ion microprobe analysis of oxygen isotopes in garnets of complex chemistry abstract accurate ion microprobe analysis of oxygen isotope ratios in garnet is possible if appropriate standards are employed to correct for instrumental bias a component of which depends on the cation chemistry of the analyzed mineral in this study 26 garnet standards including 14 new standards that span the compositional range of pyrope almandine grossular spessartine and andradite were analyzed repeatedly by ion microprobe to develop a new method of correcting for instrumental bias in garnets all analyses were normalized to a single master garnet standard uwg 2 before bias from cation composition was considered bias due to cation composition in garnet was found to correlate with grossular content in pyralspite garnets and with andradite in ugrandite garnets bias is correlated with molar volume in garnets of all compositions in this study although this correlation is suitable as a correction scheme for bias a more accurate correction scheme based on the grossular and andradite compositions of garnet is proposed this method reproduces the bias of all but one standard to within a range of 0 4 an accuracy that is on the same order as the reproducibility 0 3 2 s d of the master garnet standard uwg 2 but that remains an independent source of error the new correction scheme is used to successfully reproduce laser fluorination analyses along a traverse of a polymetamorphic zoned skarn garnet from the adirondack mountains while previous analyses were at the mm scale the new data resolve a gradient of 18 o of 2 1 over 16 m if experimentally derived diffusion coefficients are correct these new results show that granulite facies metamorphism was significantly faster than previously assumed and the thermal peak was less than 5 myr

submillimeter scale zonation of δ18o in quartz and feldspar isle of skye scotland abstract laser probe analysis of oxygen isotope ratios in submillimeter domains of quartz and feldspar in hydrothermally altered granite reveals complex intragranular zonation that can be contoured within individual grains two samples collected within 10 m of each other in the maol na gainmhich epigranite mge isle of skye scotland are similar petrographically yet display very different 18o zonation patterns sk1 has isotopically zoned quartz 18 o 1 8 8 2 with intragranular gradients of 18o as great as 5 mm and individually homogeneous grains of k feldspar 0 2 which also display a large range of values 18 o 1 7 to 7 3 oxygen isotope gradients of more than 11 mm were measured in this sample in contrast sk4 has homogeneous quartz 18o 5 7 0 3 n 14 and a zoned k feldspar phenocryst 18 o 3 3 to 6 9 isotopic heterogeneity in quartz correlates with the degree of chlorite alteration in adjacent hornblende grains the isotopic heterogeneity revealed by the laser probe in single grains of quartz and feldspar is greater than the entire range of values displayed by bulk mineral analysis of samples collected throughout the mge pluton although the average values of 18o obtained by laser probe are identical to the average bulk values values in k feldspar suggest exchange at 400 c with infiltrating meteoric water 18 o 10 the marked differences in zonation profiles between samples on the outcrop scale suggest that permeability and isotope exchange during hydrothermal alteration was highly heterogeneous these microanalytical data for quartz and feldspar provide the first oxygen isotope evidence from pervasively altered granites that paleopermeability is caused at least in part by intracrystalline microfractures

assessment of grain scale homogeneity and equilibration of carbon and oxygen isotope compositions of minerals in carbonate bearing metamorphic rocks by ion microprobe abstract nineteen samples of metamorphosed carbonate bearing rocks were analyzed for carbon and oxygen isotope ratios by ion microprobe with a 5 15 m spot three from a regional terrain and 16 from five different contact aureoles contact metamorphic rocks further represent four groups calc silicate marble and hornfels 6 brucite marble 2 samples that contain a reaction front 4 and samples with a pervasive distribution of reactants and products of a decarbonation reaction 4 the average spot to spot reproducibility of standard calcite analyses is 0 37 2 standard deviations sd for 18 o and 0 71 for 13 c ten or more measurements of a mineral in a sample that has uniform isotope composition within error of measurement can routinely return a weighted mean with a 95 confidence interval of 0 09 0 16 for 18 o and 0 10 0 29 for 13 c using a difference of 6sd as the criterion only four of 19 analyzed samples exhibit significant intracrystalline and or intercrystalline inhomogeneity in 13 c at the 100 500 m scale with differences within individual grains up to 3 7 measurements are consistent with carbon isotope exchange equilibrium between calcite and dolomite in five of six analyzed samples at the same scale because of relatively slow carbon isotope diffusion in calcite and dolomite differences in 13 c can survive intracrystalline homogenization by diffusion during cooling after peak metamorphism and likely represent the effects of prograde decarbonation and infiltration all but 2 of 11 analyzed samples exhibit intracrystalline differences in 18 o up to 9 4 intercrystalline inhomogeneity in 18 o up to 12 5 and or disequilibrium oxygen isotope fractionations among calcite dolomite calcite quartz and calcite forsterite pairs at the 100 500 m scale inhomogeneities in 18 o and 13 c are poorly correlated with only a single mineral dolomite in a single sample exhibiting both because of relatively rapid oxygen isotope diffusion in calcite intracrystalline inhomogeneities in 18 o likely represent partial equilibration between calcite and fluid during retrograde metamorphism calcite is in oxygen isotope exchange equilibrium with forsterite in one of four analyzed samples in equilibrium with dolomite in none of six analyzed samples and in equilibrium with quartz in neither of two analyzed samples there are no samples of contact metamorphic rock with analyzed reactants and products of an arrested metamorphic reaction that are in oxygen isotope equilibrium with each other the degree of departure from equilibrium in analyzed samples is variable and is often related at least in part to alteration of 18 o of calcite during retrograde fluid rock reaction in situ sub grain scale carbon and oxygen isotope analyses of minerals are advisable in the common applications of stable isotope geochemistry to metamorphic petrology correlation of sub mm scale stable isotope data with imaging will lead to improved understanding of reaction kinetics reactive fluid flow and thermal histories during metamorphism

optically continuous silcrete quartz cements of the st peter sandstone high precision oxygen isotope analysis by ion microprobe a detailed oxygen isotope study of detrital quartz and authigenic quartz overgrowths from shallowly buried 1 km quartz arenites of the st peter sandstone in sw wisconsin constrains temperature and fluid sources during diagenesis quartz overgrowths are syntaxial optically continuous and show complex luminescent zonation by cathodoluminescence detrital quartz grains were separated from 53 rocks and analyzed for oxygen isotope ratio by laser fluorination resulting

effects of cation substitutions in garnet and pyroxene on equilibrium oxygen isotope fractionations high grade metamorphic rocks were used to explore oxygen isotope fractionations between pyroxene and garnet and to investigate the effects on fractionation factors of the cation substitutions fe3 al 1 and ca fe mg 1 recrystallized granulite facies 725 c wollastonite ores from the northern adirondack highlands contain essentially only the minerals clinopyroxene a di hd solid solution garnet a grs adr solid solution wollastonite and exhibit a systematic dependence of measured fractionations on the fe3 content of calcic garnet cpx cagrt 0 14 0 12 0 78 0 20 xadr and wo cagrt 0 15 0 22 0 57 0 33 xadr in eclogites formed at t 650 c measured compositions of ca poor garnet and omphacite combined with experimental data indicate that ca poor fe rich garnet is enriched in 18o compared to both diopside and grossular extrapolating to 1000 k alm di c 0 2 and alm grs c 0 5 orthopyroxene and clinopyroxene from gore mountain new york show a constant fractionation that is independent of rock type as expected if they have the same closure temperature these data imply opx cpx c 0 7 at 1000 k measured fractionations among ca poor garnet orthopyroxene clinopyroxene and hornblende in the gore mountain rocks further indicate an 18o enrichment in ca poor garnet over grs c 0 5 at 1000 k the new measurements are indistinguishable from expected equilibrium values based on experiments for the minerals enstatite diopside grossular wollastonite and feldspar but consistently indicate a significant isotope effect for the simple octahedral cation substitutions fe3 al 1 grs vs adr and ca fe mg 1 ca poor garnet vs grs opx vs cpx neither cation substitution has been directly investigated for its effect on 18o 16o fractionation with experiments in silicates chemical characterization of minerals is required prior to petrological interpretation of oxygen isotope trends

oxygen isotope evidence for shallow emplacement of adirondack anorthosite oxygen isotopic analysis of wollastonites from the willsboro mine adirondack mountains new york reveals a 400 ft wide zone of 18o depletion at anorthosite contacts values of 18o vary more sharply with distance and are lower to 1 3 than any yet reported for a granulite fades terrain exchange with circulating hot meteoric water best explains these results and implies that the anorthosite was emplaced at relatively shallow depths 10 km in marked contrast to the depth of granulite fades metamorphism 23 km these 18o depletions offer the first strong evidence for shallow emplacement of anorthosite within the grenville province and suggest that regional metamorphism was a later and tectonically distinct event

anticorrelation between low δ13c of eclogitic diamonds and high δ18o of their coesite and garnet inclusions requires a subduction origin diamond is essentially impermeable and unreactive under many conditions and tiny mineral inclusions within natural diamonds can faithfully preserve information on the chemical and physical conditions during diamond growth the stable isotope ratios of carbon nitrogen oxygen and sulfur in diamonds and their mineral inclusions have been used to constrain models of diamond formation but interpretations of the data have differed dramatically the crux of the controversy lies in the interpretation of the carbon isotope ratios of eclogite suite diamonds which range well outside those expected for typical mantle materials such as peridotites basalts and carbonatites proposed explanations for these anomalous carbon isotope ratios include derivation from primordial mantle inhomogeneities fractionated mantle fl uids and subducted biogenic carbon working with samples from three continents we have analyzed the carbon isotope compositions of eclogite suite diamonds and the oxygen isotope composition of their mineral inclusions primarily by ion microprobe methods we have discovered a previously unrecognized remarkably consistent anticorrelation between these two isotopic systems in that virtually all diamonds with anomalously low carbon isotope ratios have silicate inclusions with anomalously high oxygen isotope ratios this is a fundamental observation that can only be explained by formation of eclogite suite diamonds through subduction of seafl oor altered basalt admixed with marine biogenic carbon into the fi eld of diamond stability

laboratory studies of aeolian sediment transport processes on planetary surfaces abstract we review selected experimental saltation studies performed in laboratory wind tunnels and collision experiments performed in splash laboratory facilities that allow detailed observations between impinging particles on a stationary bed we also discuss progress in understanding aeolian transport in nonterrestrial environments saltation studies in terrestrial wind tunnels can be divided into two groups the first group comprises studies using a short test bed typically 1 4 m long and focuses on the transitional behavior near the upwind roughness discontinuity where saltation starts the other group focuses on studies using long test beds typically 6 m or more where the saturated saltation takes place under equilibrium conditions between wind flow and the underlying rough bed splash studies using upscaled model experiments allow collision simulations with large spherical particles to be recorded with a high speed video camera the findings indicate that the number of ejected particles per impact scales linearly with the impact velocity of the saltating particles studies of saturated saltation in several facilities using predominantly particle tracking velocimetry or laser doppler velocimetry indicate that the velocity of the few particles having high trajectories increases with increasing friction velocity however the speed of the majority of particles that do not reach much higher than bagnold s focal point is virtually independent of shields parameter at least for low or intermediate u values in this case mass flux depends on friction velocity squared and not cubed as originally suggested by bagnold over short beds particle velocity shows stronger dependence on friction velocity and profiles of particle velocity deviate from those obtained over long beds measurements using horizontally segmented traps give average saltation jump lengths near 60 70 mm and appear to be only weakly dependent on friction velocity which is in agreement with some but not all older or recent wind tunnel observations similarly some measurements performed with uniform sand samples having grain diameters of the order of 0 25 0 40 mm indicate that ripple spacing depends on friction velocity in a similar way as particle jump length the observations are thus in agreement with a recent ripple model that link the typical jump length to ripple spacing a possible explanation for contradictory observations in some experiments may be that long observation sequences are required in order to assure that equilibrium exists between ripple geometry and wind flow quantitative understanding of saltation characteristics on mars still lacks important elements based upon image analysis and numerical predictions aeolian ripples have been thought to consist of relatively large grains diameter 0 6 mm and that saltation occurs at high wind speeds 26 m s involving trajectories that are significantly longer than those on earth by a factor of 10 100 however this is not supported by recent observations from the surface of mars which shows that active ripples in their geometry and composition have characteristics compatible with those of terrestrial ripples sullivan et al 2008 also the highest average wind speeds on mars have been measured to be electrification is seen as a dominant factor in the transport dynamics of dust on mars affecting the structure adhesive properties and detachment entrainment mechanisms specifically through the formation of aggregates merrison et al 2012 conversely for terrestrial conditions electric fields typically observed are not intense enough to significantly affect sand transport rates while little is known in the case of extra terrestrial environments

ion microprobe analysis of oxygen isotope ratios in granulite facies magnetites diffusive exchange as a guide to cooling history ion microprobe analysis of magnetites from the adirondack mountains ny yields oxygen isotope ratios with spatial resolution of 2 8 m and precision in the range of 1 1 sigma these analyses represent 11 orders of magnitude reduction in sample size compared to conventional analyses on this material and they are the first report of routinely reproducible precision in the 1 per mil range for analysis of 18o at this scale high precision micro analyses of this sort will permit wide ranging new applications in stable isotope geochemistry the analyzed magnetites form nearly spherical grains in a calcite matrix with diopside and monticellite textures are characteristic of granulite facies marbles and show no evidence for retrograde recrystallization of magnetite magnetites are near to fe3o4 in composition and optically and chemically homogeneous a combination of ion probe plus conventional brf5 analysis shows that individual grains are homogeneous with 18o 8 9 1 smow from the core to near the rim of 0 1 1 2 mm diameter grains depth profiling into crystal growth faces of magnetites shows that rims are 9 depleted in 18o these low 18o values increase in smooth gradients across the outer 10 m of magnetite rims in contact with calcite these are the sharpest intracrystalline gradients measured to date in geological materials this discovery is confirmed by bulk analysis of 150 350 m diameter magnetites which average 1 2 lower in 18o than coarse magnetites due to low 18o rims conventional analysis of coexisting calcite yields 18o 18 19 suggesting that bulk 18o cc mt 9 3 and yielding an apparent equilibration temperature of 525 c over 200 c below the temperature of regional metamorphism consideration of experimental diffusion data and grain size distribution for magnetite and calcite suggests two contrasting cooling histories the data for oxygen in calcite under hydrothermal conditions at high p h2o indicates that diffusion is faster in magnetite and modelling of the low 18o rims on magnetite would suggest that the adirondacks experienced slow cooling after grenville metamorphism followed by a brief period of rapid cooling possibly related to uplift conversely the data for calcite at low p h2o show slower oxygen diffusion than in magnetite modelling based on these data is consistent with geochronology that shows slow cooling through the blocking temperature of both minerals suggesting that the low 18o rims form by exchange with late low temperature fluids similar to those that infiltrated the rock to serpentinize monticellite and which infiltrated adjacent anorthosite to form late calcite veinlets in either case the ion microprobe results indicate that two distinct events are recorded in the post metamorphic exchange history of these magnetites recognition of these events is only possible through microanalysis and has important implications for geothermometry

zonation patterns of skarn garnets records of hydrothermal system evolution chemically zoned skarn garnets provide a continuous record of hydrothermal processes in lower paleozoic sedimentary rocks within the contact aureole around the drammen granite in the oslo rift southern norway major and trace element zonation profiles the latter obtained using a scanning high resolution proton microprobe reveal early infiltration controlled growth of relatively grossular rich garnets the major and trace elements compositions being buffered by local mineral dissolution subsequent rapid epitaxial growth of andradite rich garnet on grossular rich cores marks the onset of vigorous and focused fluid flow along high permeability zones during this later stage the hydrothermal fluid composition was to a large extent externally controlled and the andradite precipitating from these fluids was characterized by high as and w contents the zonation patterns of the andradite rich garnets record at least five intermittent growth periods with rapid andradite precipitation from fluid batches with high f o 2 and progressively decreasing as and w contents thin layers poor in fe as and w but relatively high in al and mn represent periods of slow growth rates between the major pulses of hydrothermal fluids the marked rimward decrease in the as and w contents of the garnets may reflect influx of meteoric waters or exhaustion of these elements in the hydrothermal fluid reservoir caused by boiling controlled distillation processes at depth

a garnet zircon oxygen isotope record of subduction and exhumation fluids from the franciscan complex california tectonic blocks of high grade metamorphic rock hosted by the franciscan me lange commonly preserve textural and geochemical evidence for metasomatism and blueschist facies overprinting within a subduction zone these exhumation events can obscure information on the nature of subduction fluids at depth that might otherwise be preserved by these rocks in this tectonic setting cation and oxygen isotope zoning in garnets from eclogite and garnet hornblende rocks with minimal textural evidence of retrogression reveals separate prograde and retrograde fluid histories garnet cores preserve a homogeneous prograde oxygen isotope history with both high do 11o and low 4o values in different samples probably recording altered ocean crust protolith compositions multiple episodes of garnet resorption and regrowth record a dramatically changing bulk oxygen isotope ratio resulting in 6 7o neoformed garnet rims with sharp core rim boundaries in both samples matrix omphacite and hornblende are in profound oxygen isotope disequilibrium with garnet cores but are in equilibrium with garnet rims despite the appearance of overall textural equilibrium in thin section this cryptic metasomatism found in samples from different locations within the franciscan complex brings into question existing thermobarometry on non inclusion phases for this complex as well as interpretations based on whole rock geochemical data zircon ages and oxygen isotope equilibrium with late forming garnet are consistent with postmetasomatic formation of zircon the ability of garnet and zircon to record multiple fluid events and tie them to p t t fluid history is a powerful tool in gaining an improved understanding of the complex fluid environments within subduction zones

andradite skarn garnet records of exceptionally low δ 18 o values within an early cretaceous hydrothermal system sierra nevada ca skarn garnets in the mineral king roof pendant of the south central sierra nevada within sequoia national park california usa reveal variable fluid chemistry with a significant component of meteoric water during metasomatism in the early cretaceous sierra nevada batholith we focus on andradite garnet associated with pb zn mineralization in the white chief mine laser fluorination oxygen isotope analyses of 18o of garnet 18o grt from sites along the skarn show a large range of values 8 8 to 4 6 vsmow ion microprobe sims analyses elucidate that individual andradite crystals are strongly zoned in 18o grt up to 7 of variation total rare earth element concentrations ree across individual garnets show progressive depletion of skarn forming fluids in these elements during garnet growth these findings support a skarn model of earliest red high 18o grandite garnet consistent with a magmatic dominated equilibrium fluid 18o h2o as high as 8 later green andradite crystallized in equilibrium with a low 18o fluid indicating a significant influx of meteoric fluid 18o h2o 6 to 5 following a hiatus in garnet growth associated with late stage pb zn mineralization latest orange overprint rims have higher 18o values 18o h2o 0 2 and depleted total rees suggesting influx of high 18o trace element depleted fluid derived from regional metamorphism of the carbonate host remarkably low 18o grt values in the white chief canyon skarn require a significant proportion of meteoric fluid available during 400 c andradite forming metasomatism fluid flow was channelized at the pluton wallrock contact evidenced by the narrow extent of skarn

dynamic growth of garnet in granitic magmas in order to improve understanding of how accessory garnet crystallizes in igneous rocks and evaluate it as a mineral recorder of magma history we analyzed 18 o of garnets from the hallowell and togus plutons in south central maine united states by laser fluorination and in situ by ion microprobe two types of garnet are recognized magmatic and locally derived peritectic traverses of some single crystals show both gradual and abrupt changes of 18 o garnet commonly 1 while other garnet grains are isotopically homogeneous rimward increase of 18 o in many crystals indicates that garnet grew while high 18 o metamorphic wall rocks were assimilated peritectic grains have a complementary record of the transfer of high 18 o melts to the plutons in some rocks 18 o varies among neighboring grains evidence that crystals grew episodically or were juxtaposed from different sources during magma mixing garnet faithfully records changing magmatic 18 o and is a valuable tool to decipher magma petrogenesis

oxygen isotope constraints on metamorphic fluid flow townshend dam vermont u s a fluid rock interaction during amphibolite facies metamorphism has been investigated for rocks exposed in a single 400 m long lithologically heterogeneous outcrop near townshend vermont usa oxygen isotopic compositions have been measured in profiles across single garnet crystals from thirteen samples and from hornblende and garnet separates from thirty three fine grained samples this outcrop was previously studied who measured large oxygen isotope gradients 3 per thousand in garnets from one sample and inferred large amounts of pervasive fluid flow all of the garnets that we have analyzed show less isotopic zonation le 1 per thousand twelve of them have zonation 0 5 per thousand and the mineral separate data imply both a strong correlation of isotopic composition with rock type and large gradients in peak metamorphic fluid isotopic compositions although devolatilization reactions in these rocks must have produced metamorphic fluids the data preclude cross foliation time integrated fluid fluxes greater than 300 600 cm sup 3 cm sup 2 during prograde amphibolite facies metamorphism the isotopic trends can all be interpreted in terms of closed system behavior channeled fluid flow or diffusive exchange of oxygen in an interconnected grain boundary fluid and within uncertainty cross strike advective fluxes could have been zero any significant flow at this locality was dominantly either layer parallel or channeled out of the system in veins more if all fluid flow occurred in veins then their spacing must have been less than 300 600 m the data are inconsistent with massive and pervasive metamorphic fluid flow across strike but do not address layer parallel flow less

quartz garnet isotope thermometry in the southern adirondack highlands grenville province new york quartz garnet oxygen isotope thermometry of quartz rich metasedimentary rocks from the southern adirondack highlands grenville province new york yields metamorphic temperatures of 700 800 c consistent with granulite facies mineral assemblages samples from the irving pond quartzite record d 18 o qtz grt 2 68 0 21 1 s d n 15 corresponding to peak metamorphic conditions of 734 38 c this agrees well with the estimates from garnet biotite exchange thermometry similar temperature estimates are obtained from swede pond 682 47 c n 3 and king s station c 700 c the whitehall area records higher temperatures 798 25 c n 3 all of these temperatures are higher than previous regional temperature estimates the c 800 c temperatures near whitehall are consistent with preservation of pre granulite contact temperatures adjacent to anorthosite the preservation of peak metamorphic temperatures in garnet of all sizes is consistent with slow oxygen diffusion in garnet and closure temperatures of at least 730 c peak metamorphic fractionations are preserved in rocks with varying quartz feldspar ratios indicating that the modal percentage of feldspar does not affect retrograde oxygen exchange in these rocks the lack of this correlation suggests slow rates of oxygen diffusion in quartz and feldspar consistent with the results of anhydrous oxygen diffusion experiments

ion microprobe survey of the grain scale oxygen isotope geochemistry of minerals in metamorphic rocks abstract the oxygen isotope compositions of calcite diopside dolomite forsterite garnet k feldspar kyanite plagioclase quartz and wollastonite were analyzed in suites of contact and regional metamorphic rocks using an ion microprobe spatial resolution was 10 m precision measured as the standard deviation of working standards averaged over the entire project was 0 13 0 18 for three carbonate standards and 0 11 0 12 for two silicate standards a total of 1176 analyses excluding standards were made of 73 minerals in 23 samples both intercrystalline and intracrystalline variability in 18 o is greater in contact than in regional metamorphic rocks of 27 minerals analyzed in contact metamorphosed rocks 70 exhibit statistically significant grain to grain variability in 18 o over areas 1 41 cm 2 with the largest range in silicates and carbonates in a single sample of 7 4 forsterite and 10 6 dolomite of 88 grains analyzed in two or more places in contact metamorphosed rocks 32 exhibit statistically significant intracrystalline variability in 18 o with the largest range in a single silicate and carbonate grain of 3 1 forsterite and 10 1 dolomite in contrast 44 of 45 minerals in regional metamorphic rocks exhibit significant grain to grain variability in 18 o over areas 1 17 cm 2 with the largest range in silicates and carbonates in a single sample of only 1 1 plagioclase and 0 9 calcite only 6 of 144 grains analyzed in two or more places in regional metamorphic rocks exhibit significant intracrystalline variability in 18 o with the largest range in a single silicate and carbonate grain of only 1 5 diopside and 0 7 calcite the difference in intercrystalline and intracrystalline variability in 18 o between contact and region metamorphic rocks is explained by the longer duration and slower reaction rates of regional metamorphism rather than to differences in temperature there is no significant difference in intercrystalline and intracrystalline variability in 18 o in regional metamorphic rocks among samples from the biotite garnet and kyanite zones calcite inclusions in forsterite and calcite and quartz inclusions in garnet either have 18 o that is statistically indistinguishable from 18 o of the same mineral occurring as nearby matrix grains or have statistically significant lower 18 o no reversed isotope fractionations were measured between coexisting mineral pairs minerals in individual samples however exhibit a wide range in the degree to which they attained and preserve oxygen isotope fractionations consistent with metamorphic temperatures recorded by mineral equilibria processes that account for grain scale departures from isotope exchange equilibrium include a overstepping of prograde mineral reactions b growth zoning in low diffusivity minerals c interaction of rocks with fluids at the peak of metamorphism and or during cooling d retrograde mineral reactions and e closed system isotope exchange between coexisting minerals during cooling this study provides new information about 1 the degree to which a variety of textural changes experienced by rocks during metamorphism are associated with changes in 18 o 2 oxygen isotope homogenization at the outcrop scale among contrasting lithologies 3 changes in 18 o with increasing grade of regional metamorphism and 4 time scales of metamorphic process

massive fluid influx beneath the colorado plateau usa related to slab removal and diatreme emplacement evidence from oxygen isotope zoning in eclogite xenoliths

evaluation of the effects of composition on instrumental mass fractionation during sims oxygen isotope analyses of glasses significant instrumental mass fractionation imf occurs during measurements of oxygen isotope ratios in magmatic glasses by sims in order to characterise and correct for this fractionation we measured oxygen isotope ratios in a range of international and internal glass standards ranging in composition from basalt 47 wt sio2 to rhyolite 72 wt sio2 and with known major element compositions oxygen isotope ratios were determined by laser fluorination at suerc east kilbride or taken from previously published values a total of 1105 18o measurements were made over nine sessions on a cameca ims 1270 ion microprobe at the university of edinburgh sims measurements on glass standards had external precision better than 0 36 1 and the reference material analysed alongside the unknown samples usgs synthetic glass gsa 1g had an average external precision of 0 14 the selected standards are thus sufficiently homogeneous in 18o to be suitable calibration standards in terms of 18o the sims measurements show that within a single session imf may vary by up to 4 7 from one glass standard to another imf is strongly correlated with sio2 and cao a least squares regression calculation was used to explore potential univariate and multivariate correction schemes for each correction scheme the correction coefficients determined for each session were then used to calculate the imf and correct the measured isotopic ratio of each glass standard a univariate correction scheme using only sio2 to correct for imf reproduced 75 of the glass standards to within 0 2 of their true 18o and 95 to within 0 4 bivariate correction schemes using sio2 cao and feo cao produced similar results but did not significantly improve on the sio2 correction the correction schemes were applied to 18o measurements made on melt inclusions and glasses from the askja volcanic system north iceland the uni and bivariate correction schemes tested produced 18o values within the published range for icelandic basalts we recommend a simple correction scheme based on the sio2 content of appropriate standards which should span a suitable compositional range from basalt to rhyolite

eclogite facies fluid infiltration constraints from δ 18 o zoning in garnet in situ analysis reveals that eclogite facies garnets are zoned in 18o with lower values in the core and rims that are 1 5 to 2 5 higher this pattern is present in 9 out of 12 garnets analyzed by sims from four orogenic eclogite terranes and correlates with an increase in the mole fraction of pyrope and mg fe ratio from core to rim indicating prograde garnet growth at the maximum temperatures and the time scales experienced by these garnets calculated intragranular diffusion distances for oxygen are small 5 from two kimberlites are homogeneous in 18o possibly due to diffusive exchange which is possible for prolonged periods at higher mantle temperatures homogeneity of 18o in garnets outside the normal mantle range 5 6 may be common in kimberlitic samples

crustal reworking and hydration insights from element zoning and oxygen isotopes of garnet in high pressure rocks sesia zone western alps subduction zones represent one of the most critical settings for fluid recycling as a consequence of dehydration of the subducting lithosphere a better understanding of fluid flows within and out of the subducting slab is fundamental to unravel the role of fluids during burial in this study major and trace element geochemistry combined with oxygen isotopes were used to investigate metasediments and eclogites from the sesia zone in order to reconstruct the effect of internal and external fluid pulses in a subducted continental margin garnet shows a variety of textures requiring dissolution precipitation processes in presence of fluids in polycyclic metasediments garnet preserves a partly resorbed core related to pre alpine high temperature low pressure metamorphism and one or multiple rim generations associated with alpine subduction metamorphism in eclogites garnet chemical zoning indicates monocyclic growth with no shift in oxygen isotopes from core to rim in metasediments pre alpine garnet relics show 18o values up to 5 3 higher than the alpine rims while no significant variation is observed among different alpine garnet generations within each sample this suggests that an extensive re equilibration with an externally derived fluid of distinct lower 18o occurred before or in correspondence to the first alpine garnet growth while subsequent influxes of fluid had 18o close to equilibrium the observed shift in garnet 18o is attributed to a possible combination of 1 interaction with sea water derived fluids during pre alpine crustal extension and 2 fluids from dehydration reactions occurring during subduction of previously hydrated rocks such as the serpentinised lithospheric mantle or hydrated portions of the basement

direct dating of adirondack massif anorthosite by u pb shrimp analysis of igneous zircon implications for amcg complexes the low abundance of igneous zircon in proterozoic massif anorthosites has presented a major obstacle to the acquisition of direct absolute ages of crystallization for these important rocks indirect dating that relies on zircon ages from associated mangerite charnockite granite granitoids assumes that they have a coeval relationship with anorthosite that requires documentation shrimp sensitive high resolution ion microprobe u pb zircon dating techniques provide a powerful means for directly dating the small populations of zircons in anorthositic rocks and for resolving problems with inheritance within the adirondack mountains 10 samples of massif anorthosite have yielded more than sufficient quantities of igneous zircon to establish directly the ages of the region9s classic anorthosite occurrences e g the marcy and oregon dome massifs in addition a ferrogabbro a ferrodiorite and a coronitic olivine metagabbro all crosscutting massif anorthosite were dated the average age of this suite of 13 anorthositic samples is 1154 6 ma mswd mean square of weighted deviates 0 26 probability 0 99 in addition eight associated granitoids have been dated by shrimp techniques and complement another five previously dated by multi grain thermal ionization mass spectrometry tims methods the 13 granitoids yield an average age of 1158 5 mswd 0 89 probability 0 60 and are broadly coeval with the massif anorthosite the overlapping ages provide evidence that these rocks constitute a single composite anorthosite mangerite charnockite granite amcg suite intruded at ca 1155 ma an age corresponding to the ages of major amcg suites in the grenville province in canada e g morin and lac st jean although rocks of the adirondack amcg suite are now documented as broadly coeval it does not follow that the constituent amcg lithologies were comagmatic field relationships and mineral disequilibria in transitional zones are inconsistent with derivation from a single parental magma moreover the presence of older ca 1 2 1 3 ga inherited cores in some zircons from amcg granitoids conflicts with derivation of these rocks from magmas that formed anorthosite gabbro or ferrodiorite or jotunite in which zircons are highly soluble the slightly older ca 1158 ma average age of the mangeritic and charnockitic members of the amcg suite is consistent with an origin as early lower crustal anatectites that left behind pyroxene plagioclase restites this refractory material then reacted by assimilation fractional crystallization afc with ponded mantle derived gabbroic magmas to produce plagioclase rich crystal mushes with crustal isotopic signatures as proposed much earlier by r f emslie these magmas are considered to be parental to the adirondack anorthosite and upon ascent they were emplaced in proximity to still hot earlier mangeritic and charnockitic bodies where they underwent further fractionation the composite nature of the marcy massif documents that this process was repeated in several sequential pulses

oxygen isotope and trace element zoning in hydrothermal garnets windows into large scale fluid flow behavior single garnet crystals from a large multicyclic hydrothermal system in far east russia are strongly growth zoned microscale ion microprobe analysis reveals consistent intracrystalline patterns in oxygen isotope composition and boron and iron contents reflecting evolution of the hydrothermal system from magmatic to meteoric dominated conditions and repetitive influx of magmatic fluids large intracrystalline variations in oxygen isotope composition 12 18 o delimit temporal evolution of magmatic and meteoric fluid input within different portions of the hydrothermal system and suggest that fluid flow regimes differed between central and distal portions of the system these results provide compelling evidence that microanalytical data can be extrapolated from intracrystalline scales to study macroscale processes in complex large scale fluid rock systems

a detailed record of shallow hydrothermal fluid flow in the sierra nevada magmatic arc from low δ18o skarn garnets garnet from skarns exposed at empire mountain sierra nevada california united states batholith have variable 18o values including the lowest known 18o values of skarn garnet 4 0 in north america such values indicate that surface derived meteoric water was a significant component of the fluid budget of the skarn forming hydrothermal system which developed in response to shallow emplacement 3 3 km of the 109 ma quartz diorite of empire mountain values of 18o measured in situ across single garnet crystals by secondary ion mass spectrometry vary considerably up to 7 and sometimes abruptly indicating variable mixing of meteoric magmatic and metamorphic water brecciation in the skarns and alteration of the empire mountain pluton suggests that fracture enhanced permeability was a critical control on the depth to which surface waters penetrated to form skarns and later alter the pluton compared to other sierran systems much greater volumes of skarn rock suggest an exceptionally vigorous hydrothermal system that saw unusually high levels of decarbonation reaction progress likely a consequence of the magma intruding relatively cold wallrocks inboard of the main locus of magmatism in the sierran arc at that time

oxygen isotope thermometry using quartz inclusions in garnet oxygen isotope ratios of quartz inclusions within garnet from granulite and amphibolite facies gneisses in the adirondack mountains ny were analyzed and used to determine metamorphic temperatures primary quartz inclusions for eight of 12 samples have 18o values significantly lower than matrix quartz the primary quartz inclusions retain 18o values representative of thermal conditions during garnet crystallization whereas the 18o values of matrix quartz were raised by diffusive exchange with other matrix minerals e g mica and feldspar during cooling the 18o differences between quartz inclusions and matrix quartz show that garnet a mineral with slow diffusion of oxygen can armour quartz inclusions from isotopic exchange with surrounding matrix even during slow cooling these differences between 18o in matrix quartz and quartz inclusions can further be used to test cooling rates by fast grain boundary diffusion modelling criteria for identifying quartz inclusions that preserve primary compositions and are suitable for thermometry were developed based on comparative tests relations between 18o and inclusion size distance of inclusion to host garnet rim core rim zonation of individual inclusions and presence or absence of petrological features healed cracks in quartz inclusions inclusions in contact with garnet cracks lined by secondary minerals and secondary minerals along the inclusion grain boundary were investigated in this study 61 of quartz inclusions preserve primary 18o and 39 were associated with features that were linked to reset 18o values if 18o in garnet is homogeneous and inclusions are removed laser fluorination 18o values of bulk garnet are more precise more accurate and best for thermometry intragrain 18o grt profiles measured in situ by ion microprobe show no 18o zonation almandine rich garnet alm 60 75 from each sample was measured by laser fluorination mass spectrometry lf ms for 18o and compared with ion microprobe measurements of 18o in quartz inclusions for thermometry the 18o qz grt values for adirondack samples range from 2 66 to 3 24 corresponding to temperatures of 640 to 740 c a qz alm 2 71 out of 12 samples that were used for thermometry nine are consistent with previous estimates of peak temperature 625 to 800 c based on petrological and carbon isotope thermometry for regional granulite and upper amphibolite facies metamorphism the three samples that disagree with independent thermometry for peak metamorphism are from the anorthosite mangerite charnockite granite suite in the central adirondacks and yield temperatures of 640 to 665 c approximately 100 c lower than previous estimates these low temperatures could be interpreted as thermal conditions during late post peak crystallization of garnet on the retrograde path this article is protected by copyright all rights reserved

delta 18 o and yttrium zoning in garnet time markers for fluid flow the relative timing of two discrete pulses of metamorphic fluid flow is constrained based on chemical zoning in several garnet crystals from kvaloya troms northern norway the garnet crystals measured 1 2 cm in diameter and were contained within c 1 6 ga staurolite grade metasediments major element zoning indicates that garnet grew under normal prograde conditions in the garnet and or staurolite zones timing constraints are based on comparisons between major and trace element chemical zoning oxygen isotope 18o zoning and deformational inclusion trail zoning in one of the garnet we interpret at least two pulses of metamorphic fluid flow the first pulse occurred during the syn tectonic growth interval the 18o zoning was reversed relative to normal prograde zoning and the 18o maximum was located within the syn tectonic growth zone displaced 3 4 mm from the garnet core the fluid might have been sourced in neighbouring calcareous pelites and may also have caused formation of an y ring the second and subsequent pulse s occurred during after the post tectonic growth interval 18o was locally increased at the garnet rim particularly where the rim was sheared the incomplete rim was also enriched in calcium transport of oxygen and calcium by metamorphic fluids is well documented transport of y is both problematic and poorly understood but might have been facilitated by complexing with f and or co2

genesis of metapelitic migmatites in the adirondack mountains new york oxygen isotope ratios and rare earth element ree concentrations provide independent tests of competing models of injection v anatexis for the origin of migmatites from amphibolite and granulite facies metasedimentary rocks of the adirondack mountains new york values of 18o and ree profiles were measured by ion microprobe in garnet zircon pairs from 10 sample localities prior u pb sims dating of zircon grains indicates that inherited cores 1 7 1 2 ga are surrounded by overgrowths crystallized during the grenville orogenic cycle 1 2 1 0 ga cathodoluminescence imaging records three populations of zircon i featureless rounded whole grains interpreted as metamorphic or anatectic and rhythmically zoned igneous cores truncated by rims that are either ii discordant rhythmically zoned igneous or iii unzoned metamorphic or anatectic these textural interpretations are supported by geochronology and oxygen isotope analysis in both the amphibolite facies nw adirondacks and the granulite facies se adirondacks 18o zrc values in overgrowths and whole zircon are highly variable for metamorphic zircon 6 1 13 4 n 95 10 m spot in contrast garnet is typically unzoned and 18o grt values are constant at each locality differing only between leucosomes and corresponding melanosomes none of the analysed metamorphic zircon garnet pairs attained oxygen isotope equilibrium indicating that zircon rims and garnet are not coeval furthermore ree profiles from zircon rims indicate zircon growth in all regions was prior to significant garnet growth thus petrological estimates from garnet equilibria e g p t cannot be associated uncritically with ages determined from zircon the unusually high 18o values 10 in zircon overgrowths from leucocratic layers are distinctly different from associated metaigneous rocks 18o zrc 10 indicating that these leucosomes are not injected magmas derived from known igneous rocks surrounding melanosomes have similarly high 18o zrc values suggesting that leucosomes are related to surrounding melanosomes and that these migmatites formed by anatexis of high 18o metasedimentary rocks

generation of forsteritic olivine fo99 8 by subsolidus oxidation in basaltic flows we identify olivine grains with compositions up to fo99 8 which are found in multiple primitive basaltic lava flows from a monogenetic volcano in the big pine volcanic field california usa in this study we show that the forsterite in these basalts formed by subsolidus recrystallization in a high fo2 environment olivine compositions are bimodal with flows having either all normal compositions fo74 9 94 4 or highly forsteritic fo97 2 99 8 compositions in many grains the subhedral forsteritic olivine has a hematite and clinopyroxene rim and internal parallel oriented planes of hematite clinopyroxene and orthopyroxene results of isotopic chemical crystallographic petrographic and mineralogical analyses show that the forsterite formed through subsolidus oxidation of olivine phenocrysts the forsteritic olivines generally occur in the thinner flows we infer that a rapidly emplaced sequence of thin vesicular spatter fed flows allowed the original olivine phenocrysts to become repeatedly reheated while exposed to air our study required sampling each flow so it was difficult to avoid the altered portions of the thinner flows other studies would tend to avoid such flows which may account for why such forsteritic olivines have not been more widely recognized

oxygen isotope heterogeneities and diffusion profile in composite metamorphic magmatic garnets from the pyrenees unusually large 1 8 o heterogeneities 4 within single crystals are reported in garnets from dioritic migmatites in the pyrenees these heterogeneities together with contrasting ca and p zoning allow the identification of different growth zones garnet cores with high 1 8 o values 12 14 are relatively poor in ca 7 9 mol grs and rich in p 400 900 ppm p 2 o 5 in contrast garnet rims with lower 1 8 o values 7 12 o are richer in ca 12 14 grs and poorer in p 100 200 ppm these growth zones can be ascribed to a metamorphic event followed by crustal partial melting and contamination by magmas from the mantle high 1 8 o intra crystalline contrasts result from mineral growth in an open magmatic system involving the interaction of partial melts with distinct 1 8 o signatures at the garnet core rim interface compositional profiles in major divalent cations are consistent with the relaxation of an initial sharp step in ca fe and mg by ca fe mg interdiffusion at the same interface an o isotope profile is documented the analogy of ca and o isotope profiles suggests that the 1 8 o distribution may also result from a diffusion process in this particular case temperature garnet composition oxygen fugacity o diffusion appears to be of the same order of magnitude as ca fe mg interdiffusion considering a duration of 10 ma for the plutono metamorphic event in the pyrenees ca and o diffusivities in the range 10 2 2 m 2 s at 850 c are retrieved from the measured profiles like ca o diffusion in garnet at magmatic temperatures 850 900 c is both slow enough to preserve large 1 8 o heterogeneities and fast enough to generate relaxation profiles

anatomy of garnets in a jurassic granite from the south eastern margin of the north china craton magma sources and tectonic implications abstract the late jurassic jingshan granite located at the south eastern margin of the north china craton contains abundant garnets which can be subdivided into three types based on texture and composition i euhedral garnet in mafic biotite and garnet rich enclave grt i ii coarse grained garnet grt ii in the host granite and iii small euhedral garnet in aplite grt iii in general grt i has higher feo cao and lower mno contents than grt ii grt iii has higher mn but lower ca contents than others grt i has lower mree and hree contents than grt ii grt iii has prominent and distinctly negative eu anomaly as well as higher mree composition compared to the others systematic variations in oxygen isotope compositions are observed among the three garnet types with 18 o values of 4 7 in grt iii some of the grt ii and grt iii display two distinct zonings with cores having similar major and trace element compositions to grt i cathodoluminescence cl images revealed that the zircons from different garnet bearing samples possess fine scale oscillatory zoned magmatic rims with inherited cores in situ zircon u pb dating and trace element analyses show that the dark luminescent magmatic rims all have jurassic concordia ages 160 ma and similar trace element patterns most of the inherited cores also display similar triassic ages of 210 236 ma which is similar to the ages of ultrahigh pressure uhp metamorphic rocks of the dabie sulu orogen 230 ma in addition jurassic concordia ages were also found in a zircon inclusion in grt i implying that the grt i was formed shortly before the main magmatic event the age data suggest that the three different garnet types may be genetically related and modified by cogenetic magmatic events based on the zircon u pb ages from different garnet bearing samples the major element trace element oxygen isotope and zoning textures of the three kinds of garnet we suggest that grt i may be peritectic garnet whereas grt ii and iii are probably the results of magmatic dissolution precipitation processes and re equilibration of garnets with changing magmatic conditions during melting differentiation crystallization and cooling within the granite we conclude from the oxygen isotopic character of the garnets and ages of the zircons that the source rocks for the jingshan granites are from dabie sulu orogen representing the south china craton

fault patterns by space remote sensing and the rotation of western oregon during cenozoic times abstract we used mss landsat images bands 6 and 7 as well as previous studies to interpret fault patterns in western oregon in terms of the rotations detected by paleomagnetism these fault zones show a great concentration between the cascade range and the idaho batholite and have several distinct trends the north south striking structures are attributed to the basin and range province while the large nw se right lateral fault zones are interpreted as resulting from an extension between the cascades arc and the olympic wallowa lineament the latter was a paleoplate boundary during pre eocene times this extension beginning during late eocene oligocene times and continuing through recent times is accompanied by a migration of the rotation pole from southeast to northwest and by a clockwise rotation of the coast range klamath mountains cascade range block induced by the subduction of the farallon plate

oxygen isotope analysis of olivine by ion microprobe matrix effects and applications to a serpentinised dunite abstract in order to resolve inter and intracrystalline oxygen isotopic heterogeneities in olivine crystals encountered in mantle peridotites basaltic lavas chondritic meteorites and metamorphic rocks in situ techniques such as ion microprobes are needed accurate ion microprobe analysis requires not only well characterised reference materials but also calibration of the matrix bias for compositional variations within a given mineral we investigated matrix bias effects related to mg fe variations in olivine during in situ analysis of oxygen isotopes with sensitive high resolution ion microprobe shrimp by analysing chemically homogenous olivine samples with forsterite contents in the range fo74 fo100 the isotopic measurements were calibrated against san carlos olivine sco fo91 the repeatability achieved for all samples was 0 21 0 50 standard deviation sd at 95 confidence level c l comparable to that of san carlos olivine 0 31 0 48 sd at 95 c l a matrix bias up to 2 0 was observed in olivine with forsterite content above 92 mol conversely to what has been reported for cameca instruments the relationship between the magnitude of matrix bias and fayalite content mol is described by the quadratic function bias fa 0 0062 fa 2 0 233 fa 1 60 the correction scheme for the matrix bias was applied to chemically zoned olivine crystals from a partly serpentinised dunite from the archean nuasahi massif eastern india olivine cores fo92 preserve their typical mantle like signature with a 18o value of 5 16 0 30 at 95 c l during a low temperature stage of serpentinisation olivine transformed to lizardite1 brucite magnetite olivine rims fo98 18o 1 92 0 60 at 95 c l and the surrounding lizardite2 4 87 0 53 at 95 c l formed during a later stage of rock fluid interaction are in isotopic equilibrium at 405 430 c with a fluid having a 18o of 5 3 6 9 evolved seawater enriched in 18o by isotopic exchange during infiltration could have been responsible for this later serpentinisation stage observed in the nuasahi massif the concomitant analysis of oxygen isotopes at the microscale in both olivine and serpentine represents a powerful tool to constrain the nature and source s of serpentinising fluid s as well as the temperature of serpentinisation

intra and intercrystalline oxygen isotope variations in minerals from basalts and peridotites igneous phenocrysts commonly exhibit zoning in major and trace element composition reflecting and potentially constraining the differentiation and or mixing histories of their parent melts to date little work has been done characterizing zonation of oxygen isotopes in minerals from mafic and ultramafic rocks we present 259 ion probe cameca ims 1280 measurements of 18 o in 34 natural magmatic and mantle olivines and pyroxenes from five hand samples from diverse igneous environments we compare 18 o variations with zonation in other elements especially p analyzed by electron microprobe analysis empa and nano secondary ionization mass spectrometry nanosims there is generally a close average within 0 1 0 2 agreement between average 18 o values of olivines measured by sims standardized against san carlos olivine and independently known values for bulk separates from the same samples measured by laser fluorination these data demonstrate that current ion microprobe techniques are not only precise but also accurate enough for study of sub per mil oxygen isotope variations in silicates within 0 2 provided samples are prepared and analyzed following strict guidelines all but one of the 34 studied grains are homogeneous in 18 o within a small multiple of analytical precision estimated 0 2 1 for most data poorer for a subset of measurements made on small 5 m spots this population of isotopically homogeneous grains includes some with oscillatory micrometer scale p banding the lack of 18 o variations suggests that whatever factors lead to this common mode of trace element zonation have no detectable effect on melt crystal partitioning of oxygen isotopes large 2 oxygen isotope variations are observed in one olivine glomerocryst from mauna kea hawaii this glomerocryst contains p rich domains that are either equant or skeletal or feathery in outline and these p rich domains are systematically low in 18 o compared with adjacent later grown p poor olivine this unusual oxygen isotope zonation pattern might reflect a kinetic fractionation during nucleation and growth of the cores of some olivine phenocrysts we tested this hypothesis through measurements of 18 o distributions in synthetic olivines grown at a range of rates and exhibiting diverse patterns of p zoning these synthetic olivines are homogeneous in 18 o within the limits of our analyses 0 3 0 4 in this case and show no connection between p zonation and oxygen isotope heterogeneity we therefore think it more plausible that unusual o isotope zonation in the mauna kea glomerocryst reflects addition of a low 18 o component to some hawaiian magmas just before nucleation of olivine more generally this study demonstrates the utility of modern sims techniques for in situ study of the subtle 1 range oxygen isotope variations characteristic of common mafic and ultramafic rocks

high resolution geochemical record of fluid rock interaction in a mid crustal shear zone a comparative study of major element and oxygen isotope transport in garnet garnet grains from an intensely metasomatized mid crustal shear zone in the reynolds range central australia exhibit a diverse assortment of textural and compositional characteristics that provide important insights into the geochemical effects of fluid rock interaction electron microprobe x ray maps and major element profiles in situ secondary ion mass spectrometry oxygen isotope analyses and u pb and sm nd geochronology are used to reconstruct their thermal temporal and fluid evolution these techniques reveal a detailed sequence of garnet growth re equilibration and dissolution during intracontinental reworking associated with the ordovician carboniferous 450 300 ma alice springs orogeny a euhedral garnet porphyroblast displays bell shaped major element profiles diagnostic of prograde growth zoning during shear zone burial coexisting granulitic garnet porphyroclasts inherited from precursor wall rocks show extensive cation re equilibration assisted by fracturing and fragmentation oxygen isotope variations in the former are inversely correlated with the molar proportion of grossular suggesting that isotopic fractionation is linked to ca substitution the latter generally show close correspondence to the isotopic composition of their precursor indicating slow intergranular diffusion of o relative to fe2 mg and mn peak metamorphism associated with shearing 550 c 5 0 6 5 kbar occurred at c 360 ma followed by rapid exhumation and cooling progressive mn enrichment in rim domains indicates that the retrograde evolution caused partial garnet dissolution accompanying intra mineral porosity production then stimulated limited oxygen isotope exchange between relict granulitic garnet grains and adjacent metasomatic biotite resulting in increased garnet 18o values over length scales 200 m spatially restricted oxygen interdiffusion was thus facilitated by increased fluid access to reaction interfaces the concentration of ca in channelled fracture networks suggests that its mobility was enhanced by a similar mechanism in contrast the intergranular diffusion of fe2 mg and mn was rock wide under the same p t regime as demonstrated by a lack of local spatial variations in the re equilibration of these components the extraction of detailed reaction histories from garnet must therefore take into account the variable length and time scales of elemental and isotopic exchange particularly where the involvement of a fluid phase enhances the possibility of measureable resetting profiles being generated for slowly diffusing components such as ca and o even at low ambient temperatures and relatively fast cooling rates

diffusion obstacles and opportunities in petrochronology many of the approaches in petrochronology are rooted in the assumption of equilibrium diffusion is an expression of disequilibrium the movement of mass in response to chemical potential gradients and isotopes in response to isotopic gradients it is extremely important that we be aware of how the effects of diffusion can place obstacles across our path towards petrochronologic enlightenment conversely the effects of diffusion also provide opportunities for understanding rates processes and conditions experienced by rocks the enormity of the field does not permit us to provide a comprehensive review of either the mathematics of diffusion or quantitative data that have been obtained relevant to the interpretation of diffusive processes in rocks and minerals many resources cover these topics including rimg volume 72 diffusion in minerals and melts zhang and cherniak 2010 and several textbooks crank 1975 glicksman 2000 particularly relevant to the discussion of petrochronology are summaries of the theory and controls on diffusion brady and cherniak 2010 zhang 2010 as well as diffusion rates in feldspar cherniak 2010a accessory minerals cherniak 2010b garnet ganguly 2010 mica pyroxene and amphibole cherniak and dimanov 2010 and melts zhang and ni 2010 zhang et al 2010 rather than duplicate that material our goal is to explore the obstacles and opportunities presented by the effects of diffusion as they inform the rates of petrologic processes to achieve this goal we emphasize key principles and illustrative examples quantitative interpretation of the effects of diffusion assumes predictability of numerous factors that may affect chemical or isotopic transport including temperature initial and boundary conditions water and oxygen fugacities activities of other components multiple mechanisms of diffusion and crystal chemistry coupling of the substitution of elements into different crystallographic sites additionally the extraction of meaningful ages durations of events and temperatures requires

dehydration melting and fluid recycling during metamorphism rangeley formation new hampshire usa reflect the dewatering of structurally lower levels after nappe emmuscovite and biotite dehydration melting reactions near the peak placement if so then nappe emplacement occurred at t 475 c of metamorphism played a significant role in the reaction and fluid history of the rangeley formation in southwestern new hampshire usa evidence for in situ melting includes 1 the consistency among theoretical phase equilibria observed reaction textures and the inferred p t conditions 2 disseminated centimeter scale

oxygen isotope zoning in garnets from franciscan eclogite blocks evidence for rock buffered fluid interaction in the mantle wedge the oxygen isotope compositions of eclogite and amphibolite garnets from franciscan complex high grade blocks and actinolite rinds encasing the blocks were determined to place constraints on their fluid histories sims oxygen isotope analysis of single garnets from five eclogite blocks from three localities ring mountain mount hamilton and jenner beach shows an abrupt decrease in the 18o value by 1 3 from core to rim at a distance of 120 50 m from the rim in nine out of the 12 garnets analyzed in contrast amphibolite garnets from one block ring mountain analyzed show a gradual increase in 18o value from core to rim implying a different history from that of the eclogite blocks values of 18o in eclogite garnet cores range from 5 7 to 11 6 preserving the composition of the eclogite protolith the abrupt decrease in the 18o values of the garnet rims to values ranging from 3 2 to 11 2 suggests interaction with a lower 18o fluid during the final stages of growth during eclogite facies metamorphism 450 600 c we hypothesize that this fluid is sourced from the serpentinized mantle wedge high mg ni and cr contents of actinolite rinds encasing the blocks also support interaction with ultramafic rock oxygen isotope thermometry using chlorite and phengite versus actinolite of rinds suggests temperatures of 185 240 c at ring mountain and mount hamilton rind formation temperatures together with the lower 18o garnet rims suggest that the blocks were in contact with ultramafic rock from the end of garnet growth through low temperature retrogression we suggest a tectonic model in which oceanic crust is subducted at the initiation of subduction and becomes embedded in the overlying mantle wedge as subduction continues metasomatic exchange between high grade blocks and surrounding ultramafic rock is recorded in low 18o garnet rims and later as temperatures decrease with rind formation