carbonate sedimentology of the early precambrian hamersley group of western australia abstract the early precambrian hamersley group of western australia contains both major and minor occurrences of well preserved carbonate sedimentary rock the carawine dolomite and the middle or paraburdoo member of the wittenoom formation are the two most extensive occurrences the carawine dolomite is restricted to the eastern part of the hamersley basin and contains abundant stromatolites oncolites and wave ripples as well as local occurrences of evaporite crystal pseudomorphs and oolitic to pisolitic textures these carbonate strata were deposited in a shallow water paleoenvironment herein referred to as the carawine platform in contrast the wittenoom formation is restricted to the centraland western parts of the hamersley basin and such shallow water features are entirely absent from its carbonate strata these strata consist largely of thinly laminated lutite but also include some thin carbonate turbidites the carbonate sedimentary rocks of the wittenoom formation as well as some in the carawine dolomite which display similar characteristics are therefore interpreted as sediments that were deposited off platform in deeper water paleoenvironments paleocurrent thickness and grain size trends of the carbonate turbidites indicate they were deposited by paleoflows moving south and west even though the carawine dolomite lies to the northeast of the wittenoom formation stratigraphic correlations using a newly recognized marker bed of probable impact origin suggest that the carbonate strata of the carawine dolomite are younger than the paraburdoo member of the wittenoom formation if true the carawine platform could not have been a source of sediment for most of the carbonate sedimentary rocks in the wittenoom formation but it may havebeen the sediment source for similar carbonate turbidites in younger formations such as the mt mcrae shale and the dales gorge member of the brockman iron formation this in turn suggests that carbonate sediments were accumulating in the shallower parts of the hamersley basin while some of the bifs were being deposited simultaneously in the deeper parts

isotopic dating of an archean bolide impact horizon hamersley basin western australia detailed geologic field work in the hamersley basin of western australia has identified a single horizon that contains predominantly sand sized spherules similar to those found in impact ejecta such as at the cretaceous tertiary boundary evidence suggests that these spherules represent a reworked distal strewn field formed by a large bolide impact in late archean time this so called spherule marker bed occurs throughout the main body of the hamersley basin and in stratigraphically equivalent but shallower water lithologies in the northeastern corner carbonate constitutes both a matrix component of the spherule marker bed and minor interbeds in the local stratigraphic section we have utilized carbonate pb pb dating methods to provide for the first time an age estimate 2541 18 15 ma for this important marker bed and therefore of the bolide impact event samples from both facies define within error an identical isochron age that is also consistent with the few zircon based age estimates for the hamersley succession these findings highlight the great potential of carbonate pb pb geochronology in the dating of archean and proterozoic sedimentary rocks

a reconstruction of archean biological diversity based on molecular fossils from the 2 78 to 2 45 billion year old mount bruce supergroup hamersley basin western australia abstract bitumens extracted from 2 7 to 2 5 billion year old ga shales of the fortescue and hamersley groups in the pilbara craton western australia contain traces of molecular fossils based on a combination of molecular characteristics typical of many precambrian bitumens their consistently and unusually high thermal maturities and their widespread distribution throughout the hamersley basin the bitumens can be characterized as probably of archean age accepting this interpretation the biomarkers open a new window on archean biodiversity the presence of hopanes in the archean rocks confirms the antiquity of the domain bacteria and high relative concentrations of 2 methylhopanes indicate that cyanobacteria were important primary producers oxygenic photosynthesis therefore evolved 2 7 ga ago and well before independent evidence suggests significant levels of oxygen accumulated in the atmosphere moreover the abundance of cyanobacterial biomarkers in shales interbedded with oxide facies banded iron formations bif indicates that although some archean bif might have been formed by abiotic photochemical processes or anoxygenic phototrophic bacteria those in the hamersley group formed as a direct consequence of biological oxygen production biomarkers of the 3 methylhopane series suggest that microaerophilic heterotrophic bacteria probably methanotrophs or methylotrophs were active in late archean environments the presence of steranes in a wide range of structures with relative abundances like those from late paleoproterozoic to phanerozoic sediments is convincing evidence for the existence of eukaryotes in the late archean 900 ma before visible fossil evidence indicates that the lineage arose sterol biosynthesis in extant eukaryotes requires molecular oxygen the presence of steranes together with biomarkers of oxygenic photosynthetic cyanobacteria suggests that the concentration of dissolved oxygen in some regions of the upper water column was equivalent to at least 1 of the present atmospheric level pal and may have been sufficient to support aerobic respiration

iron isotope constraints on fe cycling and mass balance in oxygenated earth oceans the fe isotope composition of proterozoic to modern clastic sedimentary rocks and aerosols defines a range ind 56 fe values that is only slightly more variable than the range of fe isotope com positions measured in terrestrial igneous rocks indicating that chemical weathering sedimentary transport and diagenesis play only a minor role in producing fe isotope variations in environ ments where fe redox conditions have been controlled by current levels of atmospheric oxygen in contrast the fe isotope composi tions of hot fluids 300 8c from mid ocean ridge mor spread ing centers define a narrow range that is shifted to lower d 56 fe values by 0 2 0 5 as compared to igneous rocks these new data allow a conceptual model for the fe isotope composition of the oxic oceans that predicts large ranges in fe isotope composition under conditions of changing aerosol and mor fe fluxes such as during periods of major worldwide glaciation

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

iron isotope fractionation during oceanic crust alteration abstract the purpose of this work is to study the mobility and budget of fe isotopes in the oceanic crust and in particular during low temperature interaction of seawater with oceanic basalt we carried out this investigation using samples from ocean drilling program odp site 801c drilled during leg 129 and leg 185 in jurassic pacific oceanic crust seaward of the mariana trench the site comprises approximately 450 m of sediment overlying a section of 500 m of basalt which includes intercalated pelagic and chemical sediments in the upper basaltic units and two low temperature 10 30 c ocherous si fe hydrothermal deposits fe was chemically separated from 70 selected samples and 57fe 54fe ratios were measured by mc icp ms isoprobe the isotopic ratios were measured relative to an internal standard solution and are reported relative to the international fe standard irmm 14 based on duplicate measurements of natural samples an external precision of 0 2 2 has been obtained the results indicate that the deep sea sediment section has a restricted range of 57fe which is close to the igneous rock value in contrast large variations are observed in the basaltic section with positive 57fe values up to 2 05 for highly altered basalts and negative values down to 2 49 for the associated alteration products and hydrothermal deposits secondary fe minerals such as fe oxyhydroxides or fe bearing clays celadonite and saponite have highly variable 57fe values that have been interpreted as resulting from the partial oxidation of fe2 leached during basalt alteration and precipitated as fe3 rich minerals in contrast altered basalts at site 801c which are depleted in fe up to 80 display an increase in 57fe values relative to fresh values which suggest a preferential leaching of light iron during alteration the apparent fractionation factor between dissolved fe2 and fe remaining in the mineral is from 0 5 to 1 3 and may be consistent with a kinetic isotope fractionation where light fe is stripped from the minerals alternatively the formation of secondary clays minerals such as celadonite during basalt alteration may incorporate preferentially the heavy fe isotopes resulting in the loss of light fe isotopes in the fluids because microbial processes within the oceanic crust are of potential importance in controlling rates of chemical reactions fe redox state and fe isotope fractionation we evaluated the possible effect of this deep biosphere on fe isotope signatures the fe isotope systematics presented in this study suggest that even though iron behavior during seafloor weathering may be mediated by microbes such as iron oxidizers 57fe variations of more than 4 may also be explained by abiotic processes further laboratory experiments are now required to distinguish between various processes of fe isotope fractionation during seafloor weathering

sedimentary petrography of the early proterozoic pretoria group transvaal sequence south africa implications for tectonic setting abstract sandstone petrography geochemistry and petrotectonic assemblages of the predominantly clastic sedimentary rocks of the early proterozoic pretoria group transvaal sequence point to relatively stable cratonic conditions at the beginning of sedimentation interrupted by minor rifting events basement uplift and a second period of rifting occurred towards the end of pretoria group deposition which was followed by the intrusion of mafic sill swarms and the emplacement of the bushveld complex in the kaapvaal craton at about 2050 ma the latter indicating increased extensional tectonism and incipient continental rifting an overall intracratonic lacustrine tectonic setting for the pretoria group is supported by periods of subaerial volcanic activity and palaeosol formation rapid sedimentary facies changes significant arkosic sandstones the presence of non glacial varves and a highly variable mudrock geochemistry

iridium anomaly but no shocked quartz from late archean microkrystite layer oceanic impact ejecta samples from a ca 2 54 ga layer rich in microkrystites sand size spherules of former silicate melt in the hamersley group western australia are enriched in ir up to 50 fold over associated carbonates and shales but few of the other siderophile elements display significant anomalies or chondritic interelement ratios however similar concentrations and interelement ratios are observed in ejecta from the ca 590 ma acraman impact structure and have been attributed to diagenetic redistribution the microkrystite layer also contains sand size quartz grains with internal textures typical of regionally metamorphosed rocks rather than evidence of shock metamorphism we suggest that the microkrystites were created by an impact that took place in a deep ocean basin rather than on a continent and that the associated quartz is epiclastic detritus brought in by unusually high energy waves and or currents not as ballistic ejecta

isotopic composition of disseminated sulfur in precambrian sedimentary rocks abstract isotopic analyses of trace sulfur in precambrian carbonates and clastic sedimentary rocks support the results of previous studies which have shown that 34s measurements of archean sedimentary sulfur cluster mostly around mantle like values and that a significant overall dispersion of 34 s 32 s ratios commenced at about 2 7 ga ago the outstanding feature of the proterozoic record is the predominance of heavy 34ssulfide values mostly in excess of 0 cdm consideration of these data in combination with the sparse 534s record for proterozoic sulfates suggests that 34ssulfide sulfide may have been smaller than was the case during the phanerozoic a possible scenario that is compatible with the above data is based on a proposition that the terrestrial exogenic sulfur cycle evolved in a tripartite manner in the archean it was coupled to and controlled by the magmatic endogenic cycle the proterozoic for the most part represents a transitional stage into a phanerozoic like exogenic cycle the latter essentially decoupled from its endogenic counterpart and its redox balance maintained and mediated by the biosphere the indication that the mean combined 34s of proterozoic sulfate and sulfide may have significantly exceeded the phanerozoic mean value of 2 cdm is enigmatic and poses problems for balance considerations

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

intra arc sedimentation in a low lying marginal arc eocene clarno formation central oregon abstract the clarno formation consists of andesitic volcaniclastic rocks interstratified with clayey paludal sediments and lava flows and cut locally by irregular hypabyssal stocks dikes and sills lateral lithofacies variations are pronounced and intrusive and extrusive volcanic rocks appear haphazardly emplaced throughout the formation a range of sedimentary environments is represented in the volcaniclastic sequences including near vent flow and breccia accumulations bouldery high gradient braided streams and relatively low gradient sandy tuff braidplains associated with paludal deposits we infer that the coarse grained volcaniclastic rocks of the clarno formation accumulated largely in volcanic flank and apron settings the formation s stratigraphy reflects an abundance of small volcanoes erupting into sedimentary lowlands and only a few scattered remnants of large central vent volcanoes are known the absence of systematic variation across a large outcrop belt argues against derivation of the succession from a line of volcanoes beyond the reaches of the present outcrop we infer that the arc was composed of small to medium size volcanoes arranged haphazardly across a broad area the sedimentary succession most probably accumulated in a series of intra arc depressions formed by diffuse block rotation driven by oblique subduction during the eocene

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

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

direct dating of stromatolitic carbonates from the schmidtsdrif formation transvaal dolomite south africa with implications on the age of the ventersdorp supergroup pb isotopic analyses of stromatolitic limestones from the schmidtsdrif formation transvaal dolomite of south africa give a late archean isochron age of 2 557 plus minus 49 2 sigma ma the new date significantly changes the position of the archean proterozoic boundary in the kaapvaal province and suggests that a possible division of the transvaal supergroup is necessary it also resolves the long standing controversy about the age of the ventersdorp supergroup whose zircon u pb data of ca 2 7 ga must be more acceptable than the rb sr dates of about 2 3 ga the study provides a new example that demonstrates the great potential of employing the u pb systems of carbonate rocks for direct dating of sedimentary sequences

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

geochemistry and mineralogy of sediments from the ventersdorp and transvaal supergroups south africa cratonic evolution during the early proterozoic approximately 100 pelite and 12 quartzite samples from the ventersdorp 2 7 ga and transvaal supergroups 2 6 2 1 ga have been analyzed to monitor the early proterozoic evolution of the kaapvaal craton southern africa from oldest to youngest pelites were sampled from the ventersdorp bothaville bot transvaal selati sel black reef br timeball hill th strubenkop str and silverton sil formations paleocurrent measurements in transvaal quartzites indicate sources lying predominantly to the north and east relative to the bot sel br pelites from the th str sil are enriched in heavy ree lile zr hf nb and ta depleted in k2o mgo ni and cr and have lower cr zr sc th k2o na2o and k rb ratios compared to sel br bot th str sil pelites have higher light ree contents and la yb ratios and lower eu eu ratios 0 61 0 66 relative to nasc north american shale composite thstr sil pelites are enriched in light ree th u ta nb sc cs have higher la yb ratios and are depleted in k2o and mgo bot sel br pelites are enriched in k2o mgo cr and ni have higher k2o na2o sc th and eu eu ratios and are depleted in th u heavy ree and high field strength elements hfse relative to nasc compositions of th str sil pelites suggest a provenance similar to average phanerozoic uppercontinental crust this source is more evolved than that of bot sel br pelites indicating a transformation from primitive mafic rich to evolved felsic rich upper crust at 2 2 ga this transition follows earlier primitive to evolved trends in moodies pongola 3 3 3 0 ga and witwatersrand 2 8 ga successions these data suggest that several cycles of changing upper continental crust occurred in the kaapvaal craton between 3 3 2 1 ga

iron isotope fractionation during microbial reduction of iron the importance of adsorption in experiments investigating the causes of fe isotope fractionation the d 56 54 fe value of fe ii remaining in solution fe ii aq after reduction of fe iii goethite by shewanella putrefaciens is 21 2 relative to the goethite in agreement with previous research the addition of an electron shuttle did not affect fractionation suggesting that fe isotope fractionation may not be related to the kinetics of the electron transfer furthermore in abiotic anaerobic fecl2 aq experiments in which approximately one third of fe ii aq is lost from solution due to adsorption of fe ii onto goethite the d 56 54 fe value of fe ii aq remaining in solution is shifted by 20 8 relative to fecl 2 this finding demonstrates that anaerobic nonbiological interaction between fe ii and goethite can generate signif icant fe isotope fractionation acid extraction of sorbed fe ii from goethite in experi ments reveals that heavy fe preferentially sorbs to goethite simple mass balance modeling indicates that the isotopic composition of the sorbed fe ii pool is 11 5 to 12 5 heavier than fe in the goethite 2 7 3 7 heavier than aqueous fe ii mass balance is also consistent with a pool of heavy fe that is not released to solution during acid extraction

early archean foredeep sedimentation related to crustal shortening a reinterpretation of the barberton sequence southern africa abstract the upper dominantly terrigenous sedimentary successions of the early archean barberton sequence kaapvaal province record an evolution similar to that of phanerozoic foredeeps and may represent the oldest known foredeep sequence rather than a passive continental margin sequence as previously proposed pre foredeep ocean crust the 3 5 ga old onverwacht group consists of bimodal volcanics with intercalated shallow water sediments gravity modeling and boundary shear zones indicate that deformed onverwacht crust was obducted northward onto sialic continental crust immediately before during or after burial by the synorogenic terrigenous clastic fill foredeep basin deepening due to crustal loading from the south is recorded by basinal iron formation chert and mudstone of the basal fig tree group which accumulated paraconformably on the onverwacht overlying sediments of the fig tree group consist of 2 km of submarine fan greywackes and mudstones shoaling of the basin is indicated by the transition to the overlying braided alluvial and shallow marine sediments of the ca 3 3 ga old moodies group 3 km thick changing ree patterns and relative abundances of ni cr sr th and ur in the sediments of the fig tree and moodies groups indicate a significant ultramafic mafic volcanic component diluted upward in the stratigraphic sequence by an increasing granitic contribution a similar trend is reflected in sandstone petrography in which the ratio of extrusive to intrusive rock fragments decreases upwards in the fig tree group whereas the moodies group sediments are enriched in quartz and potassium feldspar a persistent chert component in both units suggests that the tectonic setting of the basin is analogous to that of phanerozoic recycled orogens the distribution of facies in the fig tree and moodies groups and paleocurrent petrographic and geochemical data indicate progressive unroofing of a southerly source terrane consisting of the onverwacht volcanics and intercalated sediments and the 3 5 3 2 ga old ancient gneiss complex agc in addition older components of the fig tree group were recycled into overlying stratigraphie units the agc consists of mantle derived 3 5 ga old bimodal metavolcanics and metasediments a tonalite gneiss batholith metabasite dikes and meta anorthosites its structures record progressive northwestward uplift beginning around 3 4 ga ago intense homogeneous ductile strains were overprinted by northwest verging major folds rotated by large scale northwestward simple shear followed by imbricate faulting and pseudotachylite formation by 3 3 ga ago the fig tree and moodies groups had also shortened with similar kinematics to those of the agc by partly syndepositional folding and volume loss during the formation of transecting cleavage further folding and slide formation followed during subsolidus diapiric rise of the initially tabular kaap valley tonalite by 3 2 ga and emplacement of trondhjemite plutons from 3 3 to 3 0 ga ago

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

formation of an archaean continent about 30 of the earth is covered by continents but only about 10 small kernels of these continentsae known as archaean cratonsae are continental fragments formed before 2 5 gyr ago the kaapvaal craton of south africa which formed and stabilized between 3 7 and 2 7 gyr ago is one of the oldest reasonably sized examples of these continental fragments it consists of a mosaic of subdomains that have been welded together by processes similar to those of modern day plate tectonics the earliest subdomains may have owed their origin to the onset of efficient recycling from the earth s hydrosphere into the mantle

mechanical compaction and ultrasonic velocity of sands with different texture and mineralogical composition this study presents the results of experimental compaction while measuring ultrasonic velocities of sands with different grain size shape sorting and mineralogy uniaxial mechanical compaction tests up to a maximum of 50 mpa effective stress were performed on 29 dry sand aggregates derived from eight different sands to measure the rock properties a good agreement was found between the gassmann saturated bulk moduli of dry and brine saturated tests of selected sands sand samples with poor sorting showed low initial porosity while sands with high grain angularity had high initial porosity the sand compaction tests showed that at a given stress well sorted coarse grained sands were more compressible and had higher velocities vp and vs than fine grained sands when the mineralogy was similar this can be attributed to grain crushing where coarser grains lead to high compressibility and large grain to grain contact areas result in high velocities at medium to high stresses the angular coarse to medium grained sands both sorted sands and un sorted whole sands showed high compaction and velocities vp and vs the small grain to grain contact areas promote higher deformation at grain contacts more crushing and increased porosity loss resulting in high velocities compaction and velocities vp and vs increased with decreasing sorting in sands however at the same porosity the velocities in whole sands were slightly lower than in the well sorted sands indicating the presence of loose smaller grains in between the framework grains quartz poor sands containing less than 55 quartz showed higher velocities vp and vs compared to that of quartz rich sands this could be the result of sintering and enlargement of grain contacts of ductile mineral grains in the quartz poor sands increasing the effective bulk and shear stiffness tests both from wet measurements and gassmann brine substitution showed a decreasing vp vs ratio with increasing effective stress the quartz rich sands separated out towards the higher side of the vp vs range the gassmann brine substituted vp and vs plotted against effective stress provide a measure of the expected velocity range to be found in these and similar sands during mechanical compaction deviations of actual well log data from experimental data may indicate uplift the presence of hydrocarbon overpressure and or cementation data from this study may help to model velocity depth trends and to improve the characterization of reservoir sands from well log data in a low temperature 80 100o c zone where compaction of sands is mostly mechanical

was the oligocene miocene a time of fire and rain insights from brown coals of the southeastern australia gippsland basin abstract lithotype cycles ranging from 10 to 30 m thick in the brown coals of the latrobe valley gippsland basin australia display well developed lightening upward trends cycle tops are characterized by abrupt and unconformable boundaries with the overlying cycle geological geochemical palynological and macrofossil evidence is consistent with a relative drying terrestrialization upward depositional model for the cycles the abundance of charcoal in dark lithotypes near the cycle bases is explained by the fire prone and highly flammable nature of the herbaceous reed wetlands in common with similar modern wetlands in modern australasia in which the dark lithotypes are suggested to have formed this together with the greater preservation potential of charcoal in subaqueous environments results in the wettest facies of the latrobe valley coals having the highest charcoal contents despite prevailing warm wet climate conditions and the predominance of rainforests that are suggested to have characterized the cenozoic of southern australia some swamp taxa were clearly already pre adapted to tolerate fire and are likely to have been the ancestors of the fire adapted floral communities of modern arid australia

chronology of early archaean granite greenstone evolution in the barberton mountain land south africa based on precise dating by single zircon evaporation abstract we report precise 207 pb 206 pb single zircon evaporation ages for low grade felsic metavolcanic rocks within the onverwacht and fig tree groups of the barberton greenstone belt bgb south africa and from granitoid plutons bordering the belt dacitic tuffs of the hooggenoeg formation in the upper part of the onverwacht group yield ages between 3445 3 and 3416 5 ma and contain older crustal components represented by a 3504 4 ma old zircon xenocryst fig tree dacitic tuffs and agglomerates have euhedral zircons between 3259 5 and 3225 3 ma in age which we interpret to reflect the time of crystallization a surprisingly complex xenocryst population in one sample documents ages from 3323 4 to 3522 4 ma we suspect that these xenocrysts were inherited during the passage of the felsic melts to the surface from various sources such as greenstones and granitoid rocks now exposed in the form of tonalite trondhjemite plutons along the southern and western margins of the bgb and units predating any of the exposed greenstone or intrusive rocks several of the granitoids along the southern margin of the belt have zircon populations with ages between 3490 and 3440 ma coeval with or slightly older than onverwacht felsic volcanism while the kaap valley pluton along the northwestern margin of the belt is coeval with fig tree dacitic volcanism these results emphasize the comagmatic relationships between greenstone felsic volcanic units and the surrounding plutonic suites some of the volcanic and plutonic units contain zircon xenocrysts older than any exposed rocks these indicate the existence of still older units possibly stratigraphically lower and older portions of the greenstone sequence itself older granitoid intrusive rocks or bodies of older unrelated crustal material our data show that the onverwacht and fig tree felsic units have distinctly different ages and therefore do not represent a single tectonically repeated unit as proposed by others unlike the late archaean abitibi greenstone belt in canada which formed over about 30 ma exposed rocks in the bgb formed over a period of at least 220 ma the complex zircon populations encountered in this study imply that conventional multigrain zircon dating may not accurately identify the time of felsic volcanic activity in ancient greenstones a surprising similarity in rock types tectonic evolution and ages of the bgb in the kaapvaal craton of southern africa and greenstones in the pilbara block of western australia suggests that these two terrains may have been part of a larger crustal unit in early archaean times

kinetic iron stable isotope fractionation between iron ii and iii complexes in solution abstract iron stable isotope fractionation between tris 2 2 bipyridine iron ii fe ii bipy 3 2 and iron iii chloride complexes has been measured using plasma source mass spectrometry the experimental protocol involves complexing fe ii ion with 2 2 bipyridine in a fe ii fe iii chloride solution and then separating the fe ii and fe iii solution species in 6 m hcl on an anion exchange resin large isotopic variations of 57 fe and 56 fe are experimentally measured in the two separated solution fractions with isotopic fractionations increasing from fe ii fe iii 25 to 174 units for 57 fe 54 fe and 17 to 117 units for 56 fe 54 fe the increase in fractionations correlates with a decrease in the mole fraction of fe ii in the solution fe fe ii fe ii fe iii that results from the dissociation and breakdown of fe ii bipy 3 2 complex in 6 m hcl solution the data variations are mainly ascribed to a kinetic fractionation occurring during this dissociation reaction mass balance calculations assuming that a rayleigh law describes the overall isotopic trends suggest a kinetic fractionation of ca 1 010 100 units the magnitude of this fractionation is attributed to the rupturing of the strong covalent bonds between 2 2 bipyridine and fe ii ion the experimental data confirm that the coordination chemistry of iron exhibits a profound control on its isotopic behaviour and that kinetic fractionations may play an important role in its isotope geochemistry as was also found in the pioneering experimental studies of the sulphur isotopic system in solution

the stratigraphy of the 3 5 3 2 ga barberton greenstone belt revisited a single zircon ion microprobe study abstract recent field and geochemical studies indicate a need to test the stratigraphy of the ca 3 5 ga barberton greenstone belt as it is presently adopted 1 2 this work uses the ion microprobe shrimp to attempt such a test results show that 1 volcaniclastic sediments of the theespruit formation