nitrogen isotopic composition of ammoniated phyllosilicates case studies from precambrian metamorphosed sedimentary rocks ammonium concentrations in phyllosilicates from archean and proterozoic schists and carbonates were evaluated by fourier transform infrared microspectrometry aftir the y 15 nair values of structural nitrogen in these phases were subsequently measured by laser mass spectrometry a rapid estimate of the concentration of nh4 in biotite by aftir allows the preselection of the samples to be analyzed for their isotopic composition micas from 1 90 2 09 ga metasediments from finland and from 1 025 1 500 ga biotite schists from the moine succession in scotland have high concentrations of structural ammonium between 176 and 1549 ppm suggestive of a biological origin for the nitrogen the heavy nitrogen isotopic signatures y 15 n 4 9x to 19 7x of structural nh4 in these micas are considered consistent with biological denitrification in operation at the time of sedimentation evidence for denitrification in the mesoproterozoic is in agreement with geological and geochemical data for abundant free oxygen in the atmosphere facilitating the stability of marine no3 sequences of early archean ca 3 8 ga garnet mica schists from the isua supracrustal belt isb in southern west greenland contain biotite rich in nh4 between 233 and 512 ppm and nitrogen isotopic signatures y 15 n 1 9x to 5 9x which possibly point to an early evolution of ammonium assimilation and or nitrogen fixation this result appears to be consistent with molecular phylogenetic studies in the bacterial and archaeal domains which suggest that nitrogen fixation and ammonium assimilation were metabolic features of the last common ancestor lca of all organisms d 2004 elsevier b v all rights reserved

a whiff of oxygen before the great oxidation event high resolution chemostratigraphy reveals an episode of enrichment of the redox sensitive transition metals molybdenum and rhenium in the late archean mount mcrae shale in western australia correlations with organic carbon indicate that these metals were derived from contemporaneous seawater rhenium osmium geochronology demonstrates that the enrichment is a primary sedimentary feature dating to 2501 8 million years ago ma molybdenum and rhenium were probably supplied to archean oceans by oxidative weathering of crustal sulfide minerals these findings point to the presence of small amounts of o 2 in the environment more than 50 million years before the start of the great oxidation event

extreme 13ccarb enrichment in ca 2 0 ga magnesite stromatolite dolomite red beds association in a global context a case for the world wide signal enhanced by a local environment abstract the palaeoproterozoic positive excursion of 13 c carb is now considered as three positive shifts of 13 c carb separated by returns to 0 which all occurred between 2 40 and 2 06 ma this isotopic event is unique in terms of both duration 300 ma and 13 c enrichment up to 18 the mechanism responsible for one of the most significant carbon isotopic shifts in earth history remains highly debatable to date 13 c of 10 to 15 cannot be balanced by organic carbon burial forg as there is no geological evidence for an enhanced corg accumulation prior to or synchronous with the excursion instead termination of these excursions is followed by formation of a vast reservoir of 13 c depleted organic material 45 at shunga and by one of the earliest known oil generation episodes at 2 0 ga none of the three positive excursions of 13 c carb is followed by a negative isotopic shift significantly below 0 as has always been observed in younger isotopic events reflecting an overturn of a major marine carbon reservoirs this may indicate that forg was constant implying that the mechanism involved in the production of corg was different onset of intensive methane cycling resulting in c change is another possibility the majority of sampled 13 c carb rich localities represents shallow water stromatolitic dolostones red beds and evaporites formed in restricted intracratonic basins and may not reflect global 13 c carb values closely spaced drill core samples n 73 of stromatolitic dolostones from the 1980 27 ma tulomozerskaya formation in the onega palaeobasin russian karelia have been analysed for 13 c carb and 18 o carb in order to demonstrate that different processes were involved in the formation of 13 c carb rich carbonates the 800 m thick magnesite stromatolite dolomite red beds succession formed in a complex combination of environments on the karelian craton peritidal shallow marine low energy protected bights barred basins evaporative ephemeral ponds coastal sabkhas and playa lakes the carbonate rocks exhibit extreme 13 c enrichment with 13 c values ranging from 5 7 to 17 2 vs v pdb mean 9 9 2 3 and 18 o from 18 6 to 26 0 vs v smow mean 22 0 1 6 the tulomozerskaya isotopic excursion is characteristic of the global 2 4 2 06 ga positive shifts of carbonate 13 c 12 c although it reveals the greatest enrichment in 13 c known from this interval an external basin s is considered to have provided an enhanced corg burial and global seawater enrichment in 13 c the global background value for the isotopic shift at tulomozero time ca 2 0 ga is roughly estimated at around 5 an explosion of stromatolite forming microbial communities in shallow water basins evaporative and partly restricted environments high bioproductivity enhanced uptake of 12 c and pene contemporaneous recycling of organic material in cyanobacterial mats with the production and consequent loss of co2 and ch4 are believed to be additional local factors which may have enhanced 13 c from 5 up to 17 such factors should be taken into account when interpreting carbon isotopic data and attempting to discriminate between the local enrichment in 13 c and globally enhanced 13 c values we propose that many previously reported 13 c values from other localities where environmental interpretations are not available or have not been taken into account may not represent the global 13 c values

flexural plate subsidence sedimentation rates and structural development of the super deep south caspian basin abstract on a 270 km long seismic line across the west central and central parts of the south caspian basin an inverse flexural plate method is used to recover original uploaded plate parameters the original plate shows remarkable consistency of parameters determined from the 12 second deep seismic line with average rigidity d 1023 6nm bending moment m 1016n dip angle 0 14 and in line compressive stress of 1012 3n m 1 by sequentially adding the sedimentary units to the average bare basement it is shown that the geometry of the basin at jurassic time had a major downward warp and high sedimentary fill to the west leaving the eastern section open to possible erosion during early and middle cretaceous time the deep western part of the basin was then filled by sediments during late tertiary quaternary time and a new depocenter created across the central and western parts of the basin this newer depocenter was then filled during pliocene quaternary time the combined flexure of the basement plate and corresponding sediment fill behaviors with time are indicative of corresponding lithologic variations across the basin and with suspected organic rich sediments the integrated description of basement sediments and depocenter behavior points to the utility of the inverse procedure for improving our understanding of basinal evolution the value of rigidity is comparable to estimated oceanic crust values in line with the suspected tethys oceanic fragment of an island arc below the sediments the shift in depositional behavior with time from west to more northerly across the line of section is tied to the orogenic rise of the caucasus mountains to the north of the section and to the continued subduction of the talysh vandam plate fragment northward today the transpressional nature of the basin and the resolution of the in line compressive stress into components perpendicular to the great caucasus 70 and also perpendicular to the west caspian deep laid fault 25 30 are both in accord with the 25 30 km of present day sedimentary cover including the variations of thicknesses of seismic stratigraphic units along the section from azerbaijan in the west to nearly the turkmenian border in the east

evaluating the mechanical compaction of quartzarenites the importance of sorting llanos foreland basin colombia abstract mechanical compaction is the main porosity reducing process in sandstones including high reservoir quality rigid grain sandstones for such sandstones the extrapolation of theoretical or experimental compaction algorithms needs calibration with rocks having well constrained burial histories evaluating the compaction of these rocks is achieved by comparing current intergranular volume igv with depositional igv which is strongly dependent on sorting however because sandstone sorting is difficult to measure accurately its impact on depositional porosity and compaction state is largely underestimated we use the quartzarenites of the oligocene carbonera formation in the subsurface of the hydrostatically pressured llanos basin to illustrate the importance of sorting when evaluating the compaction of rigid grain sandstones igv and sorting were measured in core samples using a combination of transmitted light and cathodoluminescence images resulting in improved accuracy over standard procedures the compaction state of clean quartzarenites at given depths is best described using igv versus sorting plots which are used to derive compaction curves for specified sorting values the igv versus sorting trends are displaced to lower igv values with increasing burial depth the differences in igv caused by differences in sorting exceed the differences in igv resulting from 1000 m of burial illustrating the high impact of sorting when evaluating compaction contrasting with published experimental results the compaction of the llanos basin ductile grain poor quartzarenites is independent of grain size and grain rearrangement is the main compaction mechanism during the first 1 6 km of burial based on the llanos data we have generated igv versus depth curves for clean pure quartzarenites of specific sorting which can be used to predict their maximum primary porosity up to moderate burial depths differences with other published burial curves are probably related to unaccounted variations in sorting ductile grain content and framework strengthening cements however the llanos basin quartzarenites contain virtually no cements explaining their high degree of compaction relative to other rigid grain sandstones and making them ideal to isolate the effects of compaction on the igv of quartzarenites the llanos basin data suggest that below 2 5 km of depth clean well to moderately well sorted quartzarenites continue reducing their igv by mechanical compaction below the 26 limit which should apply only to extremely well sorted rigid grain uncemented sandstones

whole rock 26 al 26 mg systematics of amoeboid olivine aggregates from the oxidized cv3 carbonaceous chondrite allende we report on mineralogy petrography and whole rock 26 al 26 mg systematics of eight amoeboid olivine aggregates aoas from the oxidized cv chondrite allende the aoas consist of forsteritic olivine opaque nodules and variable amounts of ca al rich inclusions cais of different types and show evidence for alteration to varying degrees melilite and anorthite are replaced by nepheline sodalite and grossular spinel is enriched in feo opaque nodules are replaced by fe ni sulfides ferroan olivine and ca fe rich pyroxenes forsteritic olivine is enriched in feo and often overgrown by ferroan olivine the aoas are surrounded by fine grained matrix like rims composed mainly of ferroan olivine and by a discontinuous layer of ca fe rich silicates these observations indicate that aoas experienced in situ elemental open system iron alkali halogen metasomatic alteration during which fe na cl and si were introduced whereas ca was removed from aoas and used to form the ca fe rich silicate rims around aoas the whole rock 26 al 26 mg systematics of the allende aoas plot above the isochron of the whole rock allende cais with a slope of 5 23 0 13 10 5 reported by jacobsen et al 2008 in contrast whole rock 26 al 26 mg isotope systematics of cais and aoas from the reduced cv chondrite efremovka define a single isochron with a slope of 5 25 0 01 10 5 larsen et al 2011 we infer that the excesses in 26 mg present in allende aoas are due to their late stage open system metasomatic alteration thus the 26 al 26 mg isotope systematics of allende cais and aoas are disturbed by parent body alteration processes and may not be suitable for high precision chronology of the early solar system events and processes

karelian shungite an indication of 2 0 ga old metamorphosed oil shale and generation of petroleum geology lithology and geochemistry abstract the ca 2 0 ga old 600 m thick upper zaonezhskaya formation near lake onega nw russia contains unusually high concentrations of corg up to 98 averaging around 25 the formation contains an estimated 25 1010 tonnes of organic carbon accumulated within an area of 9000 km2 organic material is represented by shungite which forms a black dense amorphous or nanocrystalline mass consisting of c with traces of n o s and h autochthonous shungite occurs as disseminated organic material 0 1 50 corg which when mixed with migrated bitumen now pyrobitumen appears as coal like seams and lenses of semilustrous and semimat layer shungite rocks oil shales 50 75 corg the migrated bitumen originally petroleum represented by the lustrous vein and layer shungite conformably fills interbedding spaces or cross cutting joints and usually contains 80 98 corg the shungite bearing rocks of the upper zaonezhskaya formation represent one of the most richest accumulations of organic material reported from the palaeoproterozoic and one of the geologically earliest stages of petroleum generation the sediments of the zaonezhskaya formation were initially deposited in brackish water in a non euxinic lagoonal environment the high c s ratio 8 1000 with a zero intercept on the c s cross plot indicates that deposition occurred in sulphur poor water intensive synchronous volcanism may have contributed to both the enhanced delivery of nutrients and elevated sedimentation rate and eventually to the high degree of preservation of organic material the integrated data suggest that the organic material has a biogenic origin most likely algal or bacterial the organic material suffered complex catagenetic and metamorphic alteration which is reflected in 1 the four modal distribution of corg content with maxima at 5 30 65 and 95 2 highly variable 13 c org 45 to 17 3 bimodal distribution of 13 c org with maxima at 28 and 39 and 4 low h c ratios 0 005 0 2 abundant diagenetic carbonates associated with shungite rocks 13 c carb 5 to 26 and the presence of pyrite 34 s 22 to 31 reflects substantial loss of organic matter via bacterial reduction of sulphate during diagenesis the shungite rocks are characterised by a further substantial loss 50 of biologically produced organic material in the course of thermal maturation and by a depletion in 12 c 10 the isotopic composition of carbonate concretions does not indicate the involvement of fermentative diagenesis conservative estimates give 13corg of 34 as the best value of the initial biomass lustrous vein and layer shungite containing more than 80 corg are considered to be allochthonous migrated bitumen originally petroleum the semilustrous and semimat layer shungite rocks containing 55 75 corg represent oil shales with both migrated bitumen originally petroleum and autochthonous kerogen residues the oil source rocks were apparently hosted in the zaonezhskaya formation the generated oil has migrated both vertically and laterally with the highest concentration in cupola structures the locality at shunga represents the most significant volume of trapped petroleum from the study area

global nature of the paleoproterozoic lomagundi carbon isotope excursion a review of occurrences in brazil india and uruguay abstract positive carbon isotope excursion is reported from paleoproterozoic carbonates of the aravalli supergroup northwestern india the minas supergroup brazil and new sections of the paso severino formation uruguay the 2 42 ga gandarela formation minas gerais brazil contains red carbonate facies bif grading into dolostones and limestones and yielding 13 c values ranging from 1 6 to 0 4 v pdb the positive c isotope excursion up to 11 v pdb in marine shallow water carbonates in india and brazil jhamarkotra formation in northwestern india and cercadinho and fecho do funil formations in minas gerais state brazil is comparable to that observed in 2 22 2 1 ga carbonate successions worldwide that were deposited during the lomagundi excursion in uruguay 13 c values up to 11 6 v pdb in the deep water paso severino formation of the piedra alta terrane are compatible with deposition at ca 2 15 ga as indicated by the 2146 7 ma u pb age of dacites occurring at the top of the unit negative 13 c values are also present in carbonates of the paso severino formation but an origin related to organic matter remineralization cannot be ruled out thin carbonate beds in the rio itapicuru greenstone belt bahia state brazil are associated as in the paso severino formation with deep water black shales and have carbon isotope values up to 9 v pdb high metamorphic grade carbonates of the jacurici terrane in the medrado ipueira area bahia brazil have carbon isotope values up to 6 9 v pdb consistent with their minimum age of 2085 5 ma inferred from the intrusive contact with and the age of the medrado norite no evidence was found in india brazil or uruguay for paleoproterozoic glacial events recognized in the 2 45 2 22 ga sedimentary successions worldwide unconformities between the gandarela and cercadinho formations in brazil and the banded gneissic complex and the lower aravalli supergroup in india might explain the absence of glacial record compositional and isotopic data presented here for studied paleoproterozoic carbonate successions allow their integration into the global record of the paleoproterozoic evolution as well as correlation with other successions of similar age the study highlights the global nature of the lomagundi excursion furthermore it indicates that the lomagundi excursion is recorded in both shallow water aravalli and minas supergroups and deep water carbonates paso severino formation and rio itapicuru greenstone belt negating a significant impact of stromatolite productivity and hypersaline conditions on carbon isotope values of carbonates deposited in shallow water open marine and isolated basins

u rich archaean sea floor sediments from greenland indications of 3700 ma oxygenic photosynthesis abstract 3700 ma metamorphosed pelagic shale from west greenland contains up to 0 4 wt reduced carbon with 13c values down to 25 6 pdb peedee belemnite the isotopic signature and mode of occurrence suggest that the carbon derived from planktonic organisms the pb isotopic composition shows that the shale had high primary u th this indicates that organic debris produced a local reducing environment which precipitated u transported to the site of sedimentation by oxidized ocean water the existence of highly productive plankton that fractionated c isotopes strongly and set up oxidation contrast in the environment suggests that oxygenic photosynthesis evolved before 3700 ma

towards a general state variable constitutive relation to describe granular deformation triaxial compression experiments were performed on cylindrical quartz sand packs to explore the universality of statevariable constitutive relations used to describe granular deformation samples were subjected to relaxation creep experiments similar to slide hold slide tests from friction studies for relaxation creep tests a constant rate of axial shortening was interrupted by time intervals for which the applied shortening rate was set to zero during holds loadforce decayed exponentially with time and the total stress relaxation scales with the logarithm of hold time consistent with friction tests on reloading after holds stress monotonically increases to the pre hold steady state levels without displaying the restrengthening of static friction often observed from shear tests on granular layers we find that the existing rate and state variable friction laws can model the transient strength behavior during relaxation creep and subsequent reloading by using simple assumptions about the deformation of cylindrical sand packs in triaxial compression by analogy with the rate and state friction constitutive relations we propose a generalized state variable expression for granular deformation in simple and pure shear although additional experiments under a variety of load boundary geometries and load paths will be needed such a general constitutive relation may ultimately describe granular deformation under a broad range of conditions e g for large variations in loading rate shear stress normal stress mean stress and may be applicable to a variety of research problems that involve deformation within granular media d 2005 elsevier b v all rights reserved

forsterite rich accretionary rims around calcium aluminum rich inclusions from the reduced cv3 chondrite efremovka it was suggested that multilayered accretionary rims composed of ferrous olivine andradite wollastonite salite hedenbergitic pyroxenes nepheline and ni rich sulfides around allende calcium aluminum rich inclusions cais are aggregates of gas solid condensates which reflect significant fluctuations in physico chemical conditions in the slowly cooling solar nebula and grain gas separation processes in order to test this model we studied the mineralogy of accretionary rims around one type a cai e104 and one type b cai e48 from the reduced cv3 chondrite efremovka which is less altered than allende in contrast to the allende accretionary rims those in efremovka consist of coarse grained 20 40 mum anhedral forsterite fa 1 8 fe ni metal nodules amoeboid olivine aggregates aoas and fine grained cais composed of al diopside anorthite and spinel forsterite although the fine grained cais aoas and host cais are virtually unaltered a hibonite spinel perovskite cai in the e48 accretionary rim experienced extensive alteration which resulted in the formation of fe rich zn bearing spinel and a ca al si hydrous mineral forsterites in the accretionary rims typically show an aggregational nature and consist of small olivine grains with numerous pores and tiny inclusions of al rich minerals no evidence for the replacement of forsterite by enstatite was found no chondrule fragments were identified in the accretionary rims

implications of earthquake focal mechanism data for the active tectonics of the south caspian basin and surrounding regions summary the south caspian basin is a relatively aseismic block within the alpine himalayan belt but is surrounded by zones of high seismicity we used the focal mechanisms of 16 earthquakes whose source parameters we determined from inversion of body waves and the mechanisms of 15 other earthquakes to determine the style of faulting in the seismic belts surrounding the south caspian basin earthquakes beneath the talesh mountains of north west iran and immediately off shore in the south west caspian sea have shallow thrust mechanisms showing that the continental crust of north west iran is overthrusting the oceanic like crust of the south caspian basin earthquakes south of the caspian sea in northern iran show a mixture of focal mechanisms both high angle reverse faulting and left lateral strike slip faulting mechanisms are observed in the high alborz mountains farther south on the edge of the central iran plateau oblique left lateral reverse mechanisms are observed it appears that the ne direction of shortening between central iran and the south caspian basin is partitioned into pure left lateral strike slip and thrusting in the wnw trending high alborz but is accommodated by oblique faulting in lower elevations earthquakes in the kopet dag mountains east of the caspian sea also show a mixture of high angle reverse and strike slip faulting mechanisms and may be another example of the partitioning of oblique slip into strike slip and thrust motion normal faulting mechanisms at centroid depths of 35 50 km dominate in the belt of seismicity that extends across the central caspian sea the significance of the normal faulting earthquakes is enigmatic it is improbable that these events represent the motion between the southern caspian basin and eurasia for they imply a sense of motion that is incompatible with the observed topography and folding in the sediments two shallow earthquakes at about 12 km depth in this belt one a small event and the other a large second subevent of a multiple earthquake have thrusting mechanisms suggesting that shortening occurs as the continental crust of the northern caspian sea is thrust over the oceanic like crust of the southern caspian basin shortening is also suggested by the orientations of folds in the sedimentary cover south of the central caspian sea seismic belt we suggest that this shortening does indeed represent a nne motion of the caspian sea relative to eurasia but that the motion is slow and has not produced many earthquakes the deeper normal faulting events may be related to bending or down dip extension of the incipient subducted slab if the motion of the caspian sea relative to eurasia is indeed slow then the motion in the alborz between central iran and the south caspian basin will be almost the same as that between iran and eurasia as has previously been assumed the combined effect of the overthrusting of the south caspian basin by the talesh alborz mountains in the south and by the continental crust of the northern caspian sea in the north will lead to the eventual destruction of the south caspian basin and the possible formation of an intermediate depth dipping seismic zone within the continental interior similar to that presently observed in the hindu kush

genesis of upper proterozoic cambrian phosphorite deposits of india isotopic inferences from carbonate fluorapatite carbonate and organic carbon carbon and oxygen isotope analyses performed on sedimentary carbonates organic carbon kerogen and structurally bound co2 3 groups of carbonate fluorapatite francolite from four widely separated indian phosphorite provinces have shown that each of the deposits is characterized by specific basically facies dependent distribution patterns of 13ccarb 13ocarb 13corg and 13capat comparison of the carbon isotope composition of apatite co2 with that of the coexisting sedimentary carbonate has served to further constrain the genetic type of the individual phosphorite deposit investigated augmenting relevant geological evidence by an additional geochemical discriminator as a whole the results confirm the importance notably of carbon isotope work for elucidating the processes involved in sedimentary phosphorite formation

oxygen isotopes of chondritic components we review the oxygen isotopic compositions of chondrite components refractory inclusions chondrules and matrix and their inter and intra crystalline oxygen isotopic distributions primary oxygen isotopic compositions acquired before planetesimal accretion are easily disturbed by parent body processes such as aqueous alternation and thermal metamorphism primary or original oxygen isotopic compositions of refractory inclusions ca al rich inclusions and amoeboid olivine aggregates distribute along a slope 1 line on the three oxygen isotope diagram over the range of 60 17 o 18 o 16 o rich and 17 o 18 o rich during refractory inclusion formation on the other hand primary minerals of most chondrules have small isotopic variations and are enriched in 17 o and 18 o relative to refractory inclusions suggesting that chondrule formation occurred in 17 o 18 o rich nebular gas however rare 16 o rich chondrules have been found suggesting some overlap in the timing of formation of chondrules and refractory inclusions in the solar nebula oxygen isotopic compositions of matrix grains distribute along the slope 1 line over the same range as refractory inclusions and chondrules the similarity in oxygen isotopic distributions suggests that matrix was originally a mechanical mixture of nebular dusts co generated with chondrules and refractory inclusions presolar grains with oxygen isotopic compositions that are clearly distinct from those of solar nebular materials are a trace component of chondrite matrices based on these oxygen isotopic characteristics more than 99 5 of the solid materials in the nebula formed locally in the solar nebula and the remainder formed in interstellar space the astrophysical setting of chondrite component formation in the early solar system is also discussed refractory inclusions and 16 o rich matrix dusts formed around the inner edge of the solar nebula on the other hand most chondrules and 17 o 18 o rich matrix dusts seem to have formed elsewhere in the solar nebula efficient large scale radial mixing of the solar nebular materials may have been an essential process in the formation of chondritic planetesimals

mineralogy and petrology of amoeboid olivine inclusions in co3 chondrites relationship to parent body aqueous alteration petrographic and mineralogic studies of amoeboid olivine inclusions aois in co3 carbonaceous chondrites reveal that they are sensitive indicators of parent body aqueous and thermal alteration as the petrologic subtype increases from 3 0 to 3 8 forsteritic olivine fa0 1 is systematically converted into ferroan olivine fa60 75 we infer that the fe si and o entered the assemblage along grain boundaries forming ferroan olivine that filled fractures and voids as temperatures increased fe 2 from the new olivine exchanged with mg 2 from the original aoi to form diffusive haloes around low feo cores cations of mn 2 ca 2 and cr 3 were also mobilized the systematic changes in aoi textures and olivine compositional distributions can be used to refine the classification of co3 chondrites into subtypes in subtype 3 0 olivine occurs as small forsterite grains fa0 1 free of ferroan olivine in petrologic subtype 3 2 narrow veins of feo rich olivine have formed at forsterite grain boundaries with increasing alteration these veins thicken to form zones of ferroan olivine at the outside aoi margin and within the aoi interior by subtype 3 7 there is a fairly broad olivine compositional distribution in the range fa63 70 and by subtype 3 8 no forsterite remains and the high fa peak has narrowed fa64 67 even at this stage there is incomplete equilibration in the chondrite as a whole e g data for coarse olivine grains in isna co3 8 chondrules and lithic clasts show a peak at fa39 we infer that the mineral changes in aoi identified in the low petrologic types required aqueous or hydrothermal fluids whereas those in subtypes 3 3 largely reflect diffusive exchange within and between mineral grains without the aid of fluids

high δ13c paleoproterozoic carbonates from the transvaal supergroup south africa marbles from the transvaal supergroup kaapvaal craton south africa record two positive carbon isotope excursions to average 13 c carbonate values of 6 to 8 relative to v pdb separated by carbonates with normal marine 13 c values 0 2 these elevated values have been preserved through metamorphic devolatilization together with an already documented high 13 c excursion in overlying rocks three separate positive carbon isotope excursions occurred on the kaapvaal craton in the interval 2 43 to 1 93 ga it is not yet clear how many of these excursions reflect global rather than local processes

26 al 26 mg and 207 pb 206 pb systematics of allende cais canonical solar initial 26 al 27 al ratio reinstated abstract the precise knowledge of the initial 26 al 27 al ratio 26 al 27 al 0 is crucial if we are to use the very first solid objects formed in our solar system calcium aluminum rich inclusions cais as the time zero age anchor and guide future work with other short lived radio chronometers in the early solar system as well as determining the inventory of heat budgets from radioactivities for early planetary differentiation new high precision multi collector inductively coupled plasma mass spectrometry mc icp ms measurements of 27 al 24 mg ratios and mg isotopic compositions of nine whole rock cais six mineralogically characterized fragments and three micro drilled inclusions from the cv carbonaceous chondrite allende yield a well defined 26 al 26 mg fossil isochron with an 26 al 27 al 0 of 5 23 0 13 10 5 internal mineral isochrons obtained for three of these cais a44a ajef and a43 are consistent with the whole rock cai isochron the mineral isochron of ajef with 26 al 27 al 0 4 96 0 25 10 5 anchored to our precisely determined absolute 207 pb 206 pb age of 4567 60 0 36 ma for the same mineral separates reinstate the canonical 26 al 27 al 0 of 5 10 5 for the early solar system the uncertainty in 26 al 27 al 0 corresponds to a maximum time span of 20 ka thousand years suggesting that the allende cai formation events were culminated within this time span although all allende cais studied experienced multistage formation history including melting and evaporation in the solar nebula and post crystallization alteration likely on the asteroidal parent body the 26 al 26 mg and u pb isotopic systematics of the mineral separates and bulk cais behaved largely as closed system since their formation our data do not support the supra canonical 26 al 27 al ratio of individual minerals or their mixtures in cv cais suggesting that the supra canonical 26 al 27 al ratio in the cv cais may have resulted from post crystallization inter mineral redistribution of mg isotopes within an individual inclusion this redistribution must be volumetrically minor in order to satisfy the mass balance of the precisely defined bulk cai and bulk mineral data obtained by mc icp ms the radiogenic 208 pb 206 pb ratio obtained as a by product from the pb pb age dating is used to estimate time integrated 232 th 238 u ratio value of cais limited variations among the minerals within a single cai contrasted by much larger variations among the bulk cais suggest th u fractionation occurred prior to crystallization of igneous cais if interpreted as primordial heterogeneity the value can be used to calculate the mean age of the interstellar dust from which the cais condensed

origin and chronology of chondritic components a review abstract mineralogical observations chemical and oxygen isotope compositions absolute 207pb 206pb ages and short lived isotope systematics 7be 7li 10be 10b 26al 26mg 36cl 36s 41ca 41k 53mn 53cr 60fe 60ni 182hf 182w of refractory inclusions ca al rich inclusions cais and amoeboid olivine aggregates aoas chondrules and matrices from primitive unmetamorphosed chondrites are reviewed in an attempt to test i the x wind model vs the shock wave model of the origin of chondritic components and ii irradiation vs stellar origin of short lived radionuclides the data reviewed are consistent with an external stellar origin for most short lived radionuclides 7be 10be and 36cl are important exceptions and a shock wave model for chondrule formation and provide a sound basis for early solar system chronology they are inconsistent with the x wind model for the origin of chondritic components and a local irradiation origin of 26al 41ca and 53mn 10be is heterogeneously distributed among cais indicating its formation by local irradiation and precluding its use for the early solar system chronology 41ca 41k and 60fe 60ni systematics are important for understanding the astrophysical setting of solar system formation and origin of short lived radionuclides but so far have limited implications for the chronology of chondritic components the chronological significance of oxygen isotope compositions of chondritic components is limited the following general picture of formation of chondritic components is inferred cais and aoas were the first solids formed in the solar nebula 4567 4568 myr ago possibly within a period of 10 and have 26al 27al 0 similar to those in chondrules 5 nebular gas the majority of chondrules within a chondrite group may have formed over a much shorter period of time

carbon isotopes and the rise of atmospheric oxygen new data for the isotopic composition of carbon in carbonate sediments deposited between 2 6 and 1 6 ga indicate that the value of 13c in these sediments underwent a very large positive excursion between 2 22 and 2 06 ga a reassessment of the earlier 13c data for carbonate sediments shows that this excursion was probably worldwide and that it was preceded and followed by several hundred million years during which the 13c of carbonate sediments differed little from that of modern carbonates the large 13c excursion between 2 22 and 2 06 ga was probably related to an abnormally high rate of organic carbon deposition which generated an abnormally high rate of o2 production we estimate that the total excess o2 produced during the excursion was between 12 and 22 times the present atmospheric o2 inventory the 13c data therefore suggest that the o2 content of the atmosphere increased very significantly between 2 22 and 2 06 ga this inference is supported strongly by several other lines of evidence

fayalite in the vigarano cv3 carbonaceous chondrite occurrences formation age and conditions abstract we have performed petrographic characterization 53mn 53cr age determination and thermodynamic stability evaluations of fayalite in vigarano meteorite that belongs to the reduced subgroup of cv3 chondrites vigarano is a breccia consisting of clasts which are separate chondrules surrounded by olivine rich fine grained materials four out of twenty three explored clasts contain fayalites that represent materials of the bali like oxidized subgroup of cv3 chondrites the fayalites fa 80 with grain sizes typically

mechanical compaction of deeply buried sandstones of the north sea abstract sandstones experience mechanical compaction when the overburden load exceeds the compressive strength petrographic evidence is rarely sufficient to determine the timing of mechanical compaction it is often assumed from indirect evidence such as regional porosity depth trends that mechanical compaction is a process that occurs exclusively during shallow or intermediate burial mechanical compaction without grain fracturing may occur at depth following pervasive framework grain dissolution and or if anomalously high porosity has been preserved due to the presence of small amounts of cement we describe examples from the fulmar sandstone formation of the central graben north sea that experienced late stage mechanical compaction following sponge spicule dissolution and microcrystalline quartz cementation deep burial mechanical compaction involving grain crushing may occur if the rate of grain contact quartz dissolution and or quartz overgrowth development cannot compete with the rate of stress increase at grain contacts some rotliegendes sandstones of the southern north sea that have been buried to 4 5 km offer a good example where the suppression of chemical compaction due to the presence of grain coating clays resulted in pervasive grain fracturing mineral veins are frequently associated with sandstones that have experienced pervasive mechanical compaction during deep burial these may reflect the sudden development of overpressure resulting from the transfer of load to the fluid during collapse of the sandstone framework

progressive alteration in cv3 chondrites more evidence for asteroidal alteration abstract the oxidized cv3 chondrites can be divided into two major subgroups or lithologies bali like cv3oxb and allende like cv3oxa in which chondrules calcium aluminum rich inclusions cais and matrices show characteristic alteration features weisberg et al 1997 krot et al 1997d kimura and ikeda 1997 the cv3oxb lithology is present in bali kaba parts of the mokoia breccia and possibly in grosnaja and allan hills alh 85006 it is characterized by the presence of the secondary low ca phyllosilicates saponite and sodium phlogopite magnetite ni rich sulfides fayalite fa 90 ca fe rich pyroxenes fs10 50wo45 50 and andradite phyllosilicates replace primary ca rich minerals in chondrules and cais which suggests mobilization of ca during aqueous alteration magnetite nodules are replaced to various degrees by fayalite ca fe rich pyroxenes and minor andradite fayalite veins crosscut fine grained rims around chondrules and extend into the matrix thermodynamic analysis of the observed reactions indicates that they could have occurred at relatively low temperatures 300 c in the presence of aqueous solutions oxygen isotopic compositions of the coexisting magnetite and fayalite plot close to the terrestrial fractionation line with large 18ofayalite magnetite fractionation 20 we infer that phyllosilicates magnetite fayalite ca fe rich pyroxenes and andradite formed at relatively low temperatures 300 c by fluid rock interaction in an asteroidal environment secondary fayalite and phyllosilicates are virtually absent in chondrules and cais in the cv3oxa lithology which is present in allende and its dark inclusions axtell alha81258 alh 84028 lewis cliff lew 86006 and parts of the mokoia and vigarano breccias instead secondary nepheline sodalite and fayalitic olivine are common fayalitic olivine in chondrules replaces low ca pyroxenes and rims and veins forsterite grains it also forms coarse lath shaped grains in matrix secondary ca fe rich pyroxenes are abundant we infer that the cv3oxa lithology experienced alteration at higher temperatures than the cv3oxb lithology the presence of the reduced and cv3oxa lithologies in the vigarano breccia and cv3oxa and cv3oxb lithologies in the mokoia breccia indicates that all cv3 chondrites came from one heterogeneously altered asteroid the metamorphosed clasts in mokoia krot and hutcheon 1997 may be rare samples of the hotter interior of the cv asteroid we conclude that the alteration features observed in the oxidized cv3 chondrites resulted from the fluid rock interaction in an asteroid during progressive metamorphism of a heterogeneous mixture of ices and anhydrous materials mineralogically similar to the reduced cv3 chondrites

sedimentation in a discharge dominated fluvial lacustrine system the neogene productive series of the south caspian basin azerbaijan abstract the largely lower pliocene productive series and its regional equivalents contain the major hydrocarbon reservoirs of the south caspian basin examination of outcrops in the apsheron region azerbaijan has resulted in re interpretation of the depositional environments of the productive series the lower part of the productive series consists of sandstones and mudstones interpreted as channelised and sheetflood fluvial deposits intercalated with mudstones that represent short lived lacustrine transgressions of a regional caspian lake the upper productive series pereriva and younger suites comprises sandstone prone intervals interpreted as deposition during periods of increased fluvial discharge and sediment supply and mudstone prone intervals interpreted as deposition during periods of decreased discharge and therefore coarse grained sediment starvation sand prone reservoir intervals in the pereriva and overlying balakhany suites mainly comprise amalgamated low sinuosity braided fluvial sheet sandstones mudstone rich intervals form inter and intra suite seals comprising alluvial plain and lacustrine facies the succession displays an overall fining up trend which is controlled by long term climatic cooling decreased fluvial discharge and reduced coarse clastic input the modern volga caspian system is a partial analogue for the lower productive series in the apsheron region where fluvial and lacustrine conditions alternate on a low gradient ramp without evidence for a shelf break lake eyre australia may be a modern analogue for the upper productive series where there are fewer lacustrine influences discernible in the sedimentology and the overall setting resembles a dryland river terminal fan

methylhopane biomarker hydrocarbons in hamersley province sediments provide evidence for neoarchean aerobiosis abstract bacteriohopanepolyols with a ring methyl substituents are bacterial lipid biomarkers that are presently known to originate from just a few specific taxa when preserved in ancient rocks the fossilized hydrocarbon skeletons of these molecules have the potential to provide biogeochemical records of those taxa and their respective physiologies considering both their occurrences in modern organisms and their proterozoic and phanerozoic sedimentary distributions hopanes carrying 2 methyl or 3 methyl substituents are proposed to be derived from cyanobacteria and oxygen respiring methanotrophs respectively here we report the distribution of methylhopanes in 2 72 2 56 billion year old neoarchean rocks from the hamersley province on the pilbara craton the relative abundance of c 31 3 methylhopane but not that of c 31 2 methylhopane shows a strong correlation to the carbon isotopic composition of co occurring kerogen insoluble particulate organic matter the unanticipated nature of this relationship provides evidence for a shallow water locus of carbon cycling through aerobic oxidation of ch 4 and coincidentally a means to demonstrate biomarker syngenicity 2 methylhopanes are most abundant in both shale and carbonate from shallow water sediments and a positive correlation to carbonate abundance contrasts to variable but generally lower 2 methylhopane abundances of deeper water facies these observations are consistent with their origin from cyanobacteria which were likely the cornerstone of microbial communities in shallow water ecosystems providing molecular oxygen fixed carbon and possibly fixed nitrogen

mineralogy and petrography of amoeboid olivine aggregates from the reduced cv3 chondrites efremovka leoville and vigarano products of nebular condensation accretion and annealing amoeboid olivine aggregates aoas from the reduced cv chondrites efremovka leoville and vigarano are irregularly shaped objects up to 5 mm in size composed of forsteritic olivine fa 50 melting we infer that aoas are aggregates of high temperature nebular condensates which formed in cai forming regions and that they were absent from chondrule forming regions at the time of chondrule formation the absence of low ca pyroxene and depletion in moderately volatile elements mn cr na k suggest that aoas were either removed from cai forming regions prior to condensation of these elements and low ca pyroxene or gas solid condensation of low ca pyroxene was kinetically inhibited

paleoceanographic constraints on precambrian phosphorite accumulation baraga group michigan usa abstract the palaeoproterozoic baraga group ca 1850 1 ma of northern michigan is a 1200 m thick sedimentary succession of marine clastic iron formation chert and phosphatic sedimentary rocks that accumulated at the peak of the world s first major phosphogenic episode lithofacies stacking patterns are interpreted to record the flooding of the nuna continental margin during two sea level cycles the base of the first sequence is marked by a transgressive lag on archean basement that is transitional into a highstand accumulation of sandstones deposited in peritidal environments the bottom of the second sequence is characterized by a chert and carbonate unit with numerous subaerial exposure surfaces deposited in intertidal to supratidal environments this chert grades upward into subtidal deposits composed of interbedded organic rich mudstone and sandstone the highstand and falling stage systems tracts are composed of progradational deltaic deposits sequences were framed using the newly discovered sudbury impact ejecta horizon as a datum its emplacement approximately coincides with unrelated environmental changes that increased the delivery of river borne sediment to the nuna margin iron bearing minerals ankerite siderite and pyrite show that ferrous iron was present in peritidal to deep marine environments ankerite dominates nearshore settings where pyrite is absent pyrite occurs in deeper progradational deltaic deposits where sulfide was produced by bacterial sulfate reduction phosphorite is restricted to shallow water sediments of the first sequence and the lowstand of the second sequence precipitation is interpreted to be the result of fe redox pumping just below the sediment water interface where photosynthetically produced nearshore oxygen oases impinged on the seafloor such shallow water phosphorite accumulation is in stark contrast to many phanerozoic depositional systems in which phosphogenesis occurs across the shelf this difference likely reflects the dissimilarity in the oxygenation state of the seafloor in the precambrian fe redox pumping and thus phosphogenesis was restricted to shallow water settings with a suboxic seafloor in the phanerozoic phosphorite forms in the full spectrum of shelf environments because the entire seafloor is generally well oxygenated the concentration of bioavailable p in neritic environments during the proterozoic may have played a major role in the development of benthic microbial ecosystems and evolving eukaryotes

high time resolution by use of the 26al chronometer in the multistage formation of a cai the allende calcium rich inclusion cai 5241 has been found to contain distinct initial 26 al 27 al in the three consecutive igneous zones that have been identified by extensive petrogenetic studies to have formed in three distinct crystallization events the zones in order of sequence of formation from the petrologic observations are 1 spinel free islands sfi included in 2 a pyroxene spinel rich core src which in turn is included in 3 a melilite mantle mm the initial 26 al 27 al values of these zones are respectively 4 6 5 0 10 5 4 3 10 5 and 3 3 10 5 it is argued that these distinct 26 al 27 al 0 values are not the result of metamorphism but reflect the relative times of formation by crystallization from melts relative to the canonical value of 26 al 27 al 0 5 10 5 we find the following chronology t sfi 0 t src 10 5 yr and t mm 4 10 5 yr the three layer cai is inferred to have sampled a reservoir with an initial uniform 26 al 27 al ratio that decreased in value due to radioactive decay from these observations we conclude that we have resolved time differences of a few hundred thousand years at the very early stages of formation of the solar system the sfi src and mm zones reflect sequential addition of molten cai material which crystallized rapidly without seriously metamorphosing the previously formed material these additions took place over a time of about 400 000 years we believe that these sequential events are not compatible with condensation in a hot region of the solar nebula it is proposed that a scenario involving stages of protoplanetary accretion and of melt generation in protoplanetary sites heated by 26 al might provide a possible source for cais and chondrules

compaction of lithic sands experimental results and applications compaction experiments showed that the degree of physical compaction of a lithic sand is related to the amount and type of lithic material present these experiments produced a product that is texturally indistinguishable from natural lithic sandstones generally sedimentary lithic fragments are more ductile than metamorphic lithic fragments volcanic lithic fragments when altered to phyllosilicate minerals by weathering or diagenesis are extremely ductile mineralogy and intragranular microporosity influence ductility ratios based on weight percent of soft ductile minerals clay and micas to hard brittle minerals quartz and feldspar within the lithic fragments provides a good indication of ductility a ratio greater than 1 indicates the lithic material will be h ghly ductile microporous lithic fragments are more ductile than dense lithic fragments physical compaction models were developed based on experimental data from well sorted lithic sandstones for which the percentage of preserved porosities were functions of the effective stress the type of lithic material and the quantity of lithic material these models are derived from laboratory sandstones with at least 25 lithic grains in the following categories moderately ductile metamorphic lithic fragments highly ductile shale lithic fragments and extremely ductile altered volcanic lithic fragments application of the compaction models of the experimental compaction techniques to modern subsurface sand samples or outcrop equivalents can provide valuable estimates of the preserved porosities i e reservoir potential for lithic sandstones that may be exploratory objecti es in frontier basins examples using the models and experimental compaction techniques for exploration are given experimental data showed that precompaction cement and overpressure may be beneficial to porosity preservation an early formed partial cement can retard compaction and preserve porosity by stabilizing the sand pack a later cement does not have this beneficial effect overpressure when developed early retards compaction by reducing the effective stress of course a late developing overpressure is not effective at preserving porosity because compaction is an irreversible process

present status of the geochronology of the precambrian rocks of rajasthan abstract age determinations mostly by rb sr analyses of the precambrian rocks of rajasthan by us and by others are summarized and discussed broad periods of acid magmatism at 1 3000 2900 m y 2 2600 2500 m y 3 2000 1900 m y 4 1700 1500 m y and 5 850 750 m y were identified the oldest rocks in the area are the yet undated banded gneisses bgc east of udaipur intruded by the untala granite dated at 2950 m y and hence of mid archean age the basal status hitherto attributed to the berach granite dated at 2600 m y is no longer tenable the radiometric control on the beginning and duration of the overlying aravalli supergroup is not yet satisfactory though a lower limit at 2000 m y is indicated heron s original delhi rocks have recorded two magmatic events widely separate in space and time while the earliest granitic activity at 1600 m y is recorded only in the alwar basin in the northeast the younger activity between 850 750 m y is widespread as shown by the nearly concordant ages of erinpura type granites along the aravalli mountain range and the malani rhyolites in the western plains of the aravalli range

late archean molecular fossils from the transvaal supergroup record the antiquity of microbial diversity and aerobiosis abstract cores recovered during the agouron griqualand drilling project contain over 2500 m of well preserved late archean transvaal supergroup sediments dating from ca 2 67 to 2 46 ga bitumen extracts of these strata were obtained using clean drilling sampling and analysis protocols that avoided overprinting syngenetic molecular fossil signatures with contaminant hydrocarbons comparisons of biomarker contents in stratigraphically correlated intervals from diverse lithofacies in two boreholes separated by 24 km as well as across a 2 gyr unconformity provide compelling support for their syngenetic nature the suite of molecular fossils identified in the late archean bitumens includes hopanes attributable to bacteria potentially including cyanobacteria and methanotrophs and steranes of eukaryotic origin this molecular fossil record supports an origin in the archean eon of the three domains of cellular life as well as of oxygenic photosynthesis and the anabolic use of o2

biotic turnover driven by eutrophication before the sturtian low latitude glaciation a dramatic oceanic biotic shift from eukaryotic phytoplankton to bacteria occurred about 740 million years ago microfossil and geochemical data from the chuar group in the southwestern united states link this biotic turnover to widespread eutrophication of surface waters reconstructions of the diversity of precambrian microorganisms suggest a pronounced biotic turnover coinciding with the onset of neoproterozoic low latitude glaciation in which diverse assemblages of organic walled microfossils known as acritarchs were replaced by assemblages of simple smooth walled forms called leiosphaerids and the remnants of bacterial blooms1 2 3 4 this turnover has been interpreted as the mass extinction of eukaryotic phytoplankton1 2 3 4 and the subsequent proliferation of bacteria5 however the causes of this mass extinction and its exact temporal relationship to the glaciations remain unclear1 2 3 4 here we present palaeontological data from the 742 6 myr old chuar group from arizona which indicate that the biotic turnover occurred before the first low latitude sturtian glaciation constrained to be between 726 and 660 myr in age6 in our record the turnover is associated with the appearance of abundant and diverse protozoan fossils and a shift to rising total organic carbon suggestive of increased primary productivity spurred by the influx of nutrients this is followed by an increase in the ratio of highly reactive iron to total iron which we interpret as persistent water column anoxia we therefore conclude that the biotic turnover recorded in the chuar group was driven by widespread eutrophication of surface waters rather than low latitude glaciation

increased subaerial volcanism and the rise of atmospheric oxygen 2 5 billion years ago the hypothesis that the establishment of a permanently oxygenated atmosphere at the archaean proterozoic transition approximately 2 5 billion years ago occurred when oxygen producing cyanobacteria evolved is contradicted by biomarker evidence for their presence in rocks 200 million years older to sustain vanishingly low oxygen levels despite near modern rates of oxygen production from approximately 2 7 2 5 billion years ago thus requires that oxygen sinks must have been much larger than they are now here we propose that the rise of atmospheric oxygen occurred because the predominant sink for oxygen in the archaean era enhanced submarine volcanism was abruptly and permanently diminished during the archaean proterozoic transition observations are consistent with the corollary that subaerial volcanism only became widespread after a major tectonic episode of continental stabilization at the beginning of the proterozoic submarine volcanoes are more reducing than subaerial volcanoes so a shift from predominantly submarine to a mix of subaerial and submarine volcanism more similar to that observed today would have reduced the overall sink for oxygen and led to the rise of atmospheric oxygen

magnetization of extraterrestrial allende material may relate to terrestrial descend abstract the origin of magnetization in allende may have significant implications for our understanding of core formation differentiation dynamo processes in chondrite parent bodies the magnetic allende data may contain information that could constrain the magnetic history of allende the measurements on allende chondrules reveal an existence of magnetization component that was likely acquired during the meteorite transit to terrestrial conditions both the pyrrhotite carrying magnetic remanence intensity and direction of the chondrules change erratically when subjecting the allende meteorite s chondrules to temperatures near 77 k and back to room temperature chondrules with more intense original magnetization are denser and contain larger inverse thermoremanent magnetization itrm temperature dependent monitoring of itrm revealed that magnetization was acquired at temperature near 270 k such temperature is consistent with the condition when in addition to temperature increase the atmospheric uniaxial pressure applied during the meteorite entry on the porous material was responsible for meteorite break up in the atmosphere during this process collapse of the pore space in the matrix and some chondrules would generate crystalline anisotropy energy accumulation within pyrrhotite grains in form of parasitic magnetic transition

evidence of anoxic to oxic atmospheric change during 2 45 2 22 ga from lower and upper sub huronian paleosols canada paleoweathered zones in four underground drill holes in quirke ii mine and one drill hole by denison mines in elliot lake area ontario canada were studied for petrography mineralogy and whole rock chemistry these paleosols formed beneath 2 45 ga old lower huronian formations are characterized by upward depletion of fetotal and fe3 in the whole rock by upward depletion of fetotal fe mg ratios in chlorites and fine grained muscovite and by the presence of fe2 minerals e g pyrite pyrrhotite ilmenite in contrast the paleosols underlying upper huronian strata 2 22 ga old exhibit an upward increase in fe3 and fetotal and contain hematite and goethite uraninite and pyrite bearing paleoplacers occur in lower huronian strata whereas the upper huronian formations contain red beds and are devoid of detrital uraninite and pyrite these differences between the sub huronian paleoweathering profiles and mineralogical characteristics of the lower huronian strata overlying the paleosols support the previously postulated oxyatmoversion theory and restricts the time interval for its occurrence to between 2 45 and 2 22 ga assuming that few tens of millions of years were required for the deposition of lower huronian groups oxyatmoversion likely occurred at about 2 4 ga

modelling approaches to understanding fold development implications for hydrocarbon reservoirs a mechanics based approach to the evolution of buckle folds is proposed existing analytic and simple numerical models are used to demonstrate that dramatic changes in layer parallel stress occur in developing folds and that the bulk effective rheology of folding rocks is strongly reduced in relation to neighbouring rocks with no folds a methodology for estimating regions of folds more or less likely to suffer fracture is set out in this methodology a simple abstraction of the natural fold is identified and the stress history during its development is calculated using linear viscosity as a proxy for competence this simple and computationally cheap approach allows all salient features of natural multilayer folds to be recreated in numerical experiments the final step in the method is to use the stress conditions for three types of fracture failure tensile failure dilatant shear failure and grain crushing to define potential functions that indicate increased or decreased probability of failure results give predictions that agree well with observation in the simple cases studied a novel method for approximating three dimensional deformations is used to model the propagation of folds in the axial direction and it is found that this occurs rapidly and allows constructive and destructive interference of propagating folds below a certain amplitude this provides a means by which perturbations may interact over a certain distance such a mechanism was an implicit requisite of classic fold theories but its identity has been obscure for three decades it is shown that many small perturbations are needed to give patches of coherent folds and that few large perturbations give single arc folds

geochemical evaluation of hydrocarbons and their potential sources in the western south caspian depression republic of azerbaijan abstract the western south caspian depression located in offshore azerbaijan contains significant accumulations of oil and gas in upper tertiary fluvial deltaic sediments the active tertiary hydrocarbon system is a product of unique paleogeographic and tectonic events that led to paleogene deposition of organic rich source rocks rapid pliocene subsidence concurrent with voluminous supply of clastic sediments and development of anticlinal traps with abundant shale diapirs molecular characterization of selected oil samples indicates most of the oils are sourced from similar organic facies the molecular characteristics are consistent with oils sourced from a tertiary slightly calcareous marine clastic facies examination of oil molecular characteristics oil oil correlations molecular characteristics of selected source rock samples maturation models and potential migration pathways suggests the oil is not syngenetic but most likely sourced from deeper miocene and older marine shales most of the oils have low to moderate organic maturities vre 0 75 0 85 relative to conventional peak generation windows significant variations in oil gravity and whole oil gas chromatogram character suggest post emplacement bacterial and fractionation alteration several oils display characteristics consistent with multiple phases of trap charging the bulk of reservoired gases examined in this study have been sourced from mixed terrestrial marine kerogen generated at organic maturities of vre 0 80 1 00 with some biogenic low maturity mixing none of the gases examined were sourced from the thermal destruction of liquid hydrocarbons we postulate multi stage hydrocarbon emplacement into evolving structural traps the first phase of emplacement occurred in the middle pliocene when tectonic movement and increased subsidence initiated early trap reservoir formation hydrocarbon generation and migration late rapid subsidence from quaternary tectonic activity produced additional hydrocarbons to replenish older depleted traps and charge newly formed traps this late tectonic activity also extensively redistributed hydrocarbon accumulations degassed some that were breached by faults and destroyed other oil pools thermal disequilibrium from the rapid subsidence delayed hydrocarbon generation and increased the minimum depth required for the onset of liquid hydrocarbon generation

the phosphorus cycle phosphogenesis and marine phosphate rich deposits abstract phosphorus in the form of phosphate is an essential nutrient and energy carrier on many different levels of life and a key element in mediating between living and lifeless parts of the biosphere one of the most important aspects of the phosphorus cycle is its vital role in governing productivity thereby interacting with the exogenic part of the carbon cycle which in turn is important in regulating earth s climate phosphorus is a prime element to be traced in earth s history because it allows for the reconstruction of long term feedback mechanisms between climate environment and ecology and of global change as such marine sedimentary phosphate deposits are particularly suited to study aspects of the phosphorus cycle because in the case of ubiquity their origin may result from a general acceleration of the global phosphorus cycle sources of sedimentary phosphate are microbial breakdown of buried organic matter and redox driven phosphate desorption from iron and manganese oxyhydroxides dissolved sea water phosphate represents an additional source which may become important in the formation of phosphatic hardgrounds the main locus of phosphogenesis is near the sediment water interface but phosphogenesis also occurs at greater sediment depths current induced winnowing and transport processes along the sea floor concentrate phosphate precipitates into deposits which exhibit internal stratification patterns typical for the prevailing hydraulic energy regime in a sequence stratigraphic context phosphate deposits preferentially occur along marine or maximum flooding surfaces consequent sedimentary reworking may result in the transfer of phosphates to highstand or lowstand deposits bio chemical weathering on continents represents the most significant source of bioavailable phosphorus this implies that long term changes in marine phosphorus levels and with these changes in marine ecology productivity rates and ratios of exported carbonate carbon and organic carbon are a response to changes in continental weathering rates a compilation of marine sedimentary phosphorus burial rates for the last 160 myr suggests that natural variations have occurred that span one order of magnitude for the late jurassic cretaceous and most of the paleogene the phosphorus cycle appears to have been accelerated in times of climate warming which was most likely due to the spreading of zones of humid climate and more intense continental weathering in the neogene the phosphorus cycle appears to have responded to changes in glacially induced weathering this suggests that uniform interpretations with respect to the emplacement of major phosphorite deposits should be treated with caution integrated analyses of the sedimentary and biogeochemical context of phosphorite occurrences may help to identify paleoenvironmental conditions as well as to improve our understanding of periods of enhanced phosphate accumulation periods which were usually characterized by steep gradients in the development of climate and environment with regard to the complexity of feedback mechanisms between the phosphorus cycle and the biosphere the present day input rates of phosphate into the world s oceans should be of great concern they are more than doubled by anthropogenic means and affect ecological systems on a rapidly increasing scale

evolution of lower proterozoic epicontinental deposits stromatolite bearing aravalli rocks of udaipur rajasthan india abstract the aravalli rocks 2060 ma old which crop out around udaipur western india comprise a thick sequence of metasediments with stromatolites and basal volcanics resting unconformably over a peneplained basement known as the banded gneissic complex ca 2585 ma old the rocks have undergone a very low grade of metamorphism and display a complex structure resulting from two major and several minor episodes of folding there are two distinctly different facies sequences in the aravalli rocks indicating deep sea and nearshore shelf environments the stratigraphic sequence of the rocks deposited under the shelf environment starts with basic volcanics and tuffs altered to greenschists and quartizites with arkosic conglomerate in the next sequence carbonates predominate in association with orthoquartzites carbonaceous phyllites phyllites and stromatolitic rock phosphate the carbonate sequence passes upward into greywacke phyllite lithic arenite in the distal parts and conglomerate arkose orthoquartzite in proximal areas the youngest sequence comprises orthoquartzite with silty arenite the distribution of different facies particularly that of dolomite with stromatolitic rock phosphate is controlled by sea floor topography suggesting the presence of an epicontinental sea bounded by a landmass to the west and a series of islands and shoals sedimentation in the shelf and epicontinental sea was presumably triggered by development of fault controlled troughs along craton margins terrigenous debris was deposited in newly developed troughs with contemporaneous volcanicity along trough margins with the erasing of the ephemeral relief in the provenance carbonate deposition was initiated the environment encouraged algal growth and formation of stromatolitic rock phosphate carbonaceous phyllites developed in areas of restricted circulation rapid influx of terrigenous detritus with renewed tectonism in the next phase resulted in the deposition of a turbidite sequence of greywacke phyllite and lithic arenite in the deeper parts of the epicontinental sea and conglomerate arkose orthoquartizite in the marginal areas the final phase of sedimentation was presumably under fluvial conditions which marked the completion of epicontinental trough filling the nature of the terrigenous clasts indicates a predominantly granitic source of sediments supply of sediment was mainly from the continent to the east and partly from a landmass to the west the cycle of sedimentation noted in the epicontinental aravalli sea is broadly similar to the model of tectonic stages suggested by krynine 1942

implications of outcrop geology for reservoirs in the neogene productive series apsheron peninsula azerbaijan the neogene sediments of eastern azerbaijan and western turkmenistan contain significant hydrocarbon reserves in deltaic reservoirs sedimentary logging of these reservoirs at outcrop in azerbaijan has outlined four facies associations that encompass a range of paleoenvironments from alluvial braided river sandstones and conglomerates to delta front siltstones and mudstones the facies associations suggest a river dominated braid delta and are arranged into an architecture controlled by base level changes parasequences parasequence sets and sequence boundaries are key elements the facies associations and stratigraphic architecture together with outcrop observations of cementation and faulting are summarized in terms of four idealized reservoir models fluvial delta plain proximal delta front and distal delta front each reservoir model has distinctive grain size and shale distributions comparison of nearby oil fields with the studied outcrops suggests that the outcrops form good analogs from which to model reservoir architecture barriers and baffles to fluid flow reservoir heterogeneity and reservoir quality variations

oxygenation of the earth s atmosphere ocean system a review of physical and chemical sedimentologic responses abstract the great oxidation event goe is one of the most significant changes in seawater and atmospheric chemistry in earth history this rise in oxygen occurred between ca 2 4 and 2 3 ga and set the stage for oxidative chemical weathering wholesale changes in ocean chemistry and the evolution of multicelluar life most of what is known about this important event and the subsequent oxygenation history of the precambrian earth is based on either geochemistry or data mining published literature to understand the temporal abundance of bioelemental sediments bioelemental sediments include iron formation chert and phosphorite which are precipitates of the nutrient elements fe si and p respectively because biological processes leading to their accumulation often produce organic rich sediment black shale can also be included in the bioelemental spectrum thus chemistry of bioelemental sediments potentially holds clues to the oxygenation of the earth because they are not simply recorders of geologic processes but intimately involved in earth system evolution chemical proxies such as redox sensitive trace elements cu cr v cd mo u y zn and ree s and the ratio of stable isotopes 56fe 53cr 97 95mo 98 95mo 34s 33s in bioelemental sediments are now routinely used to infer the oxygenation history of paleo seawater the most robust of these is the mass independent fractionation of sulfur isotopes mif which is thought to have persisted under essentially anoxic conditions until the onset of the goe at ca 2 4 ga since most of these proxies are derived from authigenic minerals reflecting pore water composition extrapolating the chemistry of seawater from synsedimentary precipitates must be done cautiously paleoenvironmental context is critical to understanding whether geochemical trends during earth s oxygenation represent truly global or merely local environmental conditions to make this determination it is important to appreciate chemical data are primarily from authigenic minerals that are diagenetically altered and often metamorphosed because relatively few studies consider alteration in detail our ability to measure geochemical anomalies through the goe now surpasses our capacity to adequately understand them in this review we highlight the need for careful consideration of the role sedimentology stratigraphy alteration and basin geology play in controlling the geochemistry of bioelemental sediments such an approach will fine tune what is known about the goe because it permits the systematic evaluation of basin type and oceanography on geochemistry this technique also provides information on how basin hydrology and post depositional fluid movement alters bioelemental sediments thus a primary aim of any investigation focused on prominent intervals of earth history should be the integration of geochemistry with sedimentology and basin evolution to provide a more robust explanation of geochemical proxies and ocean atmosphere evolution

13c enrichment in the palaeoproterozoic carbonate rocks of the aravalli supergroup northwest india influence of depositional environment abstract the dolomitic carbonates from the jhamarkotra formation of the palaeoproterozoic aravalli supergroup are characterized by widely variable carbon isotope ratios 13 c ranging from near zero to as high as 12 v pdb the estimated maximum age ca 2150 ma of the aravalli carbonates help bracketing these with the coeval carbonate bodies of the world that show high positive carbon isotope values the intriguing existence of normal marine 13 c values in some pockets suggest influence of local scale depositional conditions prevailing in different sub basins amongst these two sub basins which showed high 13 c values a hypersaline evaporative condition is considered responsible for the necessary enrichment in one while methanogenesis possibly in conjunction with sulphate reduction processes might have caused such enrichment in the other from the empirical association of the sub basins with profuse stromatolitic phosphorite we infer that the depositional setting that favoured cyanobacterial growth leading to formation of stromatolites prevented growth of methanogenetic archaea in such anoxic environments our study therefore highlights the fact that the early palaeoproterozoic 13 c excursion in the aravalli supergroup is not essentially a time specific event but is greatly dependent on the variation in the depositional palaeoenvironment prevailing in different sub basins

isotopic evidence for massive oxidation of organic matter following the great oxidation event the stable isotope record of marine carbon indicates that the proterozoic eon began and ended with extreme fluctuations in the carbon cycle in both the paleoproterozoic 2500 to 1600 million years ago ma and neoproterozoic 1000 to 542 ma extended intervals of anomalously high carbon isotope ratios 13c indicate high rates of organic matter burial and release of oxygen to the atmosphere in the neoproterozoic the high 13c interval was punctuated by abrupt swings to low 13c indicating massive oxidation of organic matter we report a paleoproterozoic negative 13c excursion that is similar in magnitude and apparent duration to the neoproterozoic anomaly this shunga francevillian anomaly may reflect intense oxidative weathering of rocks as the result of the initial establishment of an oxygen rich atmosphere

chemostratigraphy of the paleoproterozoic duitschland formation south africa implications for coupled climate change and carbon cycling the paleoproterozoic duitschland formation lies stratigraphically beneath the timeball hill formation which contains the only unequivocal glacial unit of this era in the transvaal basin south africa lithologic evidence in paleoproterozoic successions of north america however indicates the existence of three discrete and potentially global ice ages within this 300 my interval carbonates of the duitschland formation are significantly enriched in 13c up to 10 1 permil in the upper part of the succession above a notable sequence boundary in contrast the lower part of this unit contains carbonates with consistently negative 13c values trace and major element compositions of these carbonates as well as carbon isotopic compositions of coexisting organic matter support a primary origin for the markedly positive carbon isotope anomaly the stratigraphic constraints indicate that 13c enriched carbonates were deposited prior to paleoproterozoic glaciation in southern africa similar to carbonates stratigraphically beneath neoproterozoic glacial diamictites worldwide also mirroring the neoproterozoic record are strongly negative 13c values in cap carbonates atop glacial diamictites in paleoproterozoic strata of wyoming and ontario the litho and chemostratigraphic constraints indicate that the interval of negative carbon isotope values in well preserved carbonates of the lower duitschland formation may reflect a second paleoproterozoic ice age in the transvaal succession this interpretation is further supported by recently discovered bullet shaped clasts with striations in diamictite from the basal part of the succession thus the emerging temporal pattern of carbon isotope variations and glaciation in the paleoproterozoic has a close analogue to neoproterozoic events suggesting a coupling of climatic and biogeochemical changes at both ends of the eon

structural controls on mechanical compaction within sandstones an example from the apsheron peninsula azerbaijan abstract mechanical compaction of sand rich reservoirs usually occurs during shallow burial and involves the rearrangement of framework grains and the ductile deformation of soft lithoclasts the reservoir quality porosity and permeability of some neogene sandstones of the south caspian basin has however been dramatically reduced by mechanical compaction involving extensive grain fracturing i e porosity collapse these sandstones were probably susceptible to pervasive grain fracturing because they were buried rapidly and experienced compressional deformation prior to reaching 80 c consequently they did not undergo quartz cementation and were therefore exposed to high stresses while they were extremely weak grain size and structural position are also important controls on the distribution of grain fracturing in the onshore analogue in the apsheron peninsula microstructural analysis confirms that susceptibility to distributed grain fracturing increases with increasing grain size structural position has also an important impact on the distribution of porosity collapse in particular sandstones within the hinges of folded sections have undergone much more extensive grain fracturing than within the surrounding area the increased stresses in this structural position have enhanced distributed grain fracturing and subsequent deformation band development

the formation of rims on calcium aluminum rich inclusions step i flash heating abstract wark lovering rims of six calcium aluminum rich inclusions cais representing the main cai types and groups in allende efremovka and vigarano were microsurgically separated and analysed by neutron activation analysis naa all the rims have similar 4x enrichments relative to the interiors of highly refractory lithophile and siderophile elements the naa results are confirmed by ion microprobe and scanning electron microscope sem analyses of rim perovskites and rim metal grains less refractory eu yb v sr ca and ni are less enriched in the rims the refractory element patterns in the rims parallel the patterns in the outer parts of the cais in particular the rims on type b1 cais have the igneously fractionated rare earth element ree pattern of the melilite mantle below the rim and not the ree pattern of the bulk cai proving that the refractory elements in the rims were derived from the outer mantle and were not condensates onto the cais the refractory elements were enriched in an al2o3 rich residue 50 m thick after the most volatile 80 of the outermost 200 m of each cai had been volatilized including much mg si and ca some volatilization occurred below the rim and created refractory partial melts that crystallized hibonite and gehlenitic melilite the required flash heating probably exceeded 2000 c but for only a few seconds in order to melt only the outer cai and to unselectively volatilize slow diffusing o isotopes which show no mass fractionation in the rim the volatilization did however produce heavy mass fractionated mg in rims in some cais this was later obscured when normal mg diffused in from accreted olivine grains at relatively high temperature not the lower temperature meteorite metamorphism and created the 50 m set of monomineralic rim layers of pyroxene melilite and spinel

determination of the petrologic type of cv3 chondrites by raman spectroscopy of included organic matter abstract this paper reports the first reliable quantitative determination of the thermal metamorphism grade of a series of nine cv3 chondrites allende axtell bali mokoia grosnaja efremovka vigarano leoville and kaba the maturity of the organic matter in matrix determined by raman spectroscopy has been used as a powerful metamorphic tracer independent of the mineralogical context and extent of aqueous alteration this tracer has been used along with other metamorphic tracers such as fe zoning in type i chondrules of olivine phenocrysts presolar grain abundance and noble gas abundance bulk and p3 component the study shows that the petrologic types determined earlier by induced thermoluminescence were underestimated and suggests the following values pt allende axtell 3 6 pt bali mokoia grosnaja 3 6 pt efremovka leoville vigarano 3 1 3 4 pt kaba 3 1 the most commonly studied cv3 allende is also the most metamorphosed bali is a breccia containing clasts of different petrologic types the attribution suggested by this study is that of clasts of the highest petrologic types as pointed out by iom maturity and noble gas bulk abundance cv3 chondrites have complex asteroidal backgrounds with various degrees of aqueous alteration and or thermal metamorphism leading to complex mineralogical and petrologic patterns fe mg chemical zoning in olivine phenocrysts on the borders of type i chondrules of porphyritic olivine and pyroxene rich textural types has been found to correlate with the metamorphism grade this suggests that chemical zoning in some chondrules often interpreted as exchanges between chondrules and nebular gas may well have an asteroidal origin furthermore the compositional range of olivine matrix is controlled both by thermal metamorphism and aqueous alteration this does not support evidence of a nebular origin and does not necessarily mirror the metamorphism grade through fe mg equilibration on the other hand it may provide clues on the degree of aqueous alteration vs thermal metamorphism and on the timing of both processes in particular mokoia experienced significant aqueous alteration after the metamorphism peak whereas grosnaja which has similar metamorphism grade did not

phosphorus phosphorites and skeletal evolution at the precambrian cambrian boundary clustering of sedimentary phosphate deposits around the precambrian cambrian boundary is related to a global phosphogenic event this event probably resulted from a complex interplay of factors and had a profound effect on the biota with high concentrations of phosphorus in the photic zone producing an increase in the total shallow marine biomass faunal diversification the precipitation of skeletal structures and explosive evolution

alteration of al rich inclusions inside amoeboid olivine aggregates in the allende meteorite lightly altered al rich inclusions in amoeboid olivine aggregates have cores containing primary melilite fassaite spinel perovskite and no secondary alteration products in moderately altered inclusions whose cores now contain only fassaite spinel perovskite melilite was replaced by a fine grained mixture of grossular anorthite feldspathoids and perovskite was partially replaced by ilmenite in heavily altered inclusions fassaite has been replaced by a mixture of phyllosilicates ilmenite and the remaining primary phases are spinel perovskite in very heavily altered inclusions no primary phases remain the spinel having reacted to form either phyllosilicates or a mixture of olivine feldspathoids this sequence of alteration reactions may reflect successively lower solar nebular equilibration temperatures during alteration sio2 na2o k2o feo cr2o3 h2o and cl were introduced into the inclusions and cao was lost mgo may have been lost during the melilite reaction and added during formation of phyllosilicates electron microprobe analyses indicate that the phyllosilicates are a mixture of na rich phlogopite and chlorite or alrich serpentine thermodynamic calculations suggest that at a solar nebular water fugacity of 10 6 na rich phlogopite could have formed from fassaite at 470 k and chlorite from na rich phlogopite at 328 k olivine mantling al rich inclusions is not serpentinized suggesting that these objects stopped equilibrating with the nebular gas above 274 k

postaccumulation sandstone porosity evolution by mechanical compaction and the effect on gas saturation case study of the lower shihezi formation in the bayan aobao area ordos basin china abstract porosity evolution and reservoir quality are strongly affected by mechanical compaction however the compaction induced porosity reduction process in sandstone reservoirs during the postaccumulation period and its effect on gas saturation remain poorly understood by studying the sandstones in the bayan aobao area we were able to quantify the porosity evolution and gas saturation variations caused by mechanical compaction during the postaccumulation period through fluid inclusion analysis and mathematical modeling moreover we verified our findings by compaction experiments and geological statistics fluid inclusion microthermometry was employed to determine the hydrocarbon accumulation periods and the highest homogenization temperature of the two phase aqueous fluid inclusions coexisting with natural gas fluid inclusions i e 115 c with a corresponding geological age of 140 ma was regarded as the beginning of the postaccumulation stages with these data we constructed an inversion evolution model based on the geologic statistical model of sandstone mechanical compaction for the postaccumulation period and determined the gas saturation changes based on compaction porosity evolution the modeling results indicate that the sandstone porosity decreased greatly during postaccumulation subsidence and increased slightly during late stage uplift while the gas saturation increased with both the porosity decrease during the postaccumulation subsidence and the porosity increases during the later uplift the modeling results of subsidence are concordant with the compaction experiments which also show that the larger the initial porosity the greater the porosity reduction the uplift modeling results demonstrate that an erosion induced decrease in burial depth allowed the sandstone porosity to increase which is supported by some scholars findings e g neuzil and pollock 1983 jiang et al 2004 zhang 2013 and by the positive correlation between sandstone porosities and restored geologic unit thicknesses in the study area however the inversion modeling indicates that the reason for the porosity rebound in litharenites is that the increase in elastic porosity slightly exceeds the decrease in viscoplastic porosity which would have been different if the uplift induced erosion rate had been distinctly lower gas production test data and restored geologic unit thicknesses indicate that uplift and erosion may be able to enrich sandstone gas reservoirs to a certain extent consistent with the calculated gas saturation variation results but a full understanding of gas saturation evolution awaits further studies the inversion model can provide a powerful tool for quantitative analysis of the sandstone compaction process during the postaccumulation period which could be used for reference in other similar regions

precambrian superplumes and supercontinents a record in black shales carbon isotopes and paleoclimates prominent maxima in black shale abundance and in black shale total shale ratio occur at 2 0 1 7 ga with less prominent peaks in the late neoproterozoic 800 600 ma and in the late archean 2 7 2 5 ga peaks in chemical index of alteration cia of shales at the same times suggest corresponding warm paleoclimates the peaks in cia and black shale abundance are correlated in time at a 94 confidence level the black shale and cia peaks may reflect the combined effects of mantle superplume events and supercontinent formation at 2 7 and 1 9 ga mantle superplume events may have introduced large amounts of co2 into the atmosphere ocean system increasing depositional rates of carbon and increasing global warming increased black shale deposition may reflect some combination of 1 increased oceanic hydrothermal fluxes introducing nutrients 2 anoxia on continental shelves and 3 disrupted ocean currents the apparent absence of carbon isotope anomalies at these times reflects an increase in the deposition and burial rate of both reduced and oxidized carbon peaks in black shale abundance at 2 1 ga and 800 600 ma correlate with peaks in 13 c in marine carbonates increases in atmospheric oxygen and with high cia values in shales these are all consistent with higher rates of organic carbon burial in black shales at these times these peaks may record the breakup of supercontinents at 2 2 2 0 ga and again at 800 600 ma which resulted in increased numbers of partially closed marine basins disruption of ocean currents and increased hydrothermal vents at ocean ridges all of which led to widespread anoxia 2001 elsevier science b v all rights reserved

sedimentary manganese metallogenesis in response to the evolution of the earth system abstract the concentration of manganese in solution and its precipitation in inorganic systems are primarily redox controlled guided by several earth processes most of which were tectonically induced the early archean atmosphere hydrosphere system was extremely o2 deficient thus the very high mantle heat flux producing superplumes severe outgassing and high temperature hydrothermal activity introduced substantial mn2 in anoxic oceans but prevented its precipitation during the late archean centered at ca 2 75 ga the introduction of photosystem ii and decrease of the oxygen sinks led to a limited buildup of surface o2 content locally initiating modest deposition of manganese in shallow basin margin oxygenated niches e g deposits in india and brazil rapid burial of organic matter decline of reduced gases from a progressively oxygenated mantle and a net increase in photosynthetic oxygen marked the archean proterozoic transition concurrently a massive drawdown of atmospheric co2 owing to increased weathering rates on the tectonically expanded freeboard of the assembled supercontinents caused paleoproterozoic glaciations 2 45 2 22 ga the spectacular sedimentary manganese deposits at ca 2 4 ga of transvaal supergroup south africa were formed by oxidation of hydrothermally derived mn2 transferred from a stratified ocean to the continental shelf by transgression episodes of increased burial rate of organic matter during ca 2 4 and 2 06 ga are correlatable to ocean stratification and further rise of oxygen in the atmosphere black shale hosted mn carbonate deposits in the birimian sequence ca 2 3 2 0 ga west africa its equivalents in south america and those in the francevillian sequence ca 2 2 2 1 ga gabon are correlatable to this period tectonically forced doming up attenuation and substantial increase in freeboard areas prompted increased silicate weathering and atmospheric co2 drawdown causing glaciation on the neoproterozoic rodinia supercontinent tectonic rifting and mantle outgassing led to deglaciation dissolved mn2 and fe2 concentrated earlier in highly saline stagnant seawater below the ice cover were exported to shallow shelves by transgression during deglaciation during the sturtian glacial interglacial event ca 750 700 ma interstratified mn oxide and bif deposits of damara sequence namibia was formed the varangian marinoan ca 600 ma cryogenic event produced mn oxide and bif deposits at urucum jacadigo group brazil the datangpo interglacial sequence south china liantuo nantuo varangian event contains black shale hosted mn carbonate deposits the early paleozoic witnessed several glacioeustatic sea level changes producing small mn carbonate deposits of tiantaishan early cambrian and taojiang mid ordovician in black shale sequences china and the major mn oxide carbonate deposits of karadzhal type central kazakhstan late devonian the mesozoic period of intense plate movements and volcanism produced greenhouse climate and stratified oceans during the early jurassic oae organic rich sediments host many mn carbonate deposits in europe e g urkut hungary in black shale sequences the late jurassic giant mn carbonate deposit at molango mexico was also genetically related to sea level change mn carbonates were always derived from mn oxyhydroxides during early diagenesis large mn oxide deposits of cretaceous age at groote eylandt australia and imini tasdremt morocco were also formed during transgression regression in greenhouse climate the early oligocene giant mn oxide carbonate deposit of chiatura georgia and nikopol ukraine were developed in a similar situation thereafter manganese sedimentation was entirely shifted to the deep seafloor and since ca 15 ma b p was climatically controlled glaciation deglaciation assisted by oxygenated polar bottom currents aabw nadw the changes in climate and the sea level were mainly tectonically forced

al mg isotopic evidence for episodic alteration of ca al rich inclusions from allende textures mineral assemblages and al mg isotope systematics indicate a protracted episodic secondary mineralization history for allende ca al rich inclusions cais detailed observations from one type b1 cai one b2 one compact type a cta and one fluffy type a fta indicate that these diverse types of cais are characterized by two distinct textural and mineralogic types of secondary mineralization 1 grossular rich domains concentrated along melilite grain boundaries in cai interiors and 2 feldspathoid bearing domains confined mostly to cai margins just interior to the wark lovering rim sequence the al mg isotopic compositions of most secondary minerals in the type b1 cai and some secondary minerals in the other cais show no resolvable excesses of 26mg whereas the primary cai phases mostly yield correlated excesses of 26mg with increasing al mg corresponding to canonical initial 26al 27al 4 55 10 5 these secondary minerals formed at least 3 ma after the primary cai minerals all but two analyses of secondary minerals from the fluffy type a cai define a correlated increase in 26mg 24mg with increasing al mg yielding 26al 27al 0 4 9 2 8 10 6 the secondary minerals in this cai formed 1 8 3 2 ma after the primary cai minerals in both cases the timing of secondary alteration is consistent with but does not necessarily require alteration in an asteroidal setting one grossular from the type b2 cai and several grossular and secondary feldspar analyses from the compact type a cai have excesses of 26mg consistent with initial 26al 27al 4 5 10 5 especially in the compact type a cai where 26mg 24mg in grossular correlates with increasing al mg these 26mg excesses are almost certainly due to in situ decay of 26al they indicate a nebular setting for formation of the grossular the preservation of these diverse isotopic patterns indicates that heating on the allende parent body was not pervasive enough to reset isotopic systematics of fine grained secondary minerals secondary mineralization clearly was not restricted to a short time interval and at least some alteration occurred coincident with cai formation and melting events chondrule formation in the nebula this observation supports the possibility that alteration followed by melting affected the compositional evolution of cais

oxygen silicon and mn cr isotopes of fayalite in the kaba oxidized cv3 chondrite constraints for its formation history the iron rich olivine end member fayalite occurs in the matrix chondrules ca al rich inclusions cais silicate aggregates and dark inclusions in the kaba and mokoia oxidized cv3 chondrites in most occurrences fayalite is associated with magnetite and troilite to help constrain the origin of the fayalite fa98 100 we measured oxygen and silicon isotopic compositions and mn cr systematics in fayalite from two petrographic settings of the kaba meteorite one setting consists of big fayalite laths embedded in the matrix and radiating from a core of fine grained magnetite and sulfide while the other setting consists of small fayalite magnetite sulfide assemblages within or at the surface of type i barred or porphyritic olivine chondrules oxygen in the big fayalite laths and small chondrule fayalites falls on the terrestrial fractionation line and is distinct from that in chondrule forsterites which are enriched in 16o 17o 4 oxygen in the big fayalite laths may be isotopically heavier than that in chondrule fayalites silicon isotopes suggest that forsterite is 1 amu heavier than adjacent fayalite within kaba chondrules however we were unable to confirm large silicon isotopic differences among fayalites reported previously the mn cr data for big kaba fayalites give an initial 53mn 55mn ratio of 2 07 0 17 10 6 consistent with literature results on mokoia chondrule fayalites the combined data suggest that fayalites in both petrographic settings formed at about the same time 9 7 ma after the formation of cais our data indicate that those fayalite magnetite troilite assemblages replacing metal inside and around chondrules formed by aqueous alteration on the meteorite parent body the formation site and mechanism for the big fayalite laths is less clear but the petrographic setting indicates that they did not form in situ none of the models that have been suggested for formation of these fayalites is entirely satisfactory

positive δ13c excursion in carbonate and organic fractions from the paleoproterozoic aravalli supergroup northwestern india abstract carbon and oxygen isotopic investigations have been carried out on the archean and paleoproterozoic carbonate rocks of the udaipur region in the aravalli mountain belt northwestern india the study has led to the interesting finding of 13 c enrichment in the carbonate rocks of the jhamarkotra formation 13 c carb up to 11 1 v pdb belonging to the 2200 1900 ma paleoproterozoic aravalli supergroup further it is observed that the organic carbon from phosphorite bearing stromatolitic dolomites of the same formation are also enriched in 13 c 13 c org up to 11 1 however it must be emphasized that the 13 c enriched carbonates and the organic fractions are from different stratigraphic levels although in the same formation the former being at a lower stratigraphic level a critical analysis of the field geological petrological as well as the isotopic data indicates that the observed 13 c excursion in the carbonate carbon is not due to local causes such as methanogenesis or evaporitic conditions the shallow water environment of deposition of these carbonates as well as the immediately overlying formations rules out the stratified ocean model for the observed excursion the model involving high sedimentation rates and organic carbon burial has been preferred to explain the 13 c excursion in the carbonates of the jhamarkotra formation the 13 c enrichment in organic fraction occurred in localized regions of the aravalli sedimentary basin where high productivity was supported by phosphorous supply indicating that the diffusion limited pathways of organic carbon fixation were operative in the paleoproterozoic itself the 13 c enriched carbonate rocks of the jhamarkotra formation serve as the indian example for the paleoproterozoic global 13 c excursion

constraining atmospheric oxygen and seawater sulfate concentrations during paleoproterozoic glaciation in situ sulfur three isotope microanalysis of pyrite from the turee creek group western australia abstract previous efforts to constrain the timing of paleoproterozoic atmospheric oxygenation have documented the disappearance of large mass independent sulfur isotope fractionation and an increase in mass dependent sulfur isotope fractionation associated with multiple glaciations at least one of these glacial events is preserved in diamictites of the 2 4 ga meteorite bore member of the kungarra formation turee creek group western australia outcrop exposures of this unit show the transition from the boolgeeda iron formation of the upper hamersley group into clastic glaciomarine sedimentary rocks of the turee creek group here we report in situ multiple sulfur isotope and elemental abundance measurements of sedimentary pyrite at high spatial resolution as well as the occurrence of detrital pyrite in the meteorite bore member the 15 3 range of 33 s in one sample containing detrital pyrite 3 6 to 11 7 is larger than previously reported worldwide and there is evidence for mass independent sulfur isotope fractionation in authigenic pyrite throughout the section 33 s from 0 8 to 1 0 the 90 range in 34 s observed 45 5 to 46 4 strongly suggests microbial sulfate reduction under non sulfate limiting conditions indicating significant oxidative weathering of sulfides on the continents multiple generations of pyrite are preserved typically represented by primary cores with low 34 s 34 s 4 7 and enrichments in as ni and co the preservation of extremely sharp sulfur isotope gradients 30 p o 2 first became sufficiently high to permit pervasive oxidative weathering of continental sulfides yet remained low enough to permit the production and preservation of mass independent sulfur isotope fractionation

precambrian vein pyrobitumen evidence for petroleum generation and migration 2 ga ago abstract isotopic optical reflectance and chemical analyses of large pure samples of lower proterozoic vein pyrobitumens anthraxolite and thucholite of older reports collected from five widely separated localities in the great lakes region of the united states and canada suggest that in the lower proterozoic oil was generated from kerogen and migrated in much the same way as during the phanerozoic furthermore maturation and organic metamorphism followed the same successive stages that mark the generation and destruction of phanerozoic petroleum kerogens derived from algae and bacteria were deposited with subaqueous muds that ultimately became black shales or slates some of the kerogen however yielded petroleum which migrated into fractures and subsequently became pyrobitumen the 13c values average 32 6 pdb this value compares favorably with those from phanerozoic petroleum and asphaltites and is consistent with the proposition that the carbon isotopes were fractionated by biological activity reflectance values of the pyrobitumens range from 0 9 for elliot lake ontario to 9 5 for iron river michigan and h c ratios range from 0 6 for elliot lake to 0 1 for sudbury ontario when compared with the stages of petroleum maturation these values indicate maturation which ranges from the catagenesis stage through the metagenesis stage of petroleum generation and metamorphism

high phosphate availability as a possible cause for massive cyanobacterial production of oxygen in the paleoproterozoic atmosphere abstract the deposition of major precambrian phosphorites was restricted to times of global change and atmospheric oxygenation at both ends of the proterozoic phosphorites formed after highly positive carbon isotope excursions in carbonates deposited during the paleoproterozoic lomagundi jatuli event and the neoproterozoic cryogenian and ediacaran periods the correlative step wise rise in atmospheric oxygen over the proterozoic has been linked to changes in the carbon cycle however the postulated relations between carbon isotope events phosphorites and atmospheric oxygenation remain unexplained paleoproterozoic carbonates of the aravalli supergroup india preserve evidence for cyanobacterial blooms in the form of tightly packed stromatolitic columns in the world s oldest significant sedimentary phosphate deposit restricted basins of the lower aravalli group with stromatolitic phosphorites in jhamarkotra udaipur jhabua and sallopat exhibit near zero 13 c carb values and large ranges of 13 c org values between 33 3 and 10 1 indicative of a complex carbon cycle because phosphate accumulates primarily in oxic sediments these eutrophic microbial ecosystems likely developed within the photic zone of the shallow oxygenated marine realm this is consistent with deposition during the time of increasingly more oxidizing conditions after the great oxidation event goe approximately contemporaneous basins without phosphate deposits from ghasiar karouli negadia umra and babarmal exhibit a range of positive 13 c carb excursions some with values up to 11 2 that suggest high rates of organic carbon burial and others with moderately high 13 c carb values around 6 or 3 that suggest smaller carbon cycle perturbations the 15 n values of all these rocks vary between 0 7 and 3 4 and are consistent with the predominance of nitrogen fixation during cyanobacterial blooms in all basin types such low nitrogen isotope values are interpreted to have arisen from the biological response to high phosphate availability we conclude that increased phosphate availability during and after the paleoproterozoic lomagundi jatuli event likely caused cyanobacterial blooms and was a key factor in the oxygenation of earth s atmosphere increasing oxygenation of the shallow ocean seafloor favored the removal of excess phosphate as authigenic apatite thus dampening effects of weathering increases on organic burial and marine 13 c carb after about 2 0 ga

53mn 53cr dating of fayalite formation in the cv3 chondrite mokoia evidence for asteroidal alteration fayalite grains in chondrules in the oxidized aqueously altered cv3 chondrite mokoia have large excesses of radiogenic chromium 53 these excesses indicate the in situ decay of short lived manganese 53 half life 3 7 million years and define an initial53mn 55mn ratio of 2 32 0 18 10 6 this ratio is comparable to values for carbonates in ci and cm chondrites and for several classes of differentiated meteorites mokoia fayalites formed 7 to 16 million years after allende calcium aluminum rich inclusions during hydrothermal activity on a geologically active asteroid after chondritic components had ceased forming in the solar nebula

provenance of proterozoic basal aravalli mafic volcanic rocks from rajasthan northwestern india nd isotopes evidence for enriched mantle reservoirs abstract komatiites komatiitic basalts and tholeiites from nathdwara rajasthan have been investigated for their nd isotopic characteristics 143nd 144nd vary broadly in the komatiites 0 51131 0 51252 and show a restricted range in komatiitic basalts and tholeiites 0 51120 0 51179 and 0 51141 0 51202 respectively the corresponding epsilon nd nd values indicate an enriched source for these rocks the model ages of komatiitic basalts and tholeiites cluster between 2 2 and 3 0 ga the komatiites show older model ages between 3 5 and 3 8 ga if the correlations found between nd and sm isotopic ratios can be interpreted as isochrones then the komatiites point to the age of 2300 ma and the komatiitic basalts and tholeiites constrain the age of 1800 2000 ma the age of 2300 ma for the komatiite samples is similar to the range estimated for the komatiitic basalt and tholeiite samples 1800 2000 ma considering the errors involved collectively the data suggest an age of 2300 1800 ma for the basal aravalli volcanism the variation of nd isotopic ratios between the komatiites and the associated basalts is too large to reflect analytical bias or open system behavior for sm and nd it may be due to significant mantle heterogeneity in the source region isotopically distinct sources for the komatiites and komatiitic basalts are possible but simple mixing between a depleted mantle component and a crustal component in the manner of magmatic assimilation of wall rock material is inconsistent with the observed isotopic ratios the inference of an enriched mantle component appears inevitable as the alternative model of mixing would have generated more siliceous high magnesian boninitic rocks with much lower fe and ti than are observed this enriched material may have been part of the sub continental lithospheric mantle sclm under the aravalli craton which could have generated the basal aravalli magmatic rocks we suggest that during early middle proterozoic the sclm under cratonic regions consisted of relatively fertile mantle capable of generating komatiites tholeiites and alkalic magmas

oxygen overshoot and recovery during the early paleoproterozoic abstract during the lomagundi event ca 2 22 to 2 06 ga marine carbonates recorded the largest and longest uninterrupted positive carbon isotope excursion the earliest extensive marine sulfate evaporites were deposited and the average ferric iron to total iron expressed as fe 2 o 3 fe fe2o3 ratio of shales increased dramatically at the end of the lomagundi event the first economic sedimentary phosphorites were deposited and the carbon isotope values of marine carbonates returned to 0 vpdb thereafter marine sulfate evaporites and phosphorites again became scarce while the average fe 2 o 3 fe fe2o3 ratio of shales decreased to values intermediate between those of the archean and lomagundi age shales we propose that the large isotopic and chemical excursions during the lomagundi event were caused by a positive feedback between the rise of atmospheric o 2 the weathering of sulfides in the pre 2 3 ga continental crust and the flux of phosphate to the oceans cf holland 2002 the rise in the terrestrial phosphate flux led to an increase in the burial rate of organic carbon and a major transfer of oxygen from the carbon to the sulfur cycle the end of the lomagundi event was probably caused by a decrease in the terrestrial phosphate flux related to the weathering of low pyrite sediments that were deposited during the lomagundi event the rate of deposition of organic matter and the precipitation of sulfate evaporites decreased the isotopic and chemical excesses of the lomagundi event were eliminated and the ocean atmosphere system entered the period frequently called the boring billion

the i xe record of alteration in the allende cv chondrite abstract complex i xe and mineralogical studies have been performed on four heavily altered allende fine grained spinel rich ca al rich inclusions cais and four allende dark inclusions dis showing various degrees of iron alkali metasomatic alteration the cais are largely composed of fe rich spinel al diopside and secondary nepheline and sodalite the dis consist of chondrules and allende like matrix composed of lath shaped fayalitic olivine nepheline sodalite and ca fe rich pyroxene andradite feni sulfide nodules chondrule phenocrysts are extensively or completely replaced by fayalitic olivine nepheline and sodalite metal nodules are replaced by feni sulfides andradite and ca fe rich pyroxenes the chondrules and matrices are crosscut by ca fe rich pyroxene feni sulfide fayalitic olivine veins dis are surrounded by continuous ca rich rims composed of andradite wollastonite kirschsteinite and ca fe rich pyroxenes whereas the outer portions of the inclusions are depleted in ca three cais yield well defined i xe isochrons with ages 3 1 0 2 3 0 0 2 and 3 7 0 2 ma younger than the shallowater internal standard 4566 2 ma similar release profiles suggest the same iodine carrier most probably sodalite for all four cais the allende dis yield i xe ages from 0 8 0 3 to 1 9 0 2 ma older than shallowater based on the petrographic observations we infer that the dis experienced at least two stage alteration during an early stage of the alteration which took place in an asteroidal setting but not in the current location of the dis chondrule silicates were replaced by secondary fayalitic olivine nepheline and sodalite calcium lost from the chondrules was redeposited as ca fe rich pyroxene veins and ca fe rich pyroxene andradite nodules in the matrix the second stage of alteration resulted in mobilization of ca from the dis and its re deposition as ca rich rims composed of ca fe rich pyroxenes andradite and wollastonite around the dis we interpret i xe ages of the dis as time of their alteration prior incorporation into allende the younger i xe ages of the fine grained spinel rich cais may reflect hydrothermal alteration of the allende host which could have occurred contemporaneously with the second stage of alteration of the allende dis the lack of evidence for the disturbance of i xe system in the allende dis may suggest that fluid responsible for the alteration of the allende cais was in equilibrium with the i and xe bearing phases of the dis

high primary productivity and nitrogen cycling after the paleoproterozoic phosphogenic event in the aravalli supergroup india the causes of atmospheric oxygenation in the paleoproterozoic are multifaceted yet poorly understood an increase in the level of primary productivity however may have been an important factor in producing large amounts of oxygen in the atmosphere a likely environmental consequence of atmospheric oxygenation is an increased abundance of seawater nitrate which would have resulted in a fundamental change from the archean nitrogen cycle in this study we investigate these questions using the carbon and nitrogen isotope compositions of carbonaceous shales from the paleoproterozoic aravalli supergroup india the shales occur stratigraphically above one of the oldest phosphogenic events that took place around 2 0 ga shales in the phosphate domain of the jhamarkotra formation from the lower aravalli group have distinct characteristics from coeval shales in the non phosphate domain carbonaceous shales of the phosphate domain contain relatively high v and u th typical of oxygen deficient environments these shales also have a high organic content of up to 14 wt generally homogeneous 13 corg values around 29 c nwr up to 360 and a large range of 15