability to incorporate hydroxyl in trace quantities we present measurements of the isotopic composition d h ratio of hydrogen from upper mantle derived garnet enstatite and augite employing a two step extraction procedure with infrared spectroscopic monitoring of oh removal from the samples raw d values of all samples range from 80 to 130 and blank corrected d of high purity separates with 50 blank contribution to the measured gas lie in the range 92 to 113 these d values together with predictions of fractionation behavior from ir spectroscopic systematics suggest that the d h ratio of the nominally anhydrous mineral reservoir may differ from that of other mantle hydrogen in being relatively depleted in deuterium to the extent that nominally anhydrous minerals control the distribution of water between the earth s hydrosphere and mantle isotopic fractionations between oh in these minerals and hydrous melts or fluids may contribute to the large d h fractionation between the mantle and the hydrosphere

sm nd and rb sr isotopic chronology and cooling history of ultrahigh pressure metamorphic rocks and their country rocks at shuanghe in the dabie mountains central china abstract ultrahigh pressure metamorphic uhpm rocks at shuanghe area in the dabie mountains occur as a uhpm block within the regional granitic gneiss a sm nd isochron defined by garnet omphacite rutile from coesite bearing eclogite yield an age of 226 3 3 2 ma another sm nd isochron defined by garnet two phengites form uhp gneiss yield a similar age of 226 5 2 3 ma the two consistent sm nd ages defined by three uhpm minerals suggest that nd isotopic equilibrium between uhpm minerals in these rocks during uhp metamorphism has been achieved this may correspond to the age of peak metamorphism with an average metamorphic temperature of 800 c it is demonstrated that the retrograde metamorphism of uhpm rocks occurred in an open chemical system whereas the nd and sr isotopic systematics of uhpm minerals may have remained closed nd and sr isotopic disequilibrium between uhpm minerals and retrograde metamorphic minerals has been observed therefore the tie line of garnet or phengite and whole rock containing retrograde metamorphic minerals gives an old sm nd age and a young rb sr age respectively with no geologic significance however a rb sr ages of 219 0 6 6 ma defined by phengite garnet from a uhpm gneiss indicates that the uhpm rocks at shuanghe cooled down to 500 c at that time it suggests that the uhpm rocks at shuanghe experienced the first rapid cooling during 226 219 ma on the other hand the rb sr ages of 174 7 8 to 169 2 3 3 ma defined by retrograde minerals amphibole or biotite with closure temperature ranging from 450 to 300 c and intensely retrograded metamorphic rocks reflect a second rapid cooling during this time interval this is consistent with the rapid cooling time of 190 170 ma of the orthogneiss in the dabie su lu uhpm belt obtained by ar ar dating method in contrast to uhpm rocks the nd isotopic composition of the garnet in granitic gneiss has been reset during retrograde metamorphism and is in equilibrium with those of retrograde epidote and biotite which yields a sm nd isochron age of 213 5 ma indicating the retrometamorphic time corresponding to amphibolite facies in addition the biotites from the granitic gneiss yield rb sr ages of 171 173 ma similar to those of the uhpm rocks these data suggest that the country rocks granitic gneiss may have a similar cooling history to the uhpm rocks at shuanghe two stages of rapid cooling of uhpm rocks at shuanghe may correspond two stages of fast uplift the initial rapid uplifting and cooling of uhpm rocks during 226 219 ma may be caused by compression tectonics during subducting time of the continental crust whereas the later rapid cooling may reflect the exhumation of the entire subducted continental crust by extension during the early middle jurassic

quantitative analysis of trace oh in garnet and pyroxenes to calibrate infrared ir spectroscopy for quantitative analysis of trace structural oh in specific minerals we have determined concentrations of h in pure separates of mantle derived pyrope garnet 56 6 ppm h 2o by weight augite 268 8 ppm h 2o and enstatite 217 11 ppm h 2o by manometry after heating the samples and extracting h 2 gas under vacuum ir spectroscopy confirmed the presence of intrinsic oh in these samples prior to extraction and indicated between 86 and 100 removal of h during the extraction procedure the integral specific absorption coefficients of 1 39 0 14 l 7 09 0 32 and 15 6 0 94 ppm h 2o cm 2 for pyrope augite and enstatite respectively allow precise spectroscopic determination of the oh content of upper mantle garnets and pyroxenes to concentration levels of a few parts per million uncertainties in accuracy depend on mineral composition and characteristics of the oh absorption spectrum and are estimated to range between 10 and 50

sodic amphibole exsolutions in garnet from garnet peridotite north qaidam uhpm belt nw china implications for ultradeep origin and hydroxyl defects in mantle garnets two types of amphibole exsolution lamellae were discovered in garnet from a few garnet peridotites from the north qaidam ultrahigh pressure metamorphic belt northern tibet nw china the amphibole lamellae are strictly oriented in four directions corresponding to the isometric form 111 i e octahedron planes of garnet observations by transmission electron microscopy tem show that amphibole lamellae are topotaxtially concordant with the host garnet and possess 9 8 to 10 a lattice c spacing electron microprobe analysis reveals that these exsolved amphibole lamellae are high in na and ti the tem observations and recalculated compositions indicate that the oriented amphibole lamellae exsolved from original supersilicic majorites with high concentrations of na2o 0 3 wt and hydroxyl up to 1000 ppm by weight these results imply that the host garnet peridotites were formed at depths greater than 200 km and that garnet can be an important reservoir of water at such depths in the mantle

hydroxyl contents of accessory minerals in mantle eclogites and related rocks infrared spectra in the region 3000 to 3800 cm 1 have been measured on coesite kyanite sanidine and rutile occurring in inclusions of eclogite and on garnet and spinel in an inclusion of alkremite from south african kimberites coesite and sanidine contain virtually no h 2o or oh although one sanidine crystal was observed to contain abundant h2o apparently as fluid inclusions of molecular h2o kyanite contains significant oh consistent with previous results for similar samples corundum gives no indication of the presence of h 2o or oh rutile containing significant amounts of fe cr al and nb also contains significant amounts of structural oh garnet in alkremite contains small amounts of molecular h 2o whereas the spinel coexisting with this garnet gives no indication of h 2o or oh indicating that the spinel structure is not able to accommodate significant amounts of oh ammonium contents of all samples were less than the detection limit about 10 ppm

hydroxyl defects in garnets from mantle xenoliths in kimberlites of the siberian platform a suite of more than 200 garnet single crystals extracted from 150 xenoliths covering the whole range of types of garnet parageneses in mantle xenoliths so far known from kimberlites of the siberian platform and collected from nearly all the kimberlite pipes known in that tectonic unit as well as some garnets found as inclusions in diamonds and olivine megacrysts from such kimberlites were studied by means of electron microprobe analysis and single crystal ir absorption spectroscopy in the voh vibrational range in search of the occurrence energy and intensity of the voh bands of hydroxyl defects in such garnets and its potential use in an elucidation of the nature of the fluid phase in the mantle beneath the siberian platform the voh single crystal spectra show either one or a combination of two or more of the following major voh bands i 3645 3662 cm 1 ii 3561 3583 cm 1 iii 3515 3527 cm 1 and minor bands ia 3623 3631 cm 1 iia 3593 3607 cm 1 the type of combination of such bands in the spectrum of a specific garnet depends on the type of the rock series of the host xenolith mg mg ca ca mg fe or alkremite on the xenolith type as well as on the chemical composition of the respective garnet nearly all garnets contain band systems i and ii band system iii occurs in ti rich garnets with wt tio2 ca 0 4 from xenoliths of the mg ca and mg fe series only the voh spectra do not correspond to those of oh defects in synthetic pyropes or natural ultra high pressure garnets from diamondiferous metamorphics there were no indications of voh from inclusions of other minerals within the selected 60 60 m measuring areas in the garnets the voh spectra of pyrope knorringite and pyrope knorringite uvarovite rich garnets included in diamonds do not show band systems i to iii instead they exhibit one weak broad band voh 200 460 cm 1 near 3570 cm 1 a result that was also obtained on pyrope knorringite rich garnets extracted from two olivine megacrysts the quantitative evaluation on the basis of relevant existing calibrational data bell et al 1995 of the sum of integral intensities of all voh bonds of the garnets studied yielded a wide range of water concentrations within the set of the different garnets between values below the detection limit of our single crystal ir method near 2 10 4 wt up to 163 10 4 wt the water contents vary in a complex manner in garnets from different xenolith types obviously depending on a large number of constraints inherent in the crystal chemistry as well as the formation conditions of the garnets during the crystallization of their mantle host rocks secondary alteration effects during uplift of the kimberlite play if any only a minor role despite the very complex pattern of the water contents of the garnets preventing an evaluation of a straightforward correlation between water contents of the garnets and the composition of the mantle s fluid phase during garnet formation at least two general conclusions could be drawn 1 the wide variation of water contents in garnets is not indicative of regional or local differences in the composition of the mantle s fluid phase 2 garnets formed in the high pressure high temperature diamond pyrope facies invariably contain significantly lower amounts of water than garnets formed under the conditions of the graphite pyrope facies this latter result 2 may point to significantly lower fh2o and fo2 in the former as compared to the latter facies

fluid inclusions in coesite bearing eclogites and jadeite quartzite at shuanghe dabie shan china fluid inclusions in coesite bearing eclogites and jadeite quartzite at shuanghe in dabie shan east central china have preserved remnants of early prograde and or peak metamorphic fluids reset during post uhp ultrahigh pressure metamorphic uplift inclusions occur in several minerals e g omphacite epidote notably as isolated primary inclusions in quartz included in various host minerals two major fluid types have been identified non polar fluid species n2 or co2 and aqueous the latter is by far the most predominant aqueous fluids cover a wide range of salinity from halite bearing brines to low salinity fluids for non polar fluids few n2 inclusions occur in undeformed eclogite whereas a number of co2 rich inclusions have been found in microshear zones of eclogite or jadeite quartzite in close proximity to marble occurrences the primary character of n2 and high salinity aqueous inclusions indicates that they are remnants from uhp metamorphic fluids and for some there is the distinct possibility that they are ultimately derived from pre metamorphic fluids this conclusion is supported by the preservation in some samples of microdomains containing synchronous inclusions of variable salinities which tend to relate to the chemical composition of the host crystal carbonic fluids may be derived from neighbouring rocks notably marble and carbonate bearing metasediments during post metamorphic uplift during post uhp exhumation a limited decrease of the fluid density has occurred with formation of new sets of fluid inclusions fluid movements however remained exceedingly limited at the scale of the enclosing crystal

the hydrous component in andradite garnet twenty two andradite samples from a variety of geological environments and two synthetic hydroandradite samples were studied by fourier transform ir spectroscopy their spectra show that h enters andradite in the form of oh amounts up to 6 wt h 2o occur in these samples those from low temperature formations contain the most oh some features in the absorption spectra indicate the hydrogarnet substitution sio 4 4 o 4h 4 4 whereas others indicate additional types of oh incorporation the complexity of the spectra due to multi site distribution of oh increases with increasing complexity of the garnet composition

melting experiments on lherzolite klb 1 under hydrous conditions and generation of high magnesian andesitic melts the partial melting of natural lherzolite klb 1 at 1 gpa was studied for both h2o undersaturated and saturated conditions the quenched glasses obtained at 1000 and 1050 c are andesitic in composition having 54 4 60 3 wt sio2 whereas partial melts formed at temperatures above 1100 c have basaltic compositions this suggests that high magnesian andesites can be formed by direct partial melting of the hydrous upper mantle only at relatively low temperatures these andesitic melts together with those obtained at 1100 c contain more than 3 wt h2o and have compositions characteristic of hydrous melts high sio2 and al2o3 and low feo mgo and cao the results of melting studies on klb 1 show a strong increase in the degree of melting when h2o is added to lherzolite at a given temperature

h2o contents and d h ratios of nominally anhydrous minerals from ultrahigh pressure eclogites of the dabie orogen eastern china abstract 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 d 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

faulting induced by precipitation of water at grain boundaries in hot subducting oceanic crust dehydration embrittlement has been proposed to explain both intermediate and deep focus earthquakes in subduction zones1 2 3 4 5 because such earthquakes primarily occur at shallow depths or within the core of the subducting plate dehydration at relatively low temperatures has been emphasized6 7 8 however recent careful relocation of subduction zone earthquakes9 10 shows that at depths of 100 250 km earthquakes continue in the uppermost part of the slab probably the former oceanic crust that has been converted to eclogite where temperatures are higher here we show that at such pressures and temperatures eclogite lacking hydrous phases but with significant hydroxyl incorporated as defects in pyroxene and garnet develops a faulting instability associated with precipitation of water at grain boundaries and the production of very small amounts of melt this new faulting mechanism satisfactorily explains high temperature earthquakes in subducting oceanic crust and could potentially be involved in much deeper earthquakes in connection with similar precipitation of water in the mantle transition zone 400 700 km depth of potential importance for all proposed high pressure earthquake mechanisms is the very small amount of fluid required to trigger this instability

coupled substitution of h and minor elements in rutile and the implications of high oh contents in nb and cr rich rutile from the upper mantle infrared absorption spectra of rutile crystals from a variety of geological environments carbonatite hydrothermal vein kyanite rutile lazulite association xenoliths that are kimberlite hosted and dominated by nb and cr rich rutile exhibit strong absorption in the 3300 cm 1 region due to interstitial protons bonded to structure o in general the proton is located at sites slightly displaced from 1 21 20 of the unit cell although some samples show evidence of additional protons at tetrahedral interstitial sites h contents of rutile range up to 0 8 wt h 2o the highest concentrations occurring in mantle derived nb and cr rich rutile of metasomatic origin the role of h in rutile was examined particularly with respect to its relations to other impurities protons are present in the rutile structure to compensate for trivalent substitutional cations cr fe v ai which are only partly compensated by pentavalent ions nb ta the possibility of using the h content of rutile as a geohygrometer is illustrated for the case of coexisting hematite and rutile

effect of water on melting phase relations and melt composition in the system mg2sio4mgsio3h2o up to 15 gpa melting experiments in the system mg2sio4 mgsio3 h2o up to pressures of 15 gpa show that the presence of h2o drastically changes melting temperature liquidus phases and the coexisting melt composition the system mg2sio4 h2o shows incongruent melting characterized by a high mgsi ratio of the eutectic composition exceeding 2 0 above 12 gpa whereas it exhibits congruent melting up to at least 7 7 gpa in the mgsio3 h2o system incongruent melting is observed up to 3 gpa which switches to congruent melting above 5 5 gpa and persists to at least 12 gpa the variation of the eutectic composition in the system mg2sio4 mgsio3 h2o is consistent with the variations of the melting temperatures in the systems mg2sio4 h2o and mgsio3 h2o the melting temperature solidus in the system mg2sio4 h2o decreases from 1800 c at atmospheric pressure to less than 1200 c at 10 gpa while in the system mgsio3 h2o it is reduced to a minimum value of 1250 c at approximately 5 5 gpa and then increases with pressure the composition of the initial melt in this system drastically changes at around 5 5 gpa the mgsi ratio being about 3 at 15 gpa variations of the ternary phase diagrams mgo sio2 h2o with pressure are compiled and compared with previous work on the relevant systems a modified spinel like hydrous phase is synthesized at 15 5 gpa the maximum amount of h2o accommodated in this phase is estimated to be 3 3 wt from observed chemical composition and crystal chemical considerations implying that a significant amount of h2o can be accommodated in the mantle transition zone the overall effect of h2o on ultrabasic magma genesis in the mantle is discussed a possibility is presented for the formation of komatiite magma involving the effect of h2o in the mantle of the early earth mg rich komatiite magma was possibly generated at a depth of only 200 km at temperatures much lower than that having been assumed previously

remnants of premetamorphic fluid and oxygen isotopic signatures in eclogites and garnet clinopyroxenite from the dabie sulu terranes eastern china a combined oxygen isotope and fluid inclusion study has been carried out on high and ultrahigh pressure metamorphic hp uhpm eclogites and garnet clinopyroxenite from the dabie sulu terranes in eastern china coesite bearing eclogites garnet clinopyroxenite and quartz eclogites have a wide range in whole rock 18ovsmow from 0 to 11 the high t oxygen isotope fractionations preserved between quartz and garnet preclude significant retrograde isotope exchange during exhumation and the wide range in whole rock oxygen isotope composition is thought to be a presubduction signature of the precursors aqueous fluids with variable salinities and gas species n2 co2 or ch4 rich are trapped as primary inclusions in garnet omphacite and epidote and in quartz blebs enclosed within eclogitic minerals in high 18o hp uhpm rocks from hujialin and shima high salinity brine and or n2 inclusions occur in garnet porphyroblasts which also contain inclusions of coesite cl rich blue amphibole and dolomite in contrast in low 18o eclogites from qinglongshan and huangzhen the cl concentrations in amphibole are very low 0 2 wt and low salinity aqueous inclusions occur in quartz inclusions in epidote porphyroblasts and in epidote cores these low salinity fluid inclusions are believed to be remnants of meteoric water although the fluid composition was modified during pre and syn peak hp uhpm eclogites at houshuichegou and hetang contain ch4 rich fluid inclusions coexisting with high salinity brine inclusions methane was probably formed under the influence of co2 rich aqueous fluids during serpentinisation of mantle derived peridotites prior to or during plate subduction remnants of premetamorphic low to high salinity aqueous fluid with minor n2 and or other gas species preserved in the dabie sulu hp uhpm eclogites and garnet clinopyroxenite indicate a great diversity of initial fluid composition in the precursors implying very limited fluid rock interaction during syn and post peak hp uhpm

enhancement of radiative transfer in the upper mantle by oh in minerals abstract diffusion of heat by radiation in the mantle has previously been associated with absorption of light by fe 2 the near ir absorptions of structurally incorporated oh provide another mechanism to convert the energy of photons into lattice vibrations the effective diffusive radiative thermal conductivity due to protonation k rdf wet may be important within the mantle because low absorption strengths as expected for trace to minor oh contents allow light to travel long distances in the medium available calibrations of band strength with oh content are used to develop a formula for k rdf wet as a function of temperature grain size and hydroxyl concentration that is generally applicable to mantle phases these results are compared to new data on the phonon contribution for olivine and to calculations of fe 2 radiative transfer as t increases k rdf wet increases as oh content increases k rdf wet initially increases reaches a maximum near 100 1000 ppm hydroxyl content as h 2 o and then decreases at higher concentrations a similar dependence on grain size exists with the maximum k rdf wet near d 1 cm grain sizes and oh contents of hydrous upper mantle samples foster radiative transport via protonation for example at 1500 k sub cm grain sizes with 10 100 ppm h 2 o provide k rdf wet that is 1 4 of k rdf arising from the combined effect of overtones and fe 2 transitions and 1 8 of the lattice contribution to k of olivine given that oh concentrations vary among mantle minerals the above results suggest that mantle heat flow is heterogeneous and anisotropic the dependence of both k rdf and viscosity on grain size and hydration suggests that the dynamical behavior in or near subducting slabs will be complex

seismic evidence for water deep in earth s upper mantle water in the deep upper mantle can influence the properties of seismic discontinuities in the mantle transition zone observations of converted seismic waves provide evidence of a 20 to 35 kilometer thick discontinuity near a depth of 410 kilometers most likely explained by as much as 700 parts per million of water by weight

heterogeneity of water in garnets from uhp eclogites eastern dabieshan china abstract garnets in uhp eclogites from bixiling in dabieshan were investigated by fourier transform infrared spectroscopy ftir the results indicate that all garnets contain structural water that occurs as hydroxyl oh and non structural molecular water h 2 o possibly in the form of sub microscopic fluid inclusions the structural hydroxyl contents range from 92 to 1735 ppm h 2 o wt and most are between 200 and 1000 ppm therefore garnet in eclogite can recycle surface water into the mantle various water contents were observed among different samples of the same outcrop 150 m and in different domains of the same sample 1 cm this variability in structural h 2 o contents suggests that the mobility of fluids during uhp metamorphism was very limited and that both subduction and exhumation processes of uhp rocks occurred in a short time interval

water content of mantle garnets garnet megacrysts from colorado plateau diatremes green knobs garnet ridge and the wesselton kimberlite south africa commonly contain a structural hydrous component the colorado plateau samples range from 0 0 to 0 26 wt h 2 o and the wesselton samples contain from 0 01 to 0 07 concentrations were measured using p 2 o 5 cell coulometry h 2 gas manometry and thermogravimetry these were used to calibrate infrared integrated absorbance in the 3 m region which is a more sensitive measure of total o h content than the other analytical methods infrared absorbance patterns were also used to differentiate structural hydrous component from water contained in alteration and included phases the structure of the hydrous component in these garnets appears to be the classic h 4 o 4 4 sio 4 4 profiles at 100 m intervals across these samples show flat concentration profiles or slightly increasing concentration toward the center a large range of water content among samples appears to represent real differences in water fugacity at the point where the garnets equilibrated garnets in eclogite nodules from south africa and the solomon islands were also studied but were either anhydrous or too badly altered to determine the content of structurally bound water the high concentration of hydrous component in the colorado plateau samples is consistent with other indicators of high volatile content in that region of the mantle the water content of mantle garnets may prove to be an accurate indicator of mantle water fugacities

the distribution of hydroxyl in garnets from the subcontinental mantle of southern africa 166 garnets of dominantly mantle origin were analyzed for oh content by infrared ir spectroscopy ir spectra in the 3400 3700 cm 1 region display consistent absorption patterns attributable to oh structurally bound within the garnet crystal occasionally contaminated by low intensity oh absorptions from microscopic inclusions the principal structural oh absorption occurs near 3570 cm 1 with the appearance of additional absorptions near 3512 cm 1 and 3650 cm 1 dependent on garnet composition or paragenesis samples derive from a wide variety of rock types occurring as xenoliths in kimberlites of southern africa oh abundances using the best currently available calibration range from less than 1 up to 135 ppm h 2o and increase in the general order as follows on craton eclogites group 1 basaltic kimberlite alnoite alkali basalt the oh contents of common lithospheric granets from coarse peridotites including several phlogopite bearing samples are typically less than 20 ppm h 2o for tectonic settings of kimberlites both on and off the archaean kaapvaal craton ti rich garnets from deformed peridotites are richer in oh supporting previous suggestions of association of these xenoliths with putative megacryst magmas subcalcic cr rich xenocrysts diamond inclusion garnets and garnets from diamondiferous eclogites have very low oh contents similar to eclogites and depleted peridotites without macroscopic diamonds the oh content of southern african peridotite and eclogite garnets are significantly lower on average than those previously examined from the colorado plateau diatremes while details of emplacement related h mobility in garnets remain to be established our results suggest that garnets record useful information on the role of water or other hydrous volatile species in petrological processes at their source regions in the mantle although garnets do not appear to constitute a large reservoir of mantle hydrogen the large stability range of oh bearing garnet in the crust and mantle implies wide applicability as a qualitative hydrobarometer

cluster of water molecules in garnet from ultrahigh pressure eclogite through the use of transmission electron microscopy and infrared spectroscopy hydrous components have been identified as hydroxyl and free water h 2 o in elongate garnet of ultrahigh pressure eclogite from the dabie mountains eastern china the h 2 o occurs as clusters of water molecules and as hydroxyl in garnet the clusters of water molecules are interpreted to have promoted elongation of garnet through hydrolytic weakening the presence of hydrous species in ultrahigh pressure garnet from continental crust protoliths indicates that such protoliths are able to carry water into the mantle during the subduction of continental lithosphere

hydrogen and oxygen isotope evidence for fluid rock interactions in the stages of pre and post uhp metamorphism in the dabie mountains abstract hydrogen and oxygen isotope studies were carried out on high and ultrahigh pressure metamorphic rocks in the eastern dabie mountains china the 18 o values of eclogites cover a wide range of 4 2 to 8 8 but the d values of micas from the eclogites fall within a narrow range of 87 to 71 both equilibrium and disequilibrium oxygen isotope fractionations were observed between quartz and the other minerals with reversed fractionations between omphacite and garnet in some eclogite samples the 18 o values of 4 to 1 for some of the eclogites represent the oxygen isotope compositions of their protoliths which underwent meteoric water rock interaction before the high to ultrahigh pressure metamorphism heterogeneous 18 o values for the eclogite protoliths implies not only the varying degrees of the water rock interaction before the metamorphism at different localities but also the channelized flow of fluids during progressive metamorphism due to rapid plate subduction retrograde metamorphism caused oxygen and hydrogen isotope disequilibria between some of the minerals but the fluid for retrograde reactions was internally buffered in the stable isotope compositions and could be derived from structural hydroxyls dissolved in nominally anhydrous minerals

distribution of hydrous components in jadeite of the dabie mountains two kinds of jadeite occur in the jadeite quartzite from the dabie mountains eastern china associated either with weak or strong deformation the former shows a uniform composition while the latter shows both uniform and zoning composition these jadeites were examined with infrared ir spectroscopy all jadeite displays hydroxyl oh stretching bands implying that hydrous components commonly exist in jadeite the concentration of the hydrous components in the jadeite with weak deformation is homogenous whereas the concentration of the hydrous components in strongly deformed samples is variable the correlation between the intensity of oh band absorbance and compositional zoning of jadeite with strong deformation indicates that na rich jadeite can accommodate more oh than na poor jadeite its interpretation is that there is more na associated with greater oh availability in the initial crystallization environment our data of the comparatively high oh concentrations recorded in the core of the jadeite which contains relative high vacancies in m2 site imply that both oh content and the vacancies in m2 site could decrease during exhumation of the jadeite quartzite the decrease of oh solubility in jadeite would result in the formation of h2o fluid during the early exhumation of uhp metamorphic rocks the h2o fluid transformed from oh during exhumation could trigger and enhance the early retrograde metamorphism of the host rocks and facilitate plastic deformation of jadeite grain by dislocation creep and diffusion creep

helium and carbon isotope systematics at ontake volcano japan we have measured chemical compositions he ne ratios and he and c isotopic compositions of 47 gas samples collected from crater fumaroles and hot springs associated with ontake volcano japan geographical and temporal variations of chemical compositions 3he 4he ratios and 13c values of co2 are reported here between 1981 and 1993 3he 4he ratios decreased with increasing distance from the central cone of the volcano while 13c values increased with the distance magmatic he and co2 are probably carried by a fluid flowing through the volcanic edifice and are diluted by crustal he and co2 a negative correlation of 3he 4he ratios and 13c values suggests two component mixing between magmatic and crustal end members at the sampling sites close to the fault formed by a m6 8 earthquake that occurred in september 1984 3he 4he ratios have increased significantly with time from 1984 to 1993 while except for three sites close to the fault no systematic change of 13c values is found on the other hand he and c isotopes have been constant at the sites distant from the fault the temporal variations of 3he 4he ratios may be related to the recent reactivation of ontake volcano

the oh content of pyrope at high pressure the oh contents of pyrope garnets synthesised at 1000 c and pressures between 2 and 13 gpa have been measured by infrared spectroscopy we find that under the same conditions of pressure temperature ah2o and asio2 the oh content of pyrope is similar to that of grossular this shows that observed differences in nature between water contents of pyrope and grossular are related to paragenesis rather than reflecting higher intrinsic solubility in grossular in the presence of excess sio2 the h2o content increases with pressure to 5 gpa 1000 ppm then decreases to below the detection limit at pressures above 7 gpa thus garnet becomes more hydrous with pressure to some critical value beyond which dehydration occurs even under h2o saturated conditions this observation is consistent with the measured partial molar volume of water in hydrogarnet which becomes greater than that in fluid water within the pressure range of this study when corrected to upper mantle conditions we find that pyrope should dehydrate with increasing depth below about 250 km pyrope is unlikely therefore to be a major site of water storage in the transition zone and upper mantle