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

origin of the neoproterozoic fulu iron formation south china insights from iron isotopes and rare earth element patterns abstract in the neoproterozoic era there was widespread deposition of iron formations in close association with global or near glaciations these snowball earth glaciations likely played a key role in iron formation distribution and deposition however the environmental conditions fe sources and formation mechanisms remain debated here we present the rare earth element geochemistry and fe isotope composition of the synglacial iron formation within the neoproterozoic fulu formation south china the fulu iron formation consists of layers of authigenic minerals mainly hematite and detrital components quartz feldspars fe chlorite and minor biotite positive eu anomalies in one of the fulu localities indicate a hydrothermal influence suggesting that fe was mainly sourced from distal hydrothermal systems the bulk rock fe isotope composition of the fulu iron formation shows a large range with 56fe from 0 23 to 1 78 correlation between bulk rock 56fe values and al fe ratios demonstrates that 56fe variability reflects in part varying proportions of authigenic versus detrital components the fe isotope composition of authigenic hematite is calculated by a linear regression and shows 56fe between 0 83 and 2 21 with an average at 1 54 0 50 2 n 41 using a dispersion reaction model the high 56fe values of hematite constrain local dissolved o2 concentrations of the ocean to less than 0 4 nmol l even in the shallow part of the water column this relationship is consistent with highly reducing conditions in the neoproterozoic oceans favored by isolation from the atmosphere by a sea ice we attribute the extremely positive values to partial iron oxidation in waters that were cold relative to modern surface oceans the dominant occurrence of hematite supports an abiotic precipitation pathway given that biological activity would have introduced organic matter to the sediments and led to partial reduction of fe iii oxides and subsequent formation of magnetite and or siderite as is observed in archean and paleoproterozoic iron formations oxic glacial meltwater and or o2 vertical transfer from the atmosphere to the upper ocean linked to ice dynamics is likely to have mediated the abiotic oxidation we propose that vertical transfer of o2 resulted from the deposition of snow that trapped air bubbles at the top of the glacier coupled to a melting of the bottom of the glacier which in combination delivered a limited but continuous amount of o2 to the ocean

shallow marine ironstones formed by microaerophilic iron oxidizing bacteria in terminal paleoproterozoic abstract the microbial origin of precambrian iron formations is debated due to the lack of direct fossil evidence in order to reveal the genesis of ironstones under low oxygen levels integrative studies of sedimentology petrography mineralogy and geochemistry were conducted on the intertidal to shallow subtidal ooidal and stromatolitic ironstones from the terminal paleoproterozoic chuanlinggou formation ca 1 65 1 64 ga of north china using microscopy sem eds icp oes icp ms and mc icp ms techniques mineralogical study shows that the fe rich mineral is predominantly hematite that resulted from dehydration of amorphous fe oxyhydroxide during diagenesis petrographic observation indicates that the iron was oxidized and precipitated from seawater rather than sourced from terrestrial detritus basinward increases of the ironstone abundance eu anomalies from 1 39 to 1 56 and 56fe values of the ironstones from 0 5 to 1 0 suggest that the iron was mainly sourced from seafloor hydrothermal fluids and partially oxidized and precipitated in shallow subtidal to intertidal environments the common existence of fe oxide coated sheaths spiral stalks residual extracellular polymer substances eps and other biogenic fabrics indicates that microaerophilic iron oxidizing bacteria feob may have played an important role in precipitating the chuanlinggou ironstones the extremely low oxygen concentrations implied by the proliferation of microaerophilic feob in the shallow waters the weak positive ce anomalies 0 94 1 12 and low mn concentrations in the ironstones are broadly consistent with the previous result of a cr isotope study thus the establishment of a microaerophilic feob genetic model for the widespread chuanlinggou ironstones in north china provides new insight into the origin of precambrian iron formations and the redox evolution of ocean atmosphere systems during the boring billion

mapping of monthly soil erosion risk of mainland mauritius and its aggregation with delineated basins this paper reports the mapping of monthly soil erosion risk on mauritius which was carried out using gis decision rules and readily available data namely monthly rainfall depth soil types slope and land cover slope and soil were first combined to produce soil erosion susceptibility followed by land cover to produce erosion sensitivity and then rainfall to produce erosion risk the high erosion areas of the island have been extracted from the soil erosion risk maps whereby these areas can face land degradation problems and can be responsible for sediment discharge into wetlands located at the outlet of drainage basins as such drainage basins have been delineated using automatic catchment delineation tools and their percentage of high erosion areas computed basins with the greatest percentage of high erosion areas and particularly those that directly have a wetland at the outlet can be given priority for soil and water conservation efforts the mapping reported in this paper can be adapted to other countries which need an erosion assessment for the identification of high erosion areas and priority action areas

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

hafnium and neodymium isotopes in seawater and in ferromanganese crusts the element perspective abstract hafnium and nd isotopes are increasingly used as paleoceanographic proxies comparing the mantle crust array and the seawater array in plots of e hf vs e nd it has been observed that for a given e nd value the corresponding e hf value is higher for seawater than it is for terrestrial rocks while this difference had initially been explained by significant hydrothermal input of mantle hf into seawater the currently favoured explanation is incongruent weathering of continental rocks producing radiogenic riverine hf input we here address this topic from the perspective of the behaviour of these two elements in seawater and in ferromanganese fe mn crusts we distinguish between a truly dissolved and a dissolved hf and nd pool the latter being comprised of truly dissolved and colloid bound colloidal hf and nd while there exists a hydrothermal pathway for colloid bound dissolved mantle hf into the oceans there is in marked contrast to nd no important riverine pathway for colloidal or truly dissolved continental hf owing to their respective chemical speciation in seawater there exists truly dissolved nd in the ocean while the amount of truly dissolved hf is insignificant neodymium is in exchange equilibrium between local seawater and both the hydrous fe and mn oxides hydrogenetic fe mn crusts are composed of due to continuous ad and desorption there is continuous isotopic re equilibration and the isotopic composition of nd in a fe mn crust reflects that of truly dissolved nd in local ambient seawater in contrast hf is only associated with the hydrous fe oxides on which it forms surface precipitates that do not exchange with seawater due to this lack of isotopic re equilibration the isotopic composition of hf in a fe mn crust is the average of that of all the hf scavenged during the lifetime of the hydrous fe oxide particles since the hf bearing hydrous fe oxides in a fe mn crust do not form from local ambient seawater at the crust s growth site but are advected as colloids or fine particles their hf isotopic composition depends on the origin and migration pathway of these colloids hence while nd isotopes in fe mn crusts provide reliable information on truly dissolved nd in local ambient seawater hf isotopes rather indicate the origin and pathway of hydrous fe oxide colloids and might differ from truly dissolved hf in local ambient seawater this may explain the occasional decoupling of nd and hf isotopes in fe mn crusts and supports the notion of a significant hydrothermal mantle signal of hf in seawater

opposing authigenic controls on the isotopic signature of dissolved iron in hydrothermal plumes iron is a scarce but essential micronutrient in the oceans that limits primary productivity in many regions of the surface ocean the mechanisms and rates of fe supply to the ocean interior are still poorly understood and quantified iron isotope ratios of different fe pools can potentially be used to trace sources and sinks of the global fe biogeochemical cycle if these boundary fluxes have distinct signatures seafloor hydrothermal vents emit metal rich fluids from mid ocean ridges into the deep ocean iron isotope ratios have the potential to be used to trace the input of hydrothermal dissolved iron to the oceans if the local controls on the fractionation of fe isotopes during plume dispersal in the deep ocean are understood in this study we assess the behaviour of fe isotopes in a southern ocean hydrothermal plume using a sampling program of total dissolvable fe tdfe and dissolved fe dfe we demonstrate that 56fe values of dfe 56dfe within the hydrothermal plume change dramatically during early plume dispersal ranging from 2 39 0 05 to 0 13 0 06 2 sd the isotopic composition of tdfe 56tdfe was consistently heavier than dfe values ranging from 0 31 0 03 to 0 78 0 05 consistent with fe oxyhydroxide precipitation as the plume samples age the dfe present in the hydrothermal plume includes stabilised dfe species with potential to be transported to the deep ocean we estimate that stable dfe exported from the plume will have a 56fe of 0 28 0 17 further we show that the proportion of authigenic iron sulfide and iron oxyhydroxide minerals precipitating in the buoyant plume exert opposing controls on the resultant isotope composition of dissolved fe passed into the neutrally buoyant plume we show that such controls yield variable dissolved fe isotope signatures under the authigenic conditions reported from modern vent sites elsewhere and so ought to be considered during iron isotope reconstructions of past hydrothermalism from ocean sediment records

osmium isotopes in hydrothermal fluids from the juan de fuca ridge we present os data for axial high temperature and off axial low temperature hydrothermal solutions from the juan de fuca ridge the high temperature h s bearing axial fluids have unradiogenic os isotopes pointing to a nearly complete domination of osmium isotopes from the basalts during hydrothermal circulation the ridge axis fluids typically do not show large enrichment in osmium concentration over seawater although one high temperature fluid has an os concentration enhanced by a factor of 4 above seawater it appears that the os concentration of high temperature hydrothermal fluids is typically buffered at roughly the seawater concentration we suggest that subseafloor precipitation of pyrite from the high temperature hydrothermal fluids controls the osmium transportation the axial hydrothermal activity does not supply significant amounts of unradiogenic osmium to the deep oceans in contrast a low temperature off axis fluid is enriched in non radiogenic osmium over seawater by a factor of 9 showing much less precipitation of osmium at low temperature because a large fraction of the cooling of oceanic lithosphere occurs on ridge flanks os from low temperature ridge flank hydrothermal circulation may be a significant contributor to the balance of os in the oceans a detailed balance between os contributions from dissolution of cosmic dust and hydrothermal fluids is still not possible the low temperature hydrothermal sample gives os os 0 110 0 001 this extremely unradiogenic osmium can only come from a source that underwent depletion of re over 2 6 ga ago assuming no contamination during sample collection this result suggests that the convecting upper mantle contains ancient depleted material that imparted unradiogenic osmium to intruding basaltic melts

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

iron and carbon isotope evidence for microbial iron respiration throughout the archean abstract banded iron formations bifs are voluminous chemical sediments that are rich in iron oxide carbonate and silica and whose occurrence is unique to the precambrian their preservation in the geological record offers insights to the surface chemical and biological cycling of iron and carbon on early earth however many details regarding the role of microbial activity in bif deposition and diagenesis are unresolved laboratory studies have shown that reaction between carbon and iron through microbial iron respiration 2fe2o3 nh2o ch2o 7h 4fe2 hco3 2n 4 h2o chemical energy can impart fractionation to the isotopic compositions of these elements here we report iron 56fe vs irmm 014 and carbon isotopic 13c vs v pdb compositions of magnetite and of iron rich and iron poor carbonates in bifs from the late archean 2 5 ga hamersley basin australia and the early archean 3 8 ga isua supracrustal belt isb greenland the range of 56fe values measured in the hamersley basin including light values in magnetite and heavy values in iron rich carbonates up to 1 2 are incompatible with their precipitation in equilibrium with seawater rather the data together with previously reported light 13c values in iron rich carbonates record evidence for diagenetic reduction of ferric oxide precursors to magnetite and carbonate through microbial iron respiration i e dissimilatory iron reduction dir iron and carbon isotope data of iron rich metacarbonates from the isb are similar to those of late archean bifs the isotopic signatures of these metacarbonates are supportive of an early diagenetic origin despite metasomatic overprint and preserve evidence of microbial iron respiration within the oldest recognized sedimentary rocks on earth

heat flow sediment faulting and porewater advection in the madeira abyssal plain abstract this report describes 21 closely spaced heat flow measurements which were made along two transects in an area of faulted sediments east of great meteor seamount in the madeira abyssal plain the heat flow was found to be correlated with basement topography as mapped by seismic reflection profiling data modelling suggests that this is due both to the thermal conductivity contrast between sediments and basement rocks and to the presence of hydrothermal circulation within basement highs the existence of non linear temperature profiles in sediments covering basement highs suggests that the underlying circulation is causing an upward movement of porewater there is no firm evidence to show that sediment faults act as preferred pathways for porewater advection

integrated fe and s isotope study of seafloor hydrothermal vents at east pacific rise 9 10 n abstract in this study we report on coupled fe and s isotope systematics of hydrothermal fluids and sulfide deposits from the east pacific rise at 9 10 n to better constrain processes affecting fe isotope fractionation in hydrothermal environments we aim to address three fundamental questions 1 is there significant fe isotope fractionation during sulfide precipitation 2 is there significant variability of fe isotope composition of the hydrothermal fluids reflecting sulfide precipitation in subsurface environments 3 are there any systematics between fe and s isotopes in sulfide minerals the results show that chalcopyrite precipitating in the interior wall of a hydrothermal chimney displays a limited range of 56fe values and 34s values between 0 11 to 0 33 and 2 2 to 2 6 respectively the 56fe values are on average slightly higher by 0 14 relative to coeval vent fluid composition while 34s values suggest significant s isotope fractionation 0 6 0 2 during chalcopyrite precipitation in contrast systematically lower 56fe and 34s values relative to hydrothermal fluids by up to 0 91 and 2 0 respectively are observed in pyrite and marcasite precipitating in the interior of active chimneys these results suggest isotope disequilibrium in both fe and s isotopes due to s isotopic exchange between hydrothermal h2s and seawater so42 followed by rapid formation of pyrite from fes precursors thus preserving the effects of a strong kinetic fe isotope fractionation during fes precipitation in contrast 56fe and 34s values of pyrite from inactive massive sulfides which show evidence of extensive late stage reworking are essentially similar to the hydrothermal fluids multiple stages of remineralization of ancient chimney deposits at the seafloor appear to produce minimal fe isotope fractionation similar affects are indicated during subsurface sulfide precipitation as demonstrated by the lack of systematic differences between 56fe values in both high temperature fe rich black smokers and lower temperature fe depleted vents

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

geochemistry of north cleft segment vent fluids temporal changes in chlorinity and their possible relation to recent volcanism hydrothermal vent fluids from the north cleft segment of the juan de fuca ridge between 44 54 and 45 00 n were sampled in 1988 1990 1991 and 1992 in 1988 chloride depleted relative to seawater diffuse fluids with low dissolved metal concentrations relative to other mid ocean ridge mor fluids were sampled over a distance of 10 km along axis in 1990 and 1991 both high temperature 200 c and diffuse vents were consistently metal and chloride enriched the end member compositions of high temperature vents and nearby diffuse vents were very similar there were small but significant correlated changes in diffuse and high temperature composition from 1990 to 1991 the large scale but temporary venting of low chlorinity fluids over the entire north cleft segment provides a resolution to the apparent mass imbalance implied by observations of continuous venting of chloride enriched fluids it is possible that a volcanic event along the north cleft segment prior to 1987 for which there is firm geologic evidence initially caused a boiling event which resulted in the preferential venting of vapor enriched fluids through 1988 followed by a transition to brine enriched fluids by 1990 high iron low sodium and low sr ca ratios in the high chlorinity fluids suggest that the brine phase has continued to react and approach reequilibration with an alteration mineral assemblage after the phase separation event the absence of chloride depleted fluids from 1990 onward and the systematics of lithium boron and manganese with chloride in the high temperature fluids from north cleft suggest that the evolution toward lower chlorinity at monolith vent from 1990 to 1992 is caused by progressive dilution of a brine with hydrothermal seawater

gradients in the composition of hydrothermal fluids from the endeavour segment vent field phase separation and brine loss hydrothermal fluid samples collected in 1984 1987 and 1988 from a large vent field near 47 57 n on the endeavour segment of the juan de fuca ridge jfr have been analyzed for major and minor elements and gases there are of the order of 100 individual smoker vents on 10 large sulfide structures which are localized along faults and fault intersections across the vent field each sulfide structure has a characteristic fluid composition which varies very little from one vent orifice to the next or from year to year on a given structure however there are large gradients in fluid composition across the vent field with endmember chlorinity increasing from 255 mmol kg in the sw to 505 mmol kg in the ne end member concentrations of major elements are well correlated with chlorinity and endmember volatile concentrations in the lowest chlorinity fluids are approximately twice as high as in the highest chlorinity fluids the gradients in composition across the vent field and measured vent fluid temperatures 400 c are consistent with supercritical phase separation and loss of brine phase below the seafloor the factor of 2 variation in co2 and h2s is larger than expected for loss of a very high chlorinity brine concentrations of iron and manganese are not positively correlated with chlorinity suggesting that temperature and ph are more important in controlling metal solubility elevated ammonia and bromide chloride ratios indicate that there has been subseafloor interaction between the hydrothermal fluids and organic matter and high boron concentrations point to a sedimentary source

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

multiple sulphur and iron isotope composition of detrital pyrite in archaean sedimentary rocks a new tool for provenance analysis abstract multiple s 34 s and 33 s and fe 56 fe isotope analyses of rounded pyrite grains from 3 1 to 2 6 ga conglomerates of southern africa indicate their detrital origin which supports anoxic surface conditions in the archaean rounded pyrites from meso to neoarchaean gold and uranium bearing strata of south africa are derived from both crustal and sedimentary sources the latter being characterised by non mass dependent fractionation of s isotopes 33 s as negative as 1 35 and large range of fe isotope values 56 fe between 1 1 and 1 2 most sediment sourced pyrite grains are likely derived from sulphide nodules in marine organic matter rich shales sedimentary exhalites and volcanogenic massive sulphide deposits some sedimentary pyrite grains may have been derived from in situ sulphidised fe oxides prior to their incorporation into the conglomerates as indicated by unusually high positive 56 fe values sedimentary sulphides without significant non mass dependent fractionation of s isotopes were also present in the source of some conglomerates the abundance in these rocks of detrital pyrite unstable in the oxygenated atmosphere may suggest factors other than high p o 2 as the cause for the absence of significant non mass dependent fractionation processes in the 3 2 2 7 ga atmosphere rounded pyrites from the c 2 6 ga conglomerates of the belingwe greenstone belt in zimbabwe have strongly fractionated 34 s 33 s and 56 fe values the source of which can be traced back to black shale hosted massive sulphides in the underlying strata the study demonstrates the utility of combined multiple s and fe isotope analyses for provenance reconstruction of archaean sedimentary successions

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

micro scale tracing of fe and si isotope signatures in banded iron formation using femtosecond laser ablation we have detected micrometre scale differences in fe and si stable isotope ratios between coexisting minerals and between layers of banded iron formation bif using an uv femtosecond laser ablation system connected to a mc icp ms in the magnetite carbonate chert bif from the archean old wanderer formation in the shurugwi greenstone belt zimbabwe magnetite shows neither intra nor inter layer trends giving overall uniform d 56 fe values of 0 9 but exhibits intra crystal zonation bulk iron carbonates are also relatively uniform at near zero values however their individual d 56 fe value is highly composition dependent both siderite and ankerite and mixtures between both are present and d 56 fe end member values are 0 4 for siderite and 0 7 for ankerite the data suggest either an early diagenetic origin of magnetite and iron carbonates by the reaction of organic matter with ferric oxyhydroxides catalysed by fe iii reducing bacteria or more likely an abiotic reaction of organic carbon and fe iii during low grade metamorphism si isotope composition of the old wanderer bif also shows significant variations with d 30 si values that range between 1 0 and 2 6 for bulk layers these isotope compositions suggest rapid precipitation of the silicate phases from hydrothermal rich waters interestingly fe and si isotope compositions of bulk layers are covariant and are interpreted as largely primary signatures moreover the changes of fe and si isotope signatures between bulk layers directly reflect the upwelling dynamics of hydrothermal rich water which govern the rates of fe and si precipitation and therefore also the development of layering during periods of low hydrothermal activity precipitation of only small amounts of ferric oxyhydroxide was followed by complete reduction with organic carbon during diagenesis resulting in carbonate chert layers during periods of intensive hydrothermal activity precipitation rates of ferric oxyhydroxide were high and subsequent diagenesis triggered only partial reduction forming magnetite carbonate chert layers we are confident that our micro analytical technique is able to detect both the solute flux history into the sedimentary bif precursor and the bif s diagenetic history from the comparison between coexisting minerals and their predicted fractionation factors

fe isotope fractionation in magmatic hydrothermal mineral deposits a case study from the renison sn w deposit tasmania abstract we present 50 new iron isotopic analyses of source granite and mineral separates from the renison tin deposit in western tasmania the aim of the study is to characterise the composition of minerals within a tin deposit associated with a reduced s type magma we have analysed bulk samples of granite and separates of pyrrhotite pyrite arsenopyrite magnetite chalcopyrite and siderite by multi collector inductively coupled mass spectrometry the isotopic compositions of mineral separates are consistent with theoretical predictions of equilibrium fractionation based on mossbauer spectroscopy and other parametric calculations mineral mineral pairs yield temperatures of formation that are in agreement with prior detailed fluid inclusion studies but are spatially inconsistent with declining fluid temperatures with distance from the causative intrusion limiting the use of fe isotopes as a potential geothermometer at least in this case comparison of our data with published data from other deposits clearly demonstrates that pyrite magnetite and chalcopyrite from the hottest ore fluids 300 400 c at renison are isotopically heavier than minerals sampled from a deposit formed at similar temperatures but associated with a more oxidised and less differentiated intrusion

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

nitrate reduction sulfate reduction and sedimentary iron isotope evolution during the cenomanian turonian oceanic anoxic event onset of the oae in italy have unusually low bulk d 57 fe values unlike those found in the black shale livello bonarelli deposited during the oceanic anoxic event itself these latter conform to the phanerozoic norm for organic rich sediments pyrite formation in the pre oae black shales has apparently taken place via dissimilatory iron reduction dir within the sediment a suboxic process that causes an approximately 2 fractionation between a lithogenic fe iii oxide source and fe ii aq in contrast bacterial sulfate reduction bsr at least partly in the water column characterized the oae itself and was accompanied by only minor iron isotope fractionation this change in the manner of pyrite formation is reflected in a decrease in the average pyrite framboid diameter from 10 to 7 mm the gradual albeit irregular increase in fe isotope values during the oae as recorded in the italian section is taken to demonstrate limited isotopic evolution of the dissolved iron pool consequent upon ongoing water column precipitation of pyrite under euxinic conditions given that evidence exists for both nitrate and sulfate reduction during the oae it is evident that redox conditions in the water column were highly variable in both time and space

trace elements and isotope geochemistry c o fe cr of the caue iron formation quadrilatero ferrifero brazil evidence for widespread microbial dissimilatory iron reduction at the archean paleoproterozoic transition abstract the banded iron formation bifs of the caue formation quadrilatero ferrifero brazil are part of the great volume of bifs deposited worldwide around 2 45 ga samples of carbonate ankerite dolomite bif from this unit were collected from a drill core ca 600 m deep in the alegria region geochemical data suggest low clastic contamination y ho 37 7 and seawater like signatures with positive la and y anomalies no true ce anomalies and mean eu eu 1 62 u th shows a sharp increasing downwards pattern up to ca 15 below the 535 m mark values of 13c and 18o are all negative reaching a minimum of 10 0 and 24 6 respectively in the 540 560 m interval values of 56fe are mostly positive between 0 5 and 1 3 the higher values are attained in the same interval values of authigenic 53cr range between 0 01 and 0 26 with an increasing downwards pattern which mirrors the u th variation a possible explanation for both the low 13c and the high 56fe is the activity of microorganisms in the dissimilatory iron reduction dir of the precursor ferric oxides thus we put forward a model for deposition of the caue bifs that starts with the generation of fe ii aq through hydrothermal input to the deeper basin which upon reaching a chemocline in the platform border oxidizes to fe iii and settles as iron oxy hydroxides to the basin floor when reaching the sediment layer fe iii is then reduced by microbial activity to generate magnetite and iron rich carbonates with negative 13c and positive 56fe an important issue is how u vi and cr vi were mobilized to the basin to form the positive u th and 53cr excursions these could reflect oxidative continental weathering but an alternative possibility is that those elements became available through local oxygenation in continental microenvironments which would better explain the lack of ce redox cycling in either case our results together with a growing body of data for bif sequences of similar age around the world e g kuruman south africa and hamersley australia suggest that microbial mediated dir was a common and widespread mechanism for the genesis of bifs at the archean paleoproterozoic transition

chemistry of hydrothermal solutions from the southern juan de fuca ridge fluids from three vent fields on the southern juan de fuca ridge were sampled in september 1984 using the dsrv alvin the fluids are uniquely high in both chloride which ranges up to twice the seawater value and in metal content simple vapor liquid phase separation could not have produced both the high chlorinity and gas concentrations observed in these fluids the cause of the elevated chlorinity can not be uniquely identified but may be the result of either or a combination of two processes 1 subsurface formation of a degassed brine and subsequent mixing of a small amount of this brine with a hydrothermal seawater which has not undergone a phase separation and 2 dissolution of a chloride rich phase combined with a possible small loss of gas during sampling procedures although measured temperatures were all less than 300 sup 0 c quartz geothermometry suggests that the fluids have equilibrated at greater than 340 sup 0 c quartz geobarometry is also in agreement with geophysical estimates of depth to the local magma chamber copyright american geophysical union 1987

anoxic to suboxic mesoproterozoic ocean evidence from iron isotope and geochemistry of siderite in the banded iron formations from north qilian nw china abstract banded iron formations bifs provide important constraints on geochemical cycling of fe and ancient marine environment globally the formation of bifs peaked during late archean and early paleoproterozoic with limited reappearance during neoproterozoic here we investigate a rare example of mesoproterozoic ca 1 3 ga bifs from jingtieshan in the north qilian region of nw china we present rare earth element and yttrium ree y compositions together with iron isotope features of siderite from the bifs and integrate these with our published data on carbon isotope compositions from the siderite rich bifs including carbonate facies bifs and mixed carbonate oxide facies bifs siderite from the bifs shows ree y characteristics that are consistent with submarine hydrothermal fluids mixed with seawater including positive eu eu anomalies and high y ho ratios the siderite also displays homogeneous iron isotope compositions 56fe range from 0 71 to 0 41 one sample down to 1 62 and moderate negative carbon isotope compositions 13c values 8 40 to 3 0 these findings argue against the traditional view that siderite associated with bifs was formed through microbial dissimilatory iron reduction dir instead siderite from jingtieshan bifs is in equilibrium with submarine hydrothermal fluids and seawater suggesting an inorganic origin and was directly precipitated from the co2 and fe oversaturated water column with only insignificant role for dir these mesoproterozoic bifs are also characterized by ce anomalies and the siderite falls within the pe log s t and po2 pco2 stability fields suggesting that the bifs were deposited in an anoxic to suboxic ocean the results from our study suggest the presence of iron rich mesoproterozoic deep ocean in the north qilian area

in situ fe isotope ratio determination in fe ti oxides and sulfides from drilled gabbros and basalt from the iodp hole 1256d in the eastern equatorial pacific abstract in situ fe isotope measurements have been carried out to estimate the impact of the hydrothermal metamorphic overprint on the fe isotopic composition of fe ti oxides and fe sulfides of the different lithologies of the drilled rocks from iodp hole 1256d eastern equatorial pacific 15 ma crust formed at the east pacific rise most igneous rocks normally have a very restricted range in their 56fe 54fe ratio in contrast fe isotope compositions of hot fluids 300 c from mid ocean ridge spreading centers define a narrow range that is shifted to lower 56fe values by 0 2 0 5 as compared to igneous rocks therefore it is expected that mineral phases that contain large amounts of fe are especially affected by the interaction with a fluid that fractionates fe isotopes during exsolution precipitation of those minerals we have used a femtosecond uv laser ablation system to determine mineral 56fe 54fe ratios of selected samples with a precision of one key observation is that the temperature dependent inter mineral fractionations of fe isotopes between magnetite and ilmenite are systematically shifted towards higher values when compared to theoretically expected values while synthesized well equilibrated magnetite ilmenite pairs are compatible with the theoretical predictions theoretical considerations including factors of different aqueous fe chlorides and rayleigh type fractionations in the presence of a hydrous chlorine bearing fluid can explain this observation the disagreement between observed and theoretical equilibrium fractionation the fact that magnetite in contrast to ilmenite shows a slight downhole trend in the 56fe values and the observation of small scale heterogeneities within single mineral grains imply that a general re equilibration of the magnetite ilmenite pairs is overprinted by kinetic fractionation effects caused by the interaction of magnetite ilmenite with hydrothermal fluids penetrating the upper oceanic crust during cooling or incomplete re equilibration at low temperatures furthermore the observation of significant small scale variations in the 56fe 54fe ratios of single minerals in this study highlights the importance of high spatial resolution analyses of stable isotope ratios for further investigations

the joffre banded iron formation hamersley group western australia assessing the palaeoenvironment through detailed petrology and chemostratigraphy abstract the joffre member of the brockman iron formation is by volume the largest single known banded iron formation bif in the world here we present detailed petrology and chemostratigraphy through the entire 355 m core section of this 2 45 billion year old unit oxide bif and silicate carbonate oxide bif dominate the lithology with minor amounts of interbedded stilpnomelane mudrock stilpnomelane rich tuffaceous mudrock and calcareous mudrock besides chert and magnetite the prominent mineralogy is riebeckite ankerite hematite stilpnomelane and crocidolite the bif is characterized by an average of 50 wt sio 2 and 44 5 wt fe 2 o 3 and an overall low abundance of al 2 o 3 2 sn of 0 24 the rey patterns also show a positive la sn anomaly no ce sn anomaly and a weakly developed positive y sn anomaly iron isotopes 56 fe with positive 56 fe values of 0 04 to 1 21 suggest that a large part of the hydrothermal iron was partly oxidized in the upper water column and subsequently precipitated as ferric oxyhydroxides no epiclastic grains have been found rather submarine hydrothermal fluids and fine grained volcanogenic detritus controlled bif chemistry the former source is reflected through a constant positive eu sn anomaly throughout the core average eu sn anomaly of 1 6 with a peak of 2 1 between 100 and 155 m depth while the latter source is best reflected through the stilpnomelane rich tuffaceous mudrock consisting of volcanic ash fall tuff with relict shards set in a stilpnomelane matrix the mudrock is overlain by well preserved wavy laminae and laminae sets of stilpnomelane microgranules that likely originated from re worked volcanic ash formed either on the seafloor or in the water column prior to deposition an enriched hree to lree pattern a high iron content 30 wt and a 56 fe value of 0 59 collectively imply that the mudrock facies interacted with the fe rich seawater prior to deposition the tio 2 zr ratio of the bif and the associated mudrocks suggest a felsic only source related to the same style of volcanics as the slightly younger woongarra rhyolites given the observation that the dominant control on the seawater chemistry was associated with felsic volcanics we speculate that the fine grained pelagic ash particles may have sourced bio available nutrients to the surface water this would have facilitated enhanced biological productivity including bacterial fe ii oxidation which is now recorded as the positively fractionated 56 fe iron oxide minerals in the joffre bif alongside submarine hydrothermal input to the basin the dominant control on the ocean chemistry seems to have been through volcanic and pyroclastic pathways thereby making the joffre bif poorly suited as a chemical proxy for the study of atmospheric oxygen and its weathering impact on local landmasses

iron isotope fractionation in a buoyant hydrothermal plume 5 s mid atlantic ridge fe isotopes are a potential tool for tracing the biogeochemical redox cycle of fe in the ocean specifically it is hypothesized that fe isotopes could enable estimation of the contributions from multiple fe sources to the dissolved fe budget an issue that has received much attention in recent years the first priority however is to understand any fe isotope fractionation processes that may occur as fe enters the ocean resulting in modification of original source compositions in this study we have investigated the fe inputs from a basalt hosted deep sea hydrothermal system and the fractionation processes that occur as the hot chemically reduced and acidic vent fluids mix with cold oxygen rich seawater the samples collected were both end member vent fluids taken from hydrothermal chimneys and rising buoyant plume samples collected directly above the same vents at 5 s mid atlantic ridge our analyzes of these samples reveal that for the particulate fe species within the buoyant plume 25 of the fe is precipitated as fe sulfides the isotope fractionation caused by the formation of these fe sulfides is fe ii fes 0 60 0 12 the source isotope composition for the buoyant plume samples collected above the red lion vents is calculated to be 0 29 0 05 this is identical to the value measured in end member vent fluids collected from the underlying tannenbaum chimney the resulting isotope compositions of the fe sulfide and fe oxyhydroxide species in this buoyant plume are 0 89 0 11 and 0 19 0 09 respectively from mass balance calculations we have been able to calculate the isotope composition of the dissolved fe fraction and hypothesize that the isotope composition of any stabilised dissolved fe species exported to the surrounding ocean may be heavier than the original vent fluid such species would be expected to travel some distance from areas of hydrothermal venting and hence contribute to not only the dissolved fe budget of the deep ocean but also it s dissolved fe isotope signature

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

zinc stable isotopes in seafloor hydrothermal vent fluids and chimneys many of the heaviest and lightest natural zinc zn isotope ratios have been discovered in hydrothermal ore deposits however the processes responsible for fractionating zn isotopes in hydrothermal systems are poorly understood in order to better assess the total range of zn isotopes in hydrothermal systems and to understand the factors which are responsible for this isotopic fractionation we have measured zn isotopes in seafloor hydrothermal fluids from numerous vents at 9 10 n and 21 n on the east pacific rise epr the tag hydrothermal field on the mid atlantic ridge and in the guaymas basin fluid 66zn values measured at these sites range from 0 00 to 1 04 of the many physical and chemical parameters examined only temperature was found to correlate with fluid 66zn values lower temperature fluids 250 c had both heavier and more variable 66zn values compared to higher temperature fluids from the same hydrothermal fields we suggest that subsurface cooling of hydrothermal fluids leads to precipitation of isotopically light sphalerite zn sulfide and that this process is a primary cause of zn isotope variation in hydrothermal fluids thermodynamic calculations carried out to determine saturation state of sphalerite in the vent fluids support this hypothesis with isotopically heaviest zn found in fluids that were calculated to be saturated with respect to sphalerite we have also measured zn isotopes in chimney sulfides recovered from a high temperature 383 c and a low temperature 203 c vent at 9 10 n on the epr and in both cases found that the 66zn of chimney minerals was lighter or similar to the fluid 66zn the first measurements of zn isotopes in hydrothermal fluids have revealed large variations in hydrothermal fluid 66zn and suggest that subsurface zn sulfide precipitation is a primary factor in causing variations in fluid 66zn by understanding how chemical processes that occur beneath the seafloor affect hydrothermal fluid 66zn zn isotopes may be used as a tracer for studying hydrothermal processes

coupled fe and s isotope evidence for archean microbial fe iii and sulfate reduction direct fossil evidence for early microbial life on earth is rare microbiological data indicate that sulfate and iron reduction are both among the earliest forms of microbial respiration and direct evidence for the early origin of sulfate reduction comes from sulfur isotopic anomalies in ancient sediments fe isotope geochemistry potentially provides a new way of identifying microbial iron reduction early in earth9s history we present fe isotopic data for sedimentary pyrite from the 2 7 ga belingwe sedimentary basin in zimbabwe isotopically light fe and a remarkable covariation between fe and s isotopes provide strong evidence for coexisting fe and s reduction our results are consistent with an early origin for sulfate reduction and provide direct geochemical evidence for the antiquity of bacterial fe reduction the covariation of fe and s isotopes may provide a useful new tracer of microbial evolution early in earth history

fractionation of oxygen and iron isotopes by partial melting processes implications for the interpretation of stable isotope signatures in mafic rocks abstract recycling of oceanic crust into the deep mantle via subduction is a widely accepted mechanism for creating compositional heterogeneity in the upper mantle and for explaining the distinct geochemistry of mantle plumes the oxygen isotope ratios 18o of some ocean island basalts oib span values both above and below that of unmetasomatised upper mantle 5 5 0 4 and provide support for this hypothesis as it is widely assumed that most variations in 18o are produced by near surface low temperature processes here we show a significant linear relationship between 18o and stable iron isotope ratios 57fe in a suite of pristine eclogite xenoliths the 18o values of both bulk samples and garnets range from values within error of normal mantle to significantly lighter values the observed range and correlation between 18o and 57fe is unlikely to be inherited from oceanic crust as 57fe values determined for samples of hydrothermally altered oceanic crust do not differ significantly from the mantle value and show no correlation with 18o it is proposed that the correlated 57fe and 18o variations in this particular eclogite suite are predominantly related to isotopic fractionation by disequilibrium partial melting although modification by melt percolation processes cannot be ruled out fractionation of fe and o isotopes by removal of partial melt enriched in isotopically heavy fe and o is supported by negative correlations between bulk sample 57fe and cr content and bulk sample and garnet 18o and sc contents as cr and sc are elements that become enriched in garnet and pyroxene bearing melt residues melt extraction could take place either during subduction where the eclogites represent the residues of melted oceanic lithosphere or could take place during long term residence within the lithospheric mantle in which case the protoliths of the eclogites could be of either crustal or mantle origin this modification of both 57fe and 18o by melting processes and specifically the production of low 18o signatures in mafic rocks implies that some of the isotopically light 18o values observed in oib and eclogite xenoliths may not necessarily reflect near surface processes or components

geochemistry of hydrothermal fluids from axial seamount hydrothermal emissions study vent field juan de fuca ridge subseafloor boiling and subsequent fluid rock interaction hydrothermal fluids collected from the ashes vent field in 1986 1987 and 1988 exhibit a very wide range of chemical composition over a small area 60 m in diameter compositions range from a 300 c gas enriched 285 mmol kg co2 low chlorinity 33 of seawater fluid to a 328 c relatively gas depleted 50 mmol kg co2 high chlorinity 116 of seawater fluid the entire range of measured compositions at ashes is best explained by a single hydrothermal fluid undergoing phase separation while rising through the ocean crust followed by partial segregation of the vapor and brine phases other mechanisms proposed to produce chlorinity variations in hydrothermal fluids precipitation dissolution of a chloride bearing mineral or crustal hydration cannot produce the covariation of chlorinity and gas content observed at ashes there is good agreement of the measured fluid compositions with compositions generated by a simple model of phase separation in which gases are partitioned according to henry s law and all salt remains in the liquid phase significant enrichments in silica lithium and boron in the low chlorinity fluids over levels predicted by the model are attributed to fluid rock interaction in the upflow zone depletions in iron and calcium suggest that these elements have been removed by iron sulfide and anhydrite precipitation at some time in the history of the low chlorinity fluids the distribution of low and high chlorinity venting is consistent with mechanisms of phase segregation based on differential buoyancy or relative permeability the relatively shallow depth of the seafloor 1540 m and the observed chemistry of ashes fluids are consistent with phase separation in the sub critical or near critical region

the marine environments encompassing the neoproterozoic glaciations evidence from c sr and fe isotope ratios in the hecla hoek supergroup in svalbard abstract the neoproterozoic era records several important events in earth history the associations between bif deposition snowball earth events and the redox state of seawater are the key to explain the re appearance of banded iron formations bif during the neoproterozoic unraveling ancient iron cycles provides important information about the linkage between the precipitation of bif and the redox condition in the ocean but current iron isotopic data are limited to sediments deposited only during the sturtian glaciations and ediacaran we conducted a detailed geological survey of the tonian to ediacaran sedimentary succession in nordaustlandet island svalbard our chemostratigraphies of 13 c carb from pre sturtian to post marinoan sedimentary successions in the polarisbreen group are consistent with those in coeval sediments we first analyzed iron isotope ratios 56 54 fe of individual pyrite grains with diverse shapes in carbonates black shales quartz arenites and diamictites in order to constrain the redox condition in seawater we found large variations in iron isotope ratios from ca 2 to ca 4 positive 56 54 fe values over 1 0 are only preserved in euhedral and aggregated pyrite grains in black shales of the backlundtoppen formation and the macdonaldryggen member of the elbobreen formation a partial oxidation of ferrous iron in seawater is necessary to explain such high 56 54 fe values which means that deep seawater was ferruginous ferrous iron rich before and after the sturtian glaciation this stands in opposition to the traditional idea that a glacial cover on an ocean is necessary for the accumulation of ferrous iron in neoproterozoic seawater this study presents the first evidence from iron isotopes that supports a deep ferruginous ocean around the sturtian glaciation if the deep ocean was intrinsically iron rich it is likely that neoproterozoic bifs formed by thermohaline circulation during the glaciation and by massive oxidation due to the expansion of oxic oceans after the glaciation

iron sources and dissolved particulate interactions in the seawater of the western equatorial pacific iron isotope perspectives this work presents iron isotope data in the western equatorial pacific marine aerosols and top core margin sediments display a slightly heavy fe isotopic composition 56 fe of 0 33 0 11 2sd and 0 14 0 07 respectively samples reflecting the influence of papua new guinea runoff sepik river and rabaul volcano water are characterized by crustal values in seawater fe is mainly supplied in the particulate form and is found with a 56 fe between a0 49 and 0 34 0 07 the particulate fe seems to be brought mainly by runoff and transported across continental shelves and slopes aerosols are suspected to enrich the surface vitiaz strait waters while hydrothermal activity likely enriched new ireland waters dissolved fe isotopic ratios are found between a0 03 and 0 53 0 07 they are almost systematically heavier than the corresponding particulate fe and the difference between the signature of both phases is similar for most samples with 56 fe dfe pfe 0 27 0 25 2sd this is interpreted as an equilibrium isotopic fractionation revealing exchange fluxes between both phases the dissolved phase being heavier than the particles suggests that the exchanges result in a net nonreductive release of dissolved fe this process seems to be locally significantly more intense than fe reductive dissolution documented along reducing margins it may therefore constitute a very significant iron source to the ocean thereby influencing the actual estimation of the iron residence time and sinks the underlying processes could also apply to other elements

hydrothermal plumes and the delivery of iron to banded iron formation most of the iron in banded iron formation bif was deposited during the period 2 7 1 8 ga within this period fe deposition rates were at least as high as 10 12 gm y according to new age models for the largest bifs peak deposition occurred between 2 4 2 3 ga it is likely that such high deposition rates would not be met by a solely continental source of iron unless significant quantities were remobilized in marine sediment estimates of global heat loss for the late archean early proterozoic suggest a hydrothermal cycling rate approximately three times greater than at present so hydrothermal water rock exchanges were a more important source of fe to the oceans than today hydro thermal plumes depleted in o 2 and enriched in fe were generated at mid ocean ridge crests with substantially shallower depths than present assuming hydrothermal effluent dilution factors of 10 4 plumes transported iron which had a dominantly hydrothermal source into the upper water column and transferred it to

iron isotope fractionation during skarn type metallogeny a case study of xinqiao cu s fe au deposit in the middle lower yangtze valley abstract fe isotope compositions of mineral separates and bulk samples from xinqiao cu s fe au skarn type deposit were investigated an overall variation in 57 fe values from 1 22 to 0 73 has been observed which shows some regularity the 57 fe values of endoskarn and the earliest formed fe mineral phase magnetite are ca 1 2 and ca 0 3 lower respectively relative to the quartz monzodiorite stock indicating that fluid exsolved from the stock is enriched in light fe isotopes moreover spatial and temporal variations in 57 fe values are observed which suggest iron isotope fractionation during fluid evolution precipitation of fe bearing minerals results in the fe isotope composition of residual fluids evolving with time precipitation of fe iii minerals incorporating heavy iron isotopes preferentially leaves the remaining fluid enriched in light isotopes while precipitation of fe ii minerals preferentially taking up light iron isotopes and makes the fe isotopic composition of the fluid progressively heavier the regularity of fe isotope variations occurred during fluid exsolution and evolution indicates that the dominant fe source of xinqiao deposit is magmatic overall this study demonstrates that fe isotope composition has great potential in unraveling ore forming processes as well as constraining the metal sources of ore deposits

iron isotope fractionation during leaching of granite and basalt by hydrochloric and oxalic acids abstract transport of iron fe within hydrothermal and soil environments involves the transferral into aqueous solutions by leaching of complex polyminerallic rocks understanding the isotope fractionation mechanisms during this process is key for any application of the fe isotope system to biogeochemical studies here we reacted biotite granite and tholeiite basalt with 0 5 m hydrochloric acid and 5 mm oxalic acid solutions at ambient temperature solution aliquots were recovered over a seven day period and analysed for major and trace element concentrations and fe isotopic compositions in all experiments fe initially released into solution was isotopically lighter with 56fesolution rock as low as 1 80 in the granite hydrochloric acid system the oxalic acid experiments showed similar patterns but smaller fractionation in all experiments the 56fesolution rock reduced over time which would be in line with the formation of a leached layer as proposed before brantley s l liermann l j guynn r l anbar a icopini g a and barling j 2004 fe isotopic fractionation during mineral dissolution with and without bacteria geochim cosmochim acta 68 15 3189 3204 granite and basalts reacting with hydrochloric acid reached apparent steady state values of 0 60 0 15 and 0 40 0 20 respectively whilst experimental values with oxalic acid were 1 0 0 15 and 0 50 0 15 during the granite experiments alteration of biotite to chlorite followed by dissolution of chlorite were likely the dominant processes whilst in the basalt experiments dissolution of pigeonite was likely the principal source of fe variations in ph during the hydrochloric acid experiments were minimal remaining below 0 5 at all times in oxalic acid solutions the ph increased to over 4 leading likely to precipitation of secondary minerals and adsorption co precipitation of fe onto mineral surfaces these processes could contribute to the greater fractionation observed in the final stages of the oxalic acid experiments our results highlight the importance of mineralogy and fluid composition on the fe isotope systematics during weathering the fractionation processes identified for granites and basalts are in line with those inferred from field observations in soils sediments groundwater and hydrothermal deposits and from laboratory studies of single mineral leaching

trace metals in hydrothermal solutions from cleft segment on the southern juan de fuca ridge concentrations of trace metals in fe and cl rich hydrothermal solutions from the southern juan de fuca ridge sjfr have been determined and corrected for residual precipitates formed in the sampler precipitate corrections for ag cd cu mo pb sb and zn were variable contributing an average of 20 to total solution concentrations whereas corrections for co averaged less than 5 and essentially no corrections were required for fe and mn values for cu co and mo in these solutions showed a strong dependence on temperature with sharp decreases in concentrations as temperatures decreased to less than 320 c in addition and unlike most other metals studied all vent fluids from the sjfr were almost completely depleted in mo relative to seawater values of about 110 nmol kg 1 in contrast to the cu co mo group concentrations of ag cd sb and pb correlated well with those for zn and are presumed to follow a distribution that is influenced less by temperature over the 246 to 332 c range encountered in this study and more by the combined chemical processes that control zn levels along the transport pathway from the deep reaction zone to the vent orifice

preservation of fe isotope heterogeneities during diagenesis and metamorphism of banded iron formation we present the iron isotope composition of primary diagenetic and metamorphic minerals in five samples from the contact metamorphosed biwabik iron formation these samples attained peak meta morphic temperatures of 1 on the millimeter scale minerals in the lowest grade samples consistently show a sequence in which d 56 fe of magnetite silicate carbonate the inter mineral fe isotope differences vary in a fashion that cannot be reconciled with theoretical temperature dependent fractionation factors textural evidence re veals that most if not all magnetite in the biwabik formation is diagenetic not primary and that there was tremendous element mobility during diagenesis the short duration of contact metamorphism allowed diagenetic magnetite compositions to be preserved throughout prograde metamorphism until at least the appearance of olivine magnetite compositions there fore act as an isotope record of the environment in which these sediments formed larger scale fluid flow and longer timescales may allow equilibration of fe isotopes in regionally metamorphosed rocks to lower temperatures than in contact metamorphic environ ments but weakly regionally metamorphosed rocks may preserve small scale fe isotopic heterogeneities like those observed in the biwabik iron formation importantly fe isotope compositions that are charac teristic of chemical sedimentation or hydrothermal processes are preserved at low grade in the form of large inter mineral variations and at high grade in the form of unique bulk rock compositions this observa tion confirms earlier work that has suggested that fe isotopes can be used to identify sedimentary processes in the precambrian rock record

heavy metal and sulfur transport during subcritical and supercritical hydrothermal alteration of basalt influence of fluid pressure and basalt composition and crystallinity crystalline basalt diabase and basalt glass have been reacted with a na ca k cl fluid of seawater ionic strength at 350 425 c 375 400 bars pressure and fluid rock mass ratios of 0 5 1 0 to assess the role of temperature basalt diabase chemistry and texture on heavy metal and sulfur mobility during hydrothermal alteration alteration of basalt diabase is characterized by cation fixation and hydrolysis reactions which show increased reaction progress with increasing temperature at constant pressure correspondingly ph in a series of 400 bar experiments ranges from 4 8 to 2 7 at 350 and 425 c respectively and is typically lower for alteration of a sio2 rich crystalline basalt than for other rock types due in part to relatively high sio2 concentrations in solution high sio2 concentrations stabilize hydrous na and ca rich alteration phases causing ph to decrease according to reactions such as 3 0 caal2si2o8 1 0 ca 2 0 h2o 2 0 ca2al3si3o12 oh 2 0 h phases experimentally produced include mixed layer chlorite smectite ca rich amphibole and clinozoisite clinozoisite was identified as a replacement product of plagioclase from diabase solution interaction experiments in direct response to h production dissolved fe mn and h2s concentrations increase dramatically for early stage reaction h2s typically exceeds fe and mn however at 425 c and after long term reaction at 400 c h2s is lost from solution apparently in response to pyrite replacement of oxide and silicate phases pyrrhotite formed at temperatures 375 c whereas magnetite was identified in all run products except from basalt glass alteration cu and zn concentrations in solution are not simple functions of ph these metals achieve greatest solubility in fluids from experiments at 375 400 c except when basalt glass is used as a reactant the relatively low concentrations of these species in solution during basalt glass reaction may be due to adsorption by fine grained alteration phases

redox changes in a seafloor hydrothermal system recorded in hematite chalcopyrite chimneys abstract hydrothermal chimneys composed of hematite and chalcopyrite grow at the irina ii vent site logatchev hydrothermal field mid atlantic ridge hematite and chalcopyrite form layers that repeatedly alternate within the chimney wall the repeating alternation of hematite and chalcopyrite implies for repeating changes in the physico chemical parameters of the vent fluid the modeled stability diagrams of hematite and chalcopyrite at the physico chemical conditions of the irina ii hydrothermal site showed that the precipitation of these two fe minerals is primarily governed by the activity of h2s and ph fe isotope studies suggest that the successive deposition of chalcopyrite 56 54fe 0 20 and hematite 56 54fe 0 60 layers in the irina ii chimneys is a result of redox changes in the hydrothermal fluid the replacement of hematite by either magnetite or chalcopyrite at some places also suggests for a redox inversion in the hydrothermal system from oxic to reduced chondrite normalized rare earth element distribution patterns of the hematite layers show a strong negative eu anomaly which is interpreted to be a result of crystal chemical control on the rare earth element fractionation during hematite precipitation sr isotope systematics indicate significant and variable incorporation of seawater from 40 to 80 in the hydrothermal system nd pb isotope studies show that nd and pb in chalcopyrite and hematite layers are derived mainly from the underlying mafic and ultramafic rocks the chimneys are young 5 13 1 28 kyrs b p and their wall thickened inward the duration of redox cycles oxic and reducing within the scale of a single chimney is about several hundred years the hematite layers are enriched in w in sn and u indicating that primary hematite hydrothermal deposits at the seafloor may be a potential source for these strategic trace elements high concentrations of these elements in the studied hematite layers can be explained by their easy ion substitution for fe3 in the hematite crystal lattice whereas the most plausible source of the elevated w in and sn contents are the hydrothermal fluids the seawater is the possible major source of u

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

heavy nickel isotope compositions in rivers and the oceans abstract nickel is a biologically active trace metal whose dissolved concentration depth profiles in the ocean show nutrient like behaviour if the pronounced removal of nickel from the dissolved phase in the surface ocean and its return in the deep is associated with an isotopic fractionation nickel isotopes may be able to yield constraints on the precise biogeochemical processes involved here we present the first nickel isotope data for seawater along with data for the dissolved phase of rivers one of the principal sources of nickel to the oceans the dissolved phase of rivers exhibits substantial variability in both ni concentration and 60 ni from 2 2 to 35 nmol kg 1 and 0 29 to 1 34 respectively the most striking result from the nickel isotope analyses of rivers is that they are substantially heavier by up to 1 for 60 ni than the range for silicate rocks on the continents a finding that is analogous to that for other transition metal isotope systems if the data presented here are close to representative of the global riverine flux they suggest an annual input of ni to the oceans of 3 6 10 8 moles and a discharge and concentration weighted 60 ni average of 0 80 the relationship between ni isotopes and concentrations shows similarities with those for other transition metal isotope systems where the main control has been suggested to be isotopic partitioning between the dissolved phase and particulates either in the weathering environment or during transport in stark contrast to the rivers the dataset for seawater is very homogeneous with 2sd of the entire dataset being only twice the analytical reproducibility the second main feature is that seawater is distinctly heavier in ni isotopes than rivers the average 60 ni is 1 44 0 15 2sd and only 2 of the 29 seawater analyses have a ni isotopic composition that is lighter than the heaviest river the lack of an isotopic shift associated with the drawdown of nickel concentrations in the surface ocean suggests that the cycling of nickel between the surface and deep ocean is not associated with a pronounced isotopic fractionation the isotopic data also present a mass balance problem the main output of nickel from the oceans sorption to fe mn oxides appears to be similar in isotopic composition to the dissolved phase yet the riverine input is lighter than the dissolved pool this observation either requires other inputs that are isotopically heavy or an output that is isotopically light further large inputs over and above the dissolved riverine source appear to be required by what we know of the elemental budget but the isotopic mass balance suggests that such an input needs to be isotopically much heavier than both the riverine dissolved load and the lithogenic isotopic composition of nickel

tracking the dispersal of hydrothermal plumes from the juan de fuca ridge using suspended matter compositions in 1988 and 1989 particles from on and off axis neutrally buoyant plumes over the juan de fuca ridge were sampled to study their changing composition with distance from the ridge crest plume depth and particle composition in off axis hydrothermal plumes were used to identify plume sources and trajectories iron and phosphorus concentrations and in particular p fe molar ratios were found to be sensitive indicators of hydrothermal phases in the suspended matter phosphorus vanadium and arsenic are scavenged from solution where dissolved iron from hydrothermal vents oxidizes in seawater and forms submicrometer sized particles of fe oxyhydroxide the p fe molar ratio 0 23 is essentially the same for vent fields along cleft and endeavour segments indicating that the scavenging processes are the same for both regions high p fe ratios are observed over the south and north cleft segment vent fields and to the west along the vance seamount chain the seamounts evidently function as a barrier bathymetrically steering the hydrothermal plumes to the west away from the ridge crest since particles from the endeavour vent field are greatly enriched in copper relative to hydrothermal plumes from other vent fields along the juan de fuca ridge copper concentrations in the plumes can be used to distinguish plume sources based on water column depth and elemental composition hydrothermal plume particles from specific vent fields on the juan de fuca ridge may be tracked as much as several tens of kilometers from their source using particle compositions