two pulses of mineralization and genesis of the zhaxikang sb pb zn ag deposit in southern tibet constraints from fe zn isotopes abstract zhaxikang is one large sb pb zn ag deposit located in the north himalaya of southern tibet to date the genesis of this deposit still remains controversial here we present new pyrite fe and sphalerite zn isotopic data for the first three stages of mineralization fe zn isotopic data for mn fe carbonate that formed during the first two stages of mineralization and zn isotopic data for the slate wall rocks of the jurassic ridang formation to discuss the genesis of the zhaxikang deposit the overall 56 fe and 66 zn values range from 0 80 to 0 43 and from 0 03 to 0 38 respectively the 56 fe values of mn fe carbonates are lighter than those of associated pyrite in six mineral pairs indicating that the iron carbonates are preferentially enriched in light fe isotopes relative to pyrite the sphalerite has lighter 66 zn values than associated mn fe carbonates in three mineral pairs the 56 fe values of pyrite that formed during the first three stages of mineralization gradually increase from stage 1 0 33 to 0 09 through stage 2 0 30 to 0 19 to stage 3 0 16 0 43 in comparison the sphalerite that formed during these stages has 66 zn values that gradually decrease from stage 1 0 16 0 35 through stage 2 0 09 0 23 to stage 3 0 03 to 0 22 these data in conjunction with the observations of hand specimens and thin sections suggest that the deposit was overprinted by a second pulse of mineralization this overprint would account for these fe zn isotopic variations as well as the kinetic rayleigh fractionation that occurred during mineralization the temporally increasing 56 fe and decreasing 66 zn values recorded in the deposit are also coincident with an increase in alteration again supporting the existence of two pulses of mineralization the 56 fe values of the first pulse of ore forming fluid were calculated using theoretical equations yielding values of 0 54 to 0 34 that overlap with those of submarine hydrothermal solutions 1 to 0 however the 56 fe values of the stage 3 pyrite are heavier than those of typical submarine hydrothermal solutions which suggests that the second pulse of mineralization was probably derived from a magmatic hydrothermal fluid in addition the second pulse of ore forming fluid has brought some fe and taken away parts of zn which results the lighter 66 zn values of sphalerite and heavier 56 fe values of pyrite from the second pulse of mineralization overall the zhaxikang deposit records two pulses of mineralization and the overprint by the second pulse of mineralization causes the lighter 66 zn values and heavier 56 fe values of modified samples

the source region and melting mineralogy of high titanium and low titanium lunar basalts deduced from lu hf isotope data five high ti basalts from the apollo 11 and 17 landing sites have been analyzed for their hafnium isotope composition these data serve to better constrain the hafnium isotope variation of the moon s mantle variations in initial hf and nd values of low and high ti basalts imply that the source region mineral assemblages of these lunar magma types are distinct low ti basalts have higher initial hf values at a given nd value than high ti basalts the differences in the hafnium and neodymium isotopic composition of low and high ti basalts reflect the fact that the source of low ti basalts had a lu hf n ratio approximately four times greater than its sm nd n ratio in contrast the high ti source region had subequal lu hf n and sm nd n ratios if it is assumed that mare basalts are partial melts of the moon s cumulate mantle the differences between low and high ti basalts can only be explained by these mare magma types being generated from melting sources with distinctly different mineral assemblages the large lu hf fractionations relative to sm nd fractionations of low ti basalts can best be produced by an assemblage of olivine and orthopyroxene with trace amount of clinopyroxene that crystallized early in the history of the lunar magma ocean lmo the subequal lu hf n and sm nd n fractionations of high ti basalts can be produced from a variety of ilmenite bearing mineral assemblages low and high ti basalts have similar lu hf ratios approximately 0 6 times chondrite the low lu hf ratios measured for these mare magmas contrast sharply with the high lu hf ratios greater than chondritic calculated for their sources from initial hf values and an assumed chondritic bulk moon initial hf value the difference between the measured lu hf of a lava vs the calculated lu hf of its source implies that during partial melting lu was preferentially retained in the residual source relative to hf in order to explain the extreme fractionation of measured lu hf ratios we suggest mare basalts can best be explained using a polybaric melting model initial melting of a garnet bearing source followed by continued melting in the spinel stability field can produce the required lu hf fractionations and produce a liquid that last equilibrated with a residuum of olivine and orthopyroxene

tracing metal silicate segregation and late veneer in the earth and the ureilite parent body with palladium stable isotopes abstract stable isotope studies of highly siderophile elements hse have the potential to yield valuable insights into a range of geological processes in particular the strong partitioning of these elements into metal over silicates may lead to stable isotope fractionation during metal silicate segregation making them sensitive tracers of planetary differentiation processes we present the first techniques for the precise determination of palladium stable isotopes by mc icpms using a 106pd 110pd double spike to correct for instrumental mass fractionation results are expressed as the per mil difference in the 106pd 105pd ratio 106pd relative to an in house solution standard pd ipgp in the absence of a certified pd isotopic standard repeated analyses of the pd isotopic composition of the chondrite allende demonstrate the external reproducibility of the technique of 0 032 on 106pd using these techniques we have analysed pd stable isotopes from a range of terrestrial and extraterrestrial samples we find that chondrites define a mean 106pdchondrite 0 19 0 05 ureilites reveal a weak trend towards heavier 106pd with decreasing pd content similar to recent findings based on pt stable isotopes creech et al 2017 although fractionation of pd isotopes is significantly less than for pt possibly related to its weaker metal silicate partitioning behaviour and the limited field shift effect terrestrial mantle samples have a mean 106pdmantle 0 182 0 130 which is consistent with a late veneer of chondritic material after core formation

iron isotope differences between earth moon mars and vesta as possible records of contrasted accretion mechanisms the iron isotope compositions of shergotty nakhla chassigny snc meteorites thought to come from mars eucrites and diogenites assumed to sample asteroid 4 vesta and rocks from the moon and earth have been measured using high precision plasma source mass spectrometry the means of eight samples from mars and nine samples from vesta are within error identical despite a range of rock types they are lighter by 0 1 in 57fe 54fe compared to the average of 13 terrestrial mantle derived rocks the latter value is identical within uncertainty with a previously published mean of 46 igneous rocks from the earth the average for 14 lunar basalts and highland plutonic rocks covering a broad spectrum of major element composition is heavier by 0 1 in 57fe 54fe relative to our estimate for the earth s mantle and therefore 0 2 heavier than the eucrites diogenites and snc meteorites however the data scatter somewhat and the apollo 15 green glass and apollo 17 orange glass are identical to samples from mars and vesta there is no clear relationship between petrological characteristics and fe isotope composition despite a wide spectrum of samples instead contrasted planetary isotopic signatures are clearly resolved statistically after evaluating alternative scenario it appears that the most plausible explanation for the heavier fe in the earth and moon is that both objects grew via processes that involved partial vaporisation leading to kinetic iron isotope fractionation followed by minor loss this is consistent with the theory in which the moon is thought to have originated from a giant impact between the proto earth and another planet combined with numerical simulations fe isotope data can offer the potential to provide constraints on the processes that occurred in planetary accretion

iron isotopes in the amazon river system weathering and transport signatures abstract trace metal clean plankton tows river samples aerosol leachates and porewater samples from the amazon river system were measured for their iron isotopic composition the overall isotopic range observed was 1 5 with fe isotopic variability observed between different types of tributaries dissolved fe and suspended load fe from two main channel sites were isotopically similar 0 1 to 0 3 in contrast the dissolved fe and suspended load fe from an organic rich tributary the negro river were isotopically distinct with the dissolved slightly isotopically heavy 0 3 and the suspended load isotopically light 0 9 the isotopically lightest sample from the amazon region was shelf porewater 1 3 in river water seawater mixing experiments the fe isotopic signal of dissolved fe of river water was modified by flocculation of isotopically heavy fe the variability of the fe isotopic composition of natural samples including biological and aqueous samples demonstrates that significant fractionation is associated with fe biogeochemistry in the environment

iron isotopes in hot springs along the juan de fuca ridge we present fe isotope data for high temperature hydrothermal fluids sulfides and basalts from the juan de fuca ridge usgs basalt standard bcr 2 and the canyon diablo iron meteorite the fe isotopic compositions of all samples fall within a range of 1 however there is a small but statistically significant isotopic variation between fe dissolved in hydrothermal fluids and fe in canyon diablo specifically the hydrothermal fluids are lighter compared to canyon diablo yielding 56fe 56fe 54fe sample 56fe 54fe canyon diablo 1 1000 values from 0 30 to 0 77 in contrast the bcr 2 basalt and canyon diablo are isotopically indistinguishable measurements of 56fe in juan de fuca ridge basalts and sulfides suggest that fe isotopes are fractionated in hydrothermal systems however the data do not exclude the possibility of small 56fe differences between the rocks from which fluid fe is derived and other igneous fe in which case fractionation in igneous systems is indicated regardless these results are evidence of non biological mass fractionation of fe isotopes in nature further venting of hydrothermal fluids into the overlying water column could provide a source of isotopically light fe to the deep oceans contributing to fe isotopic variations observed in deep sea sediments

natural mass dependent variations in the isotopic composition of molybdenum we present the first observations of natural mass dependent fractionation of the isotopic composition of molybdenum mo using multi collector inductively coupled plasma mass spectrometry variations in the isotopic composition of mo are reported as 97 95mo 97mo 95mo sample 97mo 95mo standard 1 1000 external analytical precision of 97 95mo is 1 between sediments deposited under anoxic conditions 97 95mo 1 02 to 1 52 relative to our in house standard and ferromanganese nodules 97 95mo 0 63 to 0 42 97 95mo of pacific ocean seawater 97 95mo 1 48 lies within the range of values for anoxic sediments closest to modern black sea anoxic sediments molybdenites from continental ore deposits have intermediate 97 95mo ranging from 0 26 to 0 09 variations in the abundances of 92mo 95mo 96mo 97mo and 98mo are consistent with mass dependent fractionation a sporadic unidentified interference occurs at mass 94 and 100mo is not measured we hypothesize that the 97 95mo offset between anoxic sediments and ferromanganese nodules results from mo isotope fractionation during inefficient scavenging of mo from seawater by mn oxides under oxic conditions the similarity in 97 95mo of anoxic sediments and seawater is consistent with the very efficient removal of mo from seawater under anoxic conditions in the presence of h2s the data can be interpreted in terms of a steady state mass balance between the mo flux into the oceans from the continents and the mo flux out of the oceans into oxic and anoxic sediments such an interpretation is quantitatively consistent with existing estimates of the removal fluxes of mo to anoxic and oxic sediments these findings suggest that 97 95mo in seawater may co vary with changes in the relative proportions of anoxic and oxic sedimentation in the oceans and that this variation may be recorded in 97 95mo of anoxic sediments hence the mo isotope system may be useful in paleoredox investigations

an assessment of iron isotope fractionation during core formation abstract iron is a ubiquitous element in terrestrial and extra terrestrial settings and can provide clues as to the conditions during which planetary scale processes occurred one example of this is determining the conditions accompanying metal core formation in rocky planets and planetesimals for at least two decades there has been a growing database of experimental and natural data aimed at understanding whether iron isotopes fractionate during the separation of silicate and metal while it has been argued that the data are not in agreement with one another it is apparent that once criteria are established that prove equilibrated samples there is good agreement amongst the different studies when looked at as a function of the metallic composition proving equilibrium is critical in these types of experiments the three isotope experimental technique for establishing equilibrium is found to be both mathematically and fundamentally sound further it is clear that the question of whether there is an equilibrium iron isotope fractionation between metal and silicate is not straightforward and that it can vary significantly as a function of temperature pressure metallic composition oxygen fugacity and silicate composition

the october 9 1995 colima jalisco mexico earthquake mw8 an aftershock study and a comparison of this earthquake with those of 1932 data from portable seismographs and a permanent local network called resco are used to locate the aftershocks of the october 9 1995 colima jalisco earthquake mw 8 0 the maximum dimension of the aftershock area which is rectangular in shape is 170 km 70 km our study shows that the mainshock nucleated 24 km south of manzanillo near the foreshock of october 6 1995 mw 5 8 and propagated 130 km to the nw and 40 km to se the aftershock area lies offshore and is oriented parallel to the coast the observed subsidence of the coast is a consequence of this offshore rupture area the aftershocks reach unusually close to the trench within 20 km this may be due to lack of sediments with high pore pressure at shallow depth there are some similarities between this earthquake and the two great earthquakes of 1932 3 june ms 8 1 18 june ms 7 8 which occurred in this region in both cases the aftershocks were located offshore and the coastline subsided the sum of seismic moments and the rupture lengths of the 1932 events 1 8 1021 n m and 280 km respectively however were greater than the 1995 earthquake also a comparison of seismograms of 1932 and 1995 earthquakes show great differences it seems that the 1995 event is not a repeat of either june 3 or june 18 1932 earthquakes

experimental quantification of the fractionation of fe isotopes during metal segregation from a silicate melt abstract fractionation of fe isotopes between a silicate melt and metallic alloys has been quantified experimentally at 1500 c the effects of oxygen fugacity and run duration have been investigated to distinguish between kinetic and equilibrium fractionations a new experimental setup is presented in which metallic fe is produced by reduction of oxidized iron from a silicate melt due to a change of redox conditions this metallic fe is physically removed from the silicate and sequestered as a pt fe alloy bulk analyses of the silicate and metallic fractions using multi collector icp ms methods are coupled with in situ analyses using an ion microprobe experimental results indicate that significant isotopic fractionation of fe occurs during metal segregation during the early stages of the experiments we find evidence for kinetic fractionation caused by faster diffusion of 54 fe along concentration gradients in the alloy this process leads to the formation of a metallic phase which is isotopically light compared to the residual silicate metal silicate fractionation up to 2 35 a m u the data are used to quantify the difference in diffusion coefficient of each isotope of iron providing a means to predict fe isotope fractionation during fe diffusion in metallic alloys on the other hand this state of affairs is transient in nature and at superliquidus temperature the systems rapidly reach a state of isotopic equilibrium in which the metal is isotopically heavier than the silicate melt by about 0 2 0 15 a m u these results are consistent with the range of variation observed in natural samples these kinetic and equilibrium data provide an experimental framework to understand the observed variability among igneous and meteoritic materials formed at high temperature particularly for iron and pallasite meteorites

iron isotopes in an archean ocean analogue abstract iron isotopes have been extensively used to trace the history of microbial metabolisms and the redox evolution of the oceans archean sedimentary rocks display greater variability in iron isotope ratios and more markedly negative values than those deposited in the proterozoic and phanerozoic this increased variability has been linked to changes in either water column iron cycling or the extent of benthic microbial iron reduction through time we tested these contrasting scenarios through a detailed study of anoxic and ferruginous lac pavin france which can serve as a modern analogue of the archean ocean a depth profile in the water column of lac pavin shows a remarkable increase in dissolved fe concentration 0 1 1200 m and 56fe values 2 14 to 0 31 across the oxic anoxic boundary to the lake bottom the largest fe isotope variability is found at the redox boundary and is related to partial oxidation of dissolved ferrous iron leaving the residual fe enriched in light isotopes the analysis of four sediment cores collected along a lateral profile one in the oxic layer one at the redox boundary one in the anoxic zone and one at the bottom of the lake indicates that bulk sediments porewaters and reactive fe mostly have 56fe values near 0 0 0 2 similar to detrital iron in contrast pyrite 56fe values in sub chemocline cores 60 65 and 92 m are highly variable and show significant deviations from the detrital iron isotope composition 56fepyrite between 1 51 and 0 09 average 0 93 importantly the pyrite 56fe values mirror the 56fe of dissolved iron at the redox boundary where near quantitative sulfate and sulfide drawdown occurs suggesting limited iron isotope fractionation during iron sulfide formation this finding has important implications for the archean environment specifically this work suggests that in a ferruginous system most of the fe isotope variability observed in sedimentary pyrites can be tied to water column cycling foremost to the oxidation of dissolved ferrous iron this supports previous suggestions that enhanced iron isotope variability in the archean may record a unique stage in earth s history where partial ferrous iron oxidation in upwelling water masses was a common process probably linked to oxygenic or anoxygenic photosynthesis

iron isotope investigation of hydrothermal and sedimentary pyrite and their aqueous dissolution products abstract oxidative dissolution experiments were carried out on pyrite from multiple petrogenetic environments hydrothermal sedimentary and coal related nodules to investigate possible variations in the iron isotopic composition of pyrite and the products of pyrite dissolution the experimental materials were leached under carefully controlled abiotic conditions and a subset of leachates and starting materials from these experiments was analyzed for 56fe 54fe by multicollector icp ms bulk pyrite 56fe values relative to irmm 014 ranged from 0 1 to 1 3 with hydrothermal bulk pyrite values

questioning fe isotopes as a provenance tool insights from bog iron ores and alternative applications in archeometry abstract provenancing metal artifacts with scientific methods is an established tool in archeometry to identify the metal deposits which were exploited for the production of ancient metal objects it is thus an important method to reconstruct ancient exchange networks and the socio economic organization of past societies previously introduced isotope based approaches pb sr os and chemical analyses of slag inclusions have severe limitations concerning their application or the amount of sample required fe isotopes were previously suggested in a quite early stage of investigation as a potential provenance tracer and it was postulated that they would not fractionate during the smelting procedure however previously published analytical data from iron ores indicate a wide overlap between deposits further the earlier studies on fe isotopes did not included bog iron ores despite their high importance in ancient metallurgy as geochemical reactions during ore formation are complex and fractionation cannot be generally excluded the applicability of fe isotopes as an alternative provenance tracer still asks for further investigation this purely methodological study focuses on specimens from two sites of the formerly mined bog iron ore deposit eyller bruch germany which are analyzed together with products of a smelting experiment based on these ores the fe isotopic composition of the bog iron ore from the investigated region suggests an intra deposit zonation caused by environmental parameters and its overall variation is comparable with that of other deposits the bog iron ore isotope signature largely overlaps with the isotope range of mineralizations in other regions as a consequence of this and although the absence of fe isotope fractionation during the smelting procedure is confirmed the study demonstrates the lack of discriminatory power of fe isotopes for provenance studies potential applications for archeometry can rather be found in the environmental parameters especially organic matter which seems to have a strong influence on fe isotope compositions of bog iron ores zonations within deposits might be identified and could help to reconstruct the exploitation history of the deposit or to reconstruct past bog landscapes

subsurface processes at the lucky strike hydrothermal field mid atlantic ridge evidence from sulfur selenium and iron isotopes at lucky strike near the azores triple junction the seafloor setting of the hydrothermal field in a caldera system with abundant low permeability layers of cemented breccia provides a unique opportunity to study the influence of subsurface geological conditions on the hydrothermal fluid evolution coupled analyses of s isotopes performed in conjunction with se and fe isotopes have been applied for the first time to the study of seafloor hydrothermal systems these data provide a tool for resolving the different abiotic and potential biotic near surface hydrothermal reactions the 34s between 1 5 and 4 6 and se values between 213 and 1640 ppm of chalcopyrite suggest a high temperature end member hydrothermal fluid with a dual source of sulfur sulfur that was leached from basaltic rocks and sulfur derived from the reduction of seawater sulfate in contrast pyrite and marcasite generally have lower 34s within the range of magmatic values 0 1 and are characterized by low concentrations of se 50 ppm for 82se 76se ratios the 82se values range from basaltic values of near 1 5 to 7 the large range and highly negative values of hydrothermal deposits observed cannot be explained by simple mixing between se leached from igneous rock and se derived from seawater we interpret the se isotope signature to be a result of leaching and mixing of a fractionated se source located beneath hydrothermal chimneys in the hydrothermal fluid at lucky strike we consider two sources for s and se 1 the end member hydrothermal fluid with basaltic se isotopic values 1 5 and typical s isotope hydrothermal values of 1 5 2 a fractionated source hosted in subsurface environment with negative 34s values probably from bacterial reduction of seawater sulfate and negative 82se values possibly derived from inorganic reduction of se oxyanions fluid trapped in the subsurface environment is conductively cooled and has restricted mixing and provide favorable conditions for subsurface microbial activity which is potentially recorded by s isotopes fe isotope systematic reveals that se rich high temperature samples have 57fe values close to basaltic values 0 whereas se depleted samples precipitated at medium to low temperature are systematically lighter 57fe values between 1 to 3 an important implication of our finding is that light fe isotope composition down to 3 2 may be explained entirely by abiotic fractionation in which a reservoir effect during sulfide precipitation was able to produce highly fractionated compositions

iron stable isotopes beyond biosignatures abstract the stable isotope geochemistry of fe has attracted intense interest in the past five years this interest was originally motivated by the possible use of fe isotopes in biosignature applications particularly in sediments from the ancient earth or mars this application is still being developed with particular attention to fractionation mechanisms understanding such mechanisms should also provide new insights into the environmental biogeochemistry of fe at the same time the fe isotope system holds promise for other exciting frontiers including applications in oceanography solid earth geochemistry and biomedicine such applications will be increasingly attractive as fe isotope analysis becomes routine

flood hazard assessment of upper jhelum basin using morphometric parameters morphometric parameters can be useful tools to provide general understanding of physical characteristics of drainage basin with respect to floods to evaluate the flood influencing factors in the upper jhelum basin we delineate the upper jhelum basin into ten sub basins followed by extraction of drainage network and morphometric parameters using advanced spaceborne thermal emission and reflection radiometer digital elevation model and topographic maps in geographic information system the overall flood potential was determined on the basis of compound value obtained for all morphometric parameters of each sub basin the analysis reveals that in general the northeastern segment of the upper jhelum basin reveals comparative higher flood potential than the southwestern segment the tributaries such as lidder veshav arapal arapat and bring exhibit greater potential to produce peak flows during rainfall events while the tributaries like dudhganga rambiara sandran romushi and sasara express moderate to low flood potential respectively the results of this study are likely to be very useful for effective flood hazard mitigation in upper jhelum floodplain

secular variation of iron isotopes in north atlantic deep water a high precision iron isotope time series for a ferromanganese crust demonstrates that the iron isotope composition in north atlantic deep water has changed substantially over the past 6 million years and that iron isotope variations in the crust are closely correlated to those of lead isotopes the close correlation between the two isotope series indicates that the observed iron isotope variations predominantly reflect those of iron input from terrigenous sources and provides no evidence for biologically induced mass fractionation within north atlantic deep water

biogeochemical cycling of iron in the archean paleoproterozoic earth constraints from iron isotope variations in sedimentary rocks from the kaapvaal and pilbara cratons abstract iron isotope compositions of low metamorphic grade samples of archean paleoproterozoic sedimentary rocks obtained from fresh drill core from the kaapvaal craton in south africa and from the pilbara craton in australia vary by 3 in 56 fe 54 fe ratios reflecting a variety of weathering and diagenetic processes depositional ages for the 120 samples studied range from 3 3 to 2 2 ga and fe c and s contents define several compositional groups including samples rich in fe organic carbon carbonate and sulfide the 56 fe values for low c org low c carb and low s sedimentary rocks are close to 0 the average of igneous rocks this range is essentially the same as that of c org poor late cenozoic loess aerosol river loads and marine sediments and those of c org poor phanerozoic proterozoic shales that these 56 fe values are the same as those of igneous rocks suggests that fe has behaved conservatively in bulk sediments during sedimentary transport diagenesis and lithification since the archean these observations indicate that if atmospheric o 2 contents rose dramatically between 2 4 and 2 2 ga as proposed by many workers such a rise did not produce a significant change in the bulk fe budget of the terrestrial sedimentary system if the archean atmosphere was anoxic and fe was lost from bedrock during soil formation any isotopic fractionation between aqueous ferrous fe fe aq 2 and fe bearing minerals must have been negligible in contrast if the archean atmosphere was oxic fe would have been retained as fe 3 hydroxides during weathering as it is today which would produce minimal net isotopic fractionation in bulk detrital sediments siderite rich samples have 56 fe values of 0 5 0 5 and experimentally determined fe aq 2 siderite fractionation factors suggest that these rocks formed from fe aq 2 that had similar or slightly higher 56 fe values the 56 fe values calculated for fe aq 2 overlaps those of modern submarine hydrothermal fluids but it is also possible that fe aq 2 had 56 fe values higher than those of modern hydrothermal fluids depending upon the fe aq 2 fe carbonate fractionation factor that is used in contrast c org rich samples and magnetite rich samples have strongly negative 56 fe values generally between 2 3 and 1 0 and available fluid mineral fractionation factors suggest that the fe bearing minerals siderite and magnetite in these rocks formed in the presence of fe aq 2 that had very low 56 fe values between 3 and 1 reduction of fe 3 hydroxide by sulfide precipitation of sulfide minerals or incongruent dissolution of silicate minerals are considered unlikely means to produce significant quantities of low 56 fe fe aq 2 we interpret microbial dissimilatory fe 3 reduction dir as the best explanation for producing such low 56 fe values for fe aq 2 and our results suggest that dir was a significant form of respiration since at least 2 9 ga

the iron isotope composition of enstatite meteorites implications for their origin and the metal sulfide fe isotopic fractionation factor abstract despite their unusual chemical composition it is often proposed that the enstatite chondrites represent a significant component of earth s building materials based on their terrestrial similarity for numerous isotope systems in order to investigate a possible genetic relationship between the fe isotope composition of enstatite chondrites and the earth we have analyzed 22 samples from different subgroups of the enstatite meteorites including eh and el chondrites aubrites main group and shallowater and the happy canyon impact melt we have also analyzed the fe isotopic compositions of separated magnetic and non magnetic phases from both enstatite chondrites and achondrites on average eh3 5 chondrites 56fe 0 003 0 042 2 standard deviation n 9 including previous literature data as well as el3 chondrites 56fe 0 030 0 038 2 sd n 2 have identical and homogeneous fe isotopic compositions indistinguishable from those of the carbonaceous chondrites and average terrestrial peridotite in contrast el6 chondrites display a larger range of isotopic compositions 0 180 enstatite achondrites aubrites also exhibit a relatively large range of fe isotope compositions all main group aubrites are enriched in the light fe isotopes 56fe 0 170 0 189 2 sd n 6 while shallowater is isotopically relatively heavy 56fe 0 045 0 101 2 sd n 4 number of chips we take this variation to suggest that the main group aubrite parent body formed a discreet heavy fe isotope enriched core whilst the shallowater meteorite is most likely from a different parent body where core and silicate material remixed this could be due to intensive impact induced shearing stress or the ultimate destruction of the shallowater parent body analysis of separated enstatite meteorite mineral phases show that the magnetic phase fe metal is systematically enriched in the heavier fe isotopes when compared to non magnetic phases fe hosted in troilite which agrees with previous experimental observations and theoretical calculations the difference between magnetic and non magnetic phases from enstatite achondrites provides an equilibrium metal sulfide fe isotopic fractionation factor of 56femetal troilite 56femetal 56fetroilite of 0 129 0 060 2 se at 1060 80 k which confirms the predictions of previous theoretical calculations

high precision iron isotope measurements of terrestrial and lunar materials we present the analytical methods that have been developed for the first high precision fe isotope analyses that clearly identify naturally occurring mass dependent isotope fractionation a double spike approach is used which allows rigorous correction of instrumental mass fractionation based on 21 analyses of an ultra pure fe standard the external precision 1 sd for measuring the isotopic composition of fe is 0 14 mass for demonstrated reproducibility on samples this precision exceeds by at least an order of magnitude that of previous attempts to empirically control instrumentally produced mass fractionation dixon et al 1993 using the double spike method 15 terrestrial igneous rocks that range in composition from peridotite to rhyolite 5 high ti lunar basalts 5 fe mn nodules and a banded iron formation have been analyzed for their iron isotopic composition the terrestrial and lunar igneous rocks have the same isotopic compositions as the ultra pure fe standard providing a reference fe isotope composition for the earth and moon in contrast fe mn nodules and a sample of a banded iron formation have iron isotope compositions that vary over a relatively wide range from 56fe 0 9 to 1 2 this range is 15 times the analytical errors of our technique these natural isotopic fractionations are interpreted to reflect biological vital effects and illustrate the great potential fe isotope studies have for studying modern and ancient biological processes

copper isotope ratios in magmatic and hydrothermal ore forming environments multi collector inductively coupled plasma mass spectrometry now provides for precise and accurate measurements of cu isotope ratios copper minerals prepared by direct dissolution with and without chromatographic purification yield identical cu isotope ratios within analytic precision of about 0 04x 1r cu isotope ratios have been measured for copper minerals from worldwide magmatic and hydrothermal copper deposits and for several weathered deposits natural variations in d65cu values relative to nbs976 range over 9x chalcopyrite samples from mafic intrusions lie within a narrow range of about 1 5x and most cluster tightly between 0 10xand 0 20x this range lies within the broader black smoker chalcopyrite and iron meteorite ranges and possibly represents a bulk mantle cu isotope ratio most values for hydrothermal native copper from the michigan native copper district also show a narrow range just larger than 0 1xand suggest a common homogeneous source for cu in this large hydrothermal system later copper sulfide and arsenide minerals from this district range to values more than 2x lower than native copper ratios for chalcopyrite and bornite from moderate to high temperature porphyry skarn and replacement deposits as a group and within individual deposits exhibit a broad range of values variations of nearly 1xare observed over distances on the order of 1 m in some cases these variations may result from multiple mineralization events or copper remobilization during retrograde or later hydrothermal activity fractionations between chalcopyrite and bornite where they occur in the same sample or in related samples cluster near 0 4x suggesting equilibrium cu isotope fractionation between them at moderate temperatures in addition weathering of hydrothermal copper minerals produces a wide range of values in secondary copper phases in the supergene environment cuprite typically has higher values than associated native copper therefore redox states appear to exert a significant control over fractionation at low temperatures significant questions remain to be answered before the source of copper in hydrothermal environments can be fully addressed source reservoir cu ratios need to be determined and chemical and physical factors that control cu isotope fractionation must be quantitatively defined d 2003 elsevier b v all rights reserved

isotope fractionation by chemical diffusion between molten basalt and rhyolite abstract experimental diffusion couples were used to study chemical diffusion between molten rhyolite and basalt with special emphasis on the associated fractionation of calcium and lithium isotopes diffusion couples were made by juxtaposing firmly packed powders of a natural basalt suny morb and a natural rhyolite lake county obsidian and then annealing them in a piston cylinder apparatus for times ranging from 0 1 to 15 7 h temperatures of 1350 1450 c and pressures of 1 2 1 3 gpa profiles of the major elements and many trace elements were measured on the recovered quenched glasses the diffusivities of all elements except lithium were found to be remarkably similar while the diffusivity of lithium was two to three orders of magnitude larger than that of any of the other elements measured chemical diffusion of calcium from molten basalt into rhyolite was driven by a concentration ratio of 18 and produced a fractionation of 44ca from 40ca of about 6 because of the relatively low concentration of lithium in the natural starting materials a small amount of spodumene lialsi2o6 was added to the basalt in order to increase the concentration difference between basalt and rhyolite which was expected to increase the magnitude of diffusive isotopic fractionation of lithium the concentration ratio between li doped basalt and natural rhyolite was 15 and the resulting diffusion of lithium into the rhyolite fractionated 7li from 6li by about 40 we anticipate that several other major rock forming elements such as magnesium iron and potassium will also exhibit similarly larger isotopic fractionation whenever they diffuse between natural melts with sufficiently large differences in the abundance of these elements

fractionation of fe isotopes by soil microbes and organic acids small natural variations in fe isotopes have been attributed to biological cycling however without understanding the mechanisms of fractionation it is impossible to interpret such variations here we show that the d 56 fe of fe dissolved from a silicate soil mineral by siderophore producing bacteria is as much as 0 8 lighter than bulk fe in the mineral a smaller isotopic shift is observed for fe released abiotically by two chelates and the magnitude of the shift increases with affinity of the ligand for fe consistent with a kinetic isotope effect during hydrolysis of fe at the mineral surface fe dissolved abiotically without chelates shows no isotopic shift the d 56 fe of the exchange fraction on soil grains is also lighter by 0 6 1 than fe from both hornblende and iron oxyhydroxides the kinetic isotope effect is therefore preserved in open systems such as soils when recorded in the rock record fe isotopic fractionation could document fe transport by organic molecules or by microbes where such entities were present in the geologic past

biological control of calcium isotopic abundances in the global calcium cycle measurements of 44ca 40ca expressed as 44ca were made on igneous rocks and on shell and bone material from modern organisms to investigate the magnitude and origins of calcium isotopic fractionation in nature the results document a span of 4 in 44ca measured with the double spike technique to a precision of 0 15 volcanic rocks including basalt and rhyolite show little variability and cluster near 44ca 0 0 2 systematic analysis of biological samples indicates that biological processing of calcium discriminates against heavy isotopes and that biological fractionation is the primary generator of calcium isotopic fractionation in nature preliminary data suggest that calcium becomes isotopically lighter as it moves through food chains calcium carbonate shells of marine microorganisms and deep sea carbonate ooze have 44ca about 1 0 lower than seawater this fractionation causes seawater to be enriched in heavy calcium 44ca 0 9 relative to igneous rocks marine organisms consequently are isotopically heavier than their terrestrial counterparts at similar trophic level the calcium isotopic composition of living and fossil organisms may record information on diet and environment

on the iron isotope homogeneity level of the continental crust abstract assessing the level of homogeneity of different planetary reservoirs is an essential step to establish a new isotopic tracer in recent studies we concluded that most igneous rocks from the continental crust were homogeneous to 71 wt sio2 that we concluded were significantly heavier than less silicic rocks from the crust on the basis of fe isotopic analyses of seven bulk rock samples from different geological settings beard and johnson beard b l johnson c m 2006 comment on heavy iron isotope composition of granites determined by high resolution mc icp ms by f poitrasson and r freydier chemical geology volume 222 pages 132 147 chem geol this issue challenge this finding on the basis of previously published data it is shown here that this controversy stems from the confusion between whole rock and mineral iron isotope analyses since this isotopic tracer like many others is more heterogeneous at the mineral scale than the bulk rock scale thus minerals cannot be used in place of bulk rock fe isotope compositions the controversy also arises from different levels of analytical uncertainties if only the best fe isotope probes of planetary reservoirs bulk rocks are considered then the conclusion that igneous rocks with sio2 71 wt are significantly heavier than the mean 57fe of the continental crust poitrasson f freydier r 2005 heavy iron isotope composition of granites determined by high resolution mc icp ms chem geol 222 132 147 remains valid nonetheless given that granites represent only a minor fraction of the continental crust this finding does not change the bulk igneous fe isotope composition estimate previously defined for the earth

the importance of a ni correction with ion counter in the double spike analysis of fe isotope compositions using a 57fe 58fe double spike we present a new method capable of measuring iron isotope ratios of igneous materials to high precision by multicollector inductively coupled plasma mass spectrometry mc icp ms using a 57fe 58fe double spike after sample purification near baseline signal levels of nickel are still present in the sample solution acting as an isobaric interference on 58 amu to correct for the interference the minor 60ni isotope is monitored and used to subtract a proportional 58ni signal from the total 58 amu beam the 60ni signal is difficult to precisely measure on the faraday detector due to johnson noise occurring at similar magnitude this noise dominated signal is subtracted from the total 58 amu beam and its error amplified during the double spike correction placing the 60ni beam on an ion counter produces a more precise measurement resulting in a near threefold improvement in 56fe reproducibility from 0 145 when measured on faraday to 0 052 faraday detectors quantify the 60ni signal poorly and fail to discern the transient 20ne40ar interference visible on the ion counter which is likely responsible for poor reproducibility another consideration is instrumental stability defined herein as drift in peak center mass which affects high resolution analyses analyses experiencing large drift relative to bracketing standards often yield non replicating data based on this we present a quantitative outlier detection method capable of detecting drift affected data after outlier rejection long term precision on individual runs of our secondary standard improves to 0 046 averaging 3 4 analyses further improves precision to 0 019 allowing distinction between ultramafic minerals this article is protected by copyright all rights reserved

significance of iron isotope mineral fractionation in pallasites and iron meteorites for the core mantle differentiation of terrestrial planets abstract seven bulk chondrites with 57 fe 54 fe values between 0 1 and 0 relative to irmm 14 tend to be slightly lighter than 11 bulk iron meteorites which have 57 fe 54 fe values ranging from 0 04 to 0 2 at the mineral scale taenite from two iron meteorites cranbourne and toluca shows 57 fe 54 fe values heavier by up to 0 3 than their kamacite counterpart thus calling into question the significance of bulk iron meteorite data on three pallasites esquel marjalahti and springwater we measured a heavier iron isotope composition for the metal fractions compared to the coexisting olivines as previously observed on two other pallasites eagle station and imilac but the range of 57 fe 54 fe differences from 0 32 to 0 07 is larger than that originally found troilite from two pallasites appears to be even heavier than the metal fraction whereas schreibersite is lighter than its olivine counterpart there is thus a general tendency for minerals within a given rock to show a heavier fe isotope composition as the coordination number of fe increases although troilite is an exception to this rule iron meteorites are classically considered as remnants of asteroid cores and pallasites as core mantle interfaces the simultaneous finding that the metal fractions of pallasites have a higher 57 fe 54 fe signature than the coexisting olivines and that the iron meteorites are slightly heavier than chondrites could be taken as an indication that planetary core mantle differentiation is accompanied by sizeable iron isotope fractionation in this hypothesis mass balance constraints imply that resultant planetary mantles should be isotopically lighter than the chondritic starting material that is not observed however since all planetary mantles analyzed so far have 57 fe 54 fe values equivalent to or heavier than those of chondrites it thus appears that the moderate temperature and pressure metal silicate fractionation that occurred in pallasite and iron parent bodies is not readily transposable to planets as far as fe isotopes are concerned instead these mantle signatures could reflect equilibrium fractionation at a higher temperature or the lack of a global core mantle equilibration at the planetary scale overall these new results show that the mass dependent isotopic scatter observed among inner solar system bodies from the bulk rock to the planetary scale 0 3 57 fe 54 fe is more restricted than previously thought this likely confirms a homogenization process that occurred in the protoplanetary accretion disk between refractory inclusion condensation and chondrule formation

geochemical signatures and processes in a stream contaminated by heavy mineral processing near ipoh city malaysia abstract the environmental impacts of a heavy mineral processing involving rare earth elements rees in the kinta river and its tributaries near ipoh city in malaysia is investigated using geochemical and isotopic signatures and geochemical modeling analysis of water sediment suspended particulate matter and rock samples reveals that stream waters close to the heavy mineral processing plant site are anthropogenically influenced as indicated by slightly low ph 4 98 6 24 and elevated concentrations of fe up to 129 mg l cl 1540 mg l total rees 1580 g l u 17 2 g l and th 0 33 g l ree patterns and pb isotope ratios of waters and sediments from a tributary are similar to those of tailings pond seepage and sediments suggesting that not only these elements but also u and th are derived from heavy mineral processing the 56fe values of water in the tributary decrease downstream accompanied by a decrease in fe concentration which is likely due to isotope fractionation via oxidative precipitation of fe hydroxides the concentrations of rees u and th decrease downstream accompanied by an increase in ph with different removal factors th u rees the influence of contamination is confined to within 1 5 km downstream of the source tamm s acid oxalate extraction to dissolve only low crystalline phases showed that th and al concentrations were lower while u and fe concentrations were higher in downstream suspended particulate samples suggesting that th and u may be removed by different mechanisms from stream water the results of geochemical modeling suggest that th precipitated as a solid phase such as an intermediate between tho2 and th oh 4 with increasing stream water ph in contrast u may have been removed by adsorption onto fe hydroxides as supported by surface complexation modeling the geochemical signatures and processes discussed in this study may be applicable for environmental assessment of ree processing