the paleoproterozoic snowball earth a climate disaster triggered by the evolution of oxygenic photosynthesis although biomarker trace element and isotopic evidence have been used to claim that oxygenic photosynthesis evolved by 2 8 giga annum before present ga and perhaps as early as 3 7 ga a skeptical examination raises considerable doubt about the presence of oxygen producers at these times geological features suggestive of oxygen such as red beds lateritic paleosols and the return of sedimentary sulfate deposits after a 900 million year hiatus occur shortly before the 2 3 2 2 ga makganyene snowball earth global glaciation the massive deposition of mn which has a high redox potential practically requires the presence of environmental oxygen after the snowball new age constraints from the transvaal supergroup of south africa suggest that all three glaciations in the huronian supergroup of canada predate the snowball event a simple cyanobacterial growth model incorporating the range of c fe and p fluxes expected during a partial glaciation in an anoxic world with high fe oceans indicates that oxygenic photosynthesis could have destroyed a methane greenhouse and triggered a snowball event on timescales as short as 1 million years as the geological evidence requiring oxygen does not appear during the pongola glaciation at 2 9 ga or during the huronian glaciations we argue that oxygenic cyanobacteria evolved and radiated shortly before the makganyene snowball

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

atmospheric oxygenation caused by a change in volcanic degassing pressure around two and a half billion years ago following the end of the archaean eon the atmosphere turned from anoxic to weakly oxic in what is known as the great oxidation event using a model of volcanic degassing gaillard et al demonstrate that a preceding period of continental crust formation may have been the trigger they propose that as continents emerged and volcanoes became increasingly subaerial rather than submarine magmatic volatiles were degassed at lower pressures leading to a progressive oxidation of the gases released this shift to a release of sulphur as sulphur dioxide rather than as hydrogen sulphide could then have fed marine sulphate reduction and the eventual oxygenation of earth s atmosphere the precambrian history of our planet is marked by two major events a pulse of continental crust formation at the end of the archaean eon and a weak oxygenation of the atmosphere the great oxidation event that followed at 2 45 billion years ago this oxygenation has been linked to the emergence of oxygenic cyanobacteria1 2 and to changes in the compositions of volcanic gases3 4 but not to the composition of erupting lavas geochemical constraints indicate that the oxidation state of basalts and their mantle sources has remained constant since 3 5 billion years ago5 6 here we propose that a decrease in the average pressure of volcanic degassing changed the oxidation state of sulphur in volcanic gases initiating the modern biogeochemical sulphur cycle and triggering atmospheric oxygenation using thermodynamic calculations simulating gas melt equilibria in erupting magmas we suggest that mostly submarine archaean volcanoes produced gases with so2 h2s 1 and low sulphur content emergence of the continents due to a global decrease in sea level and growth of the continental crust in the late archaean then led to widespread subaerial volcanism which in turn yielded gases much richer in sulphur and dominated by so2 dissolution of sulphur in sea water and the onset of sulphate reduction processes could then oxidize the atmosphere

seismotectonics of jamaica summary this is the first seismological investigation of the stress regime in the jamaican crust the fault plane solutions of 32 well recorded local earthquakes were determined and used as inputs for determining stress directions the results consistently show that a strike slip fault regime sh sv sh e xists in three homogeneous crustal areas namely the blue mountain wagwater restraining bend of eastern jamaica the rio minho crawle river rmcr fault of central jamaica and the montpelier newmarket belt mnb of western jamaica however for the island as a whole a thrust faulting regime sh sh sv w as found but inhomogeneity is implied by the higher level of misfit obtained these results are in keeping with results of other recent studies in the jamaica cuba region and with the strike slip regime of the gonave microplate boundaries

burial of organic carbon and pyrite sulfur in sediments over phanerozoic time a new theory in present day marine sediments almost all of which are deposited in normal oxygenated seawater rates of burial of organic carbon c and pyrite sulfur s correlate positively and bear a constant ratio to one another c s 3 on a weight basis by contrast calculations based on the isotopic model of garrels and lerman 1981 indicate that at various times during the phanerozoic the worldwide burial ratio must have been considerably different than the present day value this ratio change is caused by the requirement that increases in the worldwide mass of organic carbon must be accompanied by equivalent decreases in the mass of sedimentary pyrite sulfur in order to maintain a roughly constant level of o2 in the atmosphere such apparently contradictory behavior can be explained if the locus of major organic carbon burial has shifted over time from normal marine environments as at present to non marine freshwater or to euxinic environments in the geologic past a shift to predominantly freshwater burial can help explain predicted high c s ratios in permo carboniferous sediments and a shift to euxinic environments can help explain predicted low c s ratios during the early paleozoic it is demonstrated that the three environments today exhibit distinguishably different average c s ratios

uv induced mass independent sulfur isotope fractionation in stratospheric volcanic sulfate 1 sulfuric acid aerosols produced in the stratosphere following massive volcanic eruptions possess a mass independent sulfur isotopic signature acquired when volcanic so2 experiences uv photooxidation the volcanic data are consistent with laboratory so2 photooxidation experiments using uv light at 248 nm maximum absorption of ozone whereas sulfur isotopic anomalies previously observed in archean samples are consistent with photodissociation at 190 220 nm a mechanism of so2 photooxidation occurring in the early stage of a stratospheric volcanic plume in the range of 220 320 nm weak band absorption of so2 is also proposed since mass independent sulfur isotope anomalies in stratospheric volcanic sulfate appear to depend on the exposure of so2 to uv radiation their measurements might therefore offer the possibility to determine the degree of uv penetration in the ozone absorption window for the present and past atmospheres they can also be used to determine the stratospheric or tropospheric nature of volcanic eruptions preserved in glaciological records offering the possibility to reassess the climatic impact of past volcanic eruptions

multiple sulfur isotopes from paleoproterozoic huronian interglacial sediments and the rise of atmospheric oxygen mass dependently fractionated mdf sulfur isotopes in sedimentary sulfides and sulfates can provide information on the past activity of microbial metabolisms and serve as a proxy for the concentration of seawater sulfate in conjunction with these proxies mass independently fractionated mif sulfur isotopes can be used to track the rise of atmospheric oxygen the anoxic oxic transition of the surface environment in the paleoproterozoic has been constrained by mif sulfur in 2 47 ga sulfides from western australian banded iron formations and the absence of mif in diagenetic sulfides from 2 32 ga black shales in the transvaal supergroup south africa we report new multicollector ion microprobe data for individual sulfides from water lain sedimentary units in the 2 45 2 22 ga huronian supergroup ontario canada the authigenecity of sulfides in these units is interpreted on the basis of host lithology mode of distribution sulfide chemistry and mdf sulfur isotopes sulfides interpreted to have an authigenicsedimentary origin from the mckim fm have a range of 0 7 in 33 s values and those in the pecors fm preserve small magnitude mif 33 s values up to 0 88 which we propose represents the last remnants of an anoxic atmosphere high 34 s values up to 31 2 and near zero 33 s values in authigenic sulfides from the stratigraphically higher espanola and gordon lake fms suggest local variations of seawater sulfate concentrations and or 34 ssulfate consistent with increased atmospheric o2 levels mif sulfur is absent from the marine record after the second huronian glaciation which is analogous to the record of the transvaal supergroup where mif is absent from the upper part of the interglacial sequence our results suggest that the possible simultaneous demise of mif sulfur isotopes at these two localities may serve as a useful global geochemical marker to correlate paleoproterozoic supergroups we propose a new biogeochemical model where enhanced weathering rates during paleoproterozoic post glacial thawing served as a critical stimulus for interglacial blooms of oxygenic photosynthesis the demise of methane and ultimately to the irreversible rise in atmospheric oxygen

the origin of carbonaceous matter in pre 3 0 ga greenstone terrains a review and new evidence from the 3 42 ga buck reef chert abstract the geological record of carbonaceous matter from at least 3 5 ga to the end of the precambrian is fundamentally continuous in terms of carbonaceous matter structure composition environments of deposition preservation and abundance in host rocks no abiotic processes are currently known to be capable of producing continuity in all four of these properties although this broad view of the geological record does not prove that life had arisen by 3 5 ga the end of the early archean it suggests a working hypothesis most if not all carbonaceous matter present in rocks older than 3 0 ga was produced by living organisms this hypothesis must be tested by studies of specific early geological units designed to explore the form distribution and origin of enclosed carbonaceous matter the carbonaceous environmentally diverse 3416 ma buck reef chert brc of the barberton greenstone belt south africa provides an opportunity for such a study upward facies progressions in the brc reflect deposition in environments ranging from shallow marine evaporitic brine ponds to a storm and wave active shelf to a deep low energy basinal setting below storm wave base abundances and ratios of al2o3 zr tio2 and cr track inputs of various types of volcaniclastic and terrigenous clastic materials in particular zr al2o3 and zr serve as proxies for concentration of windblown dust and indirectly as proxies for sedimentation rate cu zn ni and feo were concentrated in the most slowly deposited transitional and basinal sediments inconsistent with a hydrothermal setting but consistent with a normal marine setting the distribution of microfacies defined by associations and layering of clastic ferruginous and carbonaceous grains correlates with facies transitions fine carbonaceous laminations which occur only in shallow platform settings represent photosynthetic microbial mats these were ripped up and the debris widely redistributed in shallow and deep water by waves and storms the isotopic composition of carbonaceous matter ranges from 35 to 30 in shallow water settings and to 20 in deep water units the heavier 13c in deep water carbonaceous matter is thought to reflect microbial processing possibly by fermentation and methanogenesis of organic matter originally produced in shallow water hydrothermal origins for brc carbonaceous matter are clearly excluded by the inferred depositional setting of the rocks as a whole an inference supported by field petrographic and geochemical analysis we suggest that the biological model proposed here for brc carbonaceous matter is the best currently available the hypothesis that at least some carbonaceous matter present in rocks older than 3 0 ga was produced by living organisms should be regarded as likely until extraordinary contradictory evidence is presented

detrital pyrite in witwatersrand gold reefs x ray diffraction evidence and implications for atmospheric evolution pyrite is easily oxidized and therefore unambiguous evidence of detrital pyrite grains in metasediments is a significant constraint on when an oxygenated atmosphere developed compact rounded pyrite in the witwatersrand gold reefs of south africa has a detrital habit and is texturally equivalent to and spatially associated with detrital zircon and chromite x ray precession photography reveals that petrographically featureless as poor grains are untwinned single crystals of high diffraction quality this new evidence from crystallography is consistent with mechanically abraded pyrite from primary lode gold deposits and excludes an origin by replacement of a pre existing detrital phase further evidence of a detrital origin for the compact rounded pyrite is afforded by isolated grains of arsenian pyrite displaying truncated as rich growth bands the geographically extensive witwatersrand fluvial conglomerates evidently had a matrix of quartz and pyrite sand and pyritic mud in their unconsolidated state and thus the late archean atmosphere of earth was likely essentially anoxic

tropical laterites life on land and the history of atmospheric oxygen in the paleoproterozoic the ca 2 2 ga hekpoort paleosol of the transvaal supergroup in southern africa has been considered a type example and the youngest iron depleted paleosol formed under a reducing atmosphere in the early precambrian however the mineralogical and geochemical data on recently acquired deep drill core intersections indicate that the hekpoort paleosol represents part of an ancient lateritic weathering profile with an iron depleted pallid lower zone and an iron enriched lateritic upper zone previous studies of the paleosol took place in areas where only the lower pallid zone was preserved from erosion prior to deposition of cover beds the laterite profile is comparable to that of modern tropical laterites formed under an oxic atmosphere in the presence of abundant terrestrial biomass revised stratigraphic correlation indicates that the hekpoort laterite profile is a correlative to highly ferruginous laterite profiles of wolhaarkop in griqualand west this information indicates that the oxygen evolution curve based on loss or retention of iron in paleosols should be reexamined

pyrite paragenesis and multiple sulfur isotope distribution in late archean and early paleoproterozoic hamersley basin sediments abstract the sulfur isotope record in late archean and early paleoproterozoic rocks is of considerable importance because it provides evidence for changes in early earth atmospheric oxygen levels and potentially constrains the origin and relative impact of various microbial metabolisms during the transition from an anoxic to oxic atmosphere mass independently fractionated mif sulfur isotopes reveal late archean and early paleoproterozoic sulfur sources in different pyrite morphologies in western australia s hamersley basin multiple sulfur isotope values in late archean pyrite vary according to morphology fine grained pyrite has positive sulfur mif indicating a reduced elemental sulfur source whereas pyrite nodules have negative sulfur mif potentially derived from soluble sulfate via microbial sulfate reduction the hamersley basin 34 s 33 s record suggests that the extent of oxygenation of the surface ocean fluctuated through the late archean from at least 2 6 ga more than 150 million yr before the great oxidation event in the early paleoproterozoic there is less distinction between pyrite morphologies with respect to sulfur isotope fractionation and pyrite from the brockman iron formation trends toward modern sulfur isotope values an important exception to this is the strong negative mif recorded in layer parallel pyrite in paleoproterozoic carbonate facies iron formation this may suggest that deeper water hydrothermal environments remained anoxic while shallower water environments became more oxidised by the early paleoproterozoic the results of the current study indicate that sulfide paragenesis is highly significant when investigating archean and early paleoproterozoic multiple sulfur isotope compositions and sulfur sources

a multiple sulfur and organic carbon isotope record from non conglomeratic sedimentary rocks of the mesoarchean witwatersrand supergroup south africa abstract multiple sulfur isotope ratios 36 s 34 s 33 s 32 s and organic carbon isotope ratios 13 c 12 c were measured from 198 non conglomeratic sedimentary samples that were collected from five deep diamond drill cores that cover the majority of the ca 2 96 2 82 ga witwatersrand supergroup 13 c org 34 s py and 33 s py values of the sample set range from 44 3 to 21 9 3 7 to 16 5 and 4 0 to 1 9 respectively these geochemical data vary relative to depositional facies proximal marine distal marine and fluvial dominated and tectonic setting trailing margin and foreland basin in the trailing margin setting of the 2 96 ga hospital hill subgroup the proximal marine depofacies is characterized by relatively high organic carbon contents up to 0 9 wt and 13 c org values around 28 in contrast to the distal marine depofacies that yields low organic carbon contents 0 01 wt and high 13 c org values up to 22 both depofacies yield low sulfur contents 0 02 wt a narrow range of 34 s values 3 2 and positive 33 s values up to 1 9 this data is consistent with photoautotrophic carbon fixation in shallow marine environments and limited organic carbon production preservation in deeper water settings due to longer transport distances and effective biological degradation e g fe reducing microbes positive 33 s values imply that sulfur was largely derived from a photochemical elemental sulfur reservoir in the foreland basin tectonic setting of the 2 94 ga government and 2 92 ga jeppestown subgroups shelf deposits associated with fluvial braidplain depofacies are characterized by 13 c depleted organic carbon 44 to 38 relatively high sulfur contents 0 2 1 3 wt variable 34 s values 3 7 to 16 5 and small negative 33 s values 0 4 these data suggest that the microbial community in the fluvial dominated depofacies may have consisted of photoautotrophs methanogens anaerobic methanotrophs and sulfate reducers sulfate was derived from a variety of sources that include photochemical crustal and marine sulfur reservoirs the occurrence of three regionally persistent diamictite deposits in the government subgroup coincides with the onset of compressional tectonics and development of pyritic shales with highly 13 c depleted organic carbon suggesting that an increase in continental sulfur flux and methane oxidation may have triggered the mesoarchean glaciations drawdown of h 2 and ch 4 however the link between large 33 s anomalies 4 0 to 1 2 and diamictite suggests low levels of atmospheric oxygen and minimal dilution of photochemical signatures

origin of two distinct multiple sulfur isotope compositions of pyrite in the 2 5ga klein naute formation griqualand west basin south africa abstract quadruple sulfur isotope ratios 32s 33s 34s 36s were measured by a high precision sf6 method for early diagenetic pyrite in the 2 5 ga upper prieska facies of the griqualand west basin from the agouron drill core gkp01 measured 33s 33s 0 515 34s values range between 2 3 and 8 5 with no apparent meter scale stratigraphic trend for 70 m section it was found that early diagenetic pyrites occur in two texturally and isotopically distinct populations such that bulk rock isotope data would reflect mixing of these two sulfur pools nodular and layered pyrite yield mostly negative down to 2 3 and relatively constant 33s values over a few tens of cm scale disseminated pyrites in contrast yield positive 0 0 8 5 33s values that are heterogeneous in sub cm scales the former pyrite sulfur was likely derived from seawater sulfate through microbial sulfate reduction and the latter preferentially sampled aqueous h2s s0 reservoirs in late archean oceans relatively constant 33s values for layered pyrite suggest archean sulfate reservoirs had residence times of a few million years most data yield a well defined 36s 33s ratios of 0 9 suggesting predominance of a single s mif source reaction four analyses of a two cm length sample 306 5 m yield 36s 33s slope of 1 6 this slope is consistent with the relationship expected for a symmetry breaking isotope effect during the s s2 reaction but deviations from the main archean array i e 36s 33s 0 9 may also result from various combinations of so photolysis and so2 oxidation high spatial resolution high precision sf6 measurements of archean pyrite provide significant new insights into the origin of archean sulfur mass independent fractionation s mif and the late archean sulfur cycle

sulphur isotope evidence for an oxic archaean atmosphere the presence of mass independently fractionated sulphur isotopes mif s in many sedimentary rocks older than approximately 2 4 billion years gyr and the absence of mif s in younger rocks has been considered the best evidence for a dramatic change from an anoxic to oxic atmosphere around 2 4 gyr ago this is because the only mechanism known to produce mif s has been ultraviolet photolysis of volcanic sulphur dioxide gas in an oxygen poor atmosphere here we report the absence of mif s throughout approximately 100 m sections of 2 76 gyr old lake sediments and 2 92 gyr old marine shales in the pilbara craton western australia we propose three possible interpretations of the mif s geologic record 1 the level of atmospheric oxygen fluctuated greatly during the archaean era 2 the atmosphere has remained oxic since approximately 3 8 gyr ago and mif s in sedimentary rocks represents times and regions of violent volcanic eruptions that ejected large volumes of sulphur dioxide into the stratosphere or 3 mif s in rocks was mostly created by non photochemical reactions during sediment diagenesis and thus is not linked to atmospheric chemistry

relationship between detrital zircon age spectra and the tectonic evolution of the late archaean witwatersrand basin south africa abstract shrimp u pb detrital zircon age spectra for 14 samples from the west rand and central rand groups of the witwatersrand basin indicate that felsic source rocks mostly formed at 3090 3060 and 3000 2870 ma with a smaller proportion formed prior to 3100 ma provenance evaluation indicates that source rocks have largely vanished through erosion such that greenstone terrains extending from the amalia kraaipan belt in the southwest to the murchison belt in the northeast are models of but not the actual source areas analysis of detrital zircon age modes reveals that the west rand and central rand groups record different basins the west rand group is characterised by age subpopulations with a much smaller range and less complex distribution than those in the central rand group furthermore detrital zircon age spectra for the west rand group generally decrease in complexity up section whereas they become increasingly more complex in the central rand group it is concluded that the source area for the west rand group is consistent with a passive margin setting with the decrease in complexity up section of zircon age spectra being the consequence of increasing maturity of the hinterland conversely the source area of the central rand group was far more dynamic with an increasing age range of source rocks being exposed through time pulsed tectonic rejuvenation of the source area is implied contemporaneous emplacement uplift and erosion of granitoids supports a magmatic fold thrust belt as the source and a complementary retroarc basin setting detrital xenotime grains record the ages of high u granitoids emplaced in the fold thrust belt during deposition of the central rand group and are much closer to depositional ages than are detrital zircon grains change from a passive margin to a retroarc basin across the west rand central rand boundary is emphasised by change from simple to increasingly complex detrital zircon age spectra this study establishes that detrital zircon geochronology can overcome the problem of overly quartzose compositions in archaean sandstones due to severe chemical weathering and authigenic alteration thereby enabling distinction between passive margin and retroarc basin stages through systematic changes in the age complexity of the source area

reconstructing earth s surface oxidation across the archean proterozoic transition the archean proterozoic transition is characterized by the widespread deposition of organic rich shale sedimentary iron formation glacial diamictite and marine carbonates recording profound carbon isotope anomalies but notably lacks bedded evaporites all deposits refl ect environmental changes in oceanic and atmospheric redox states in part associated with earth s earliest ice ages time series data for multiple sulfur isotopes from carbonateassociated sulfate as well as sulfi des in sediments of the transvaal supergroup south africa capture the concomitant buildup of sulfate in the ocean and the loss of atmospheric massindependent sulfur isotope fractionation in phase with sulfur is the earliest recorded positive carbon isotope anomaly convincingly linking these environmental perturbations to the great oxidation event ca 2 3 ga

the cycling and redox state of nitrogen in the archaean ocean organisms that produce oxygen through photosynthesis existed during the late archaean eon about 2 500 million years ago but controversial evidence suggests that they may have evolved several hundred million years earlier oxygen is expected to react with oceanic nitrogen altering its redox state the reaction leaves a signature in the isotopic composition of the nitrogen bound in organic matter here we present a record of the nitrogen isotopic composition of kerogen extracted from minimally altered shales from the campbellrand malmani platform in south africa between the palaeo archaean and about 2 670 million years ago the 15n values of the kerogen rose by about 2 we interpret this increase as an indication of the onset of coupled nitrification and denitrification or anammox reactions in the surface oceans which require the presence of free oxygen a second increase in nitrogen isotopic composition around 2 520 million years ago implies instability of the n cycle with loss of fixed n this evidence for available oxygen in the oceans occurs at least 200 million years before geochemical indications of the presence of significant levels of atmospheric oxygen we suggest that coupled nitrification and denitrification drove the loss of fixed inorganic nitrogen leading to nitrogen limitation and conclude that the low levels of biologically available nitrogen limited the growth of oxygen producing plankton delaying the accumulation of oxygen in the atmosphere the initial production of oxygen in early earth s oceans altered the redox chemistry and cycling of nitrogen a record of nitrogen isotopes from preserved organic matter indicates nitrogen cycling in the presence of free oxygen 2 67 billion years ago about 200 million years before the first geochemical evidence for atmospheric free oxygen

evolution of the oceanic sulfur cycle at the end of the paleoproterozoic here we present new measurements of 32 s 33 s 34 s and 36 s in sedimentary sulfides and couple these measurements with modeling treatments to study the sulfur cycle of a late paleoproterozoic marine basin we target the transition in ocean chemistry from the deposition of paleoproterozoic iron formations gunflint formation biwabik formation trommald formation and mahnomen iron formations to the inferred sulfidic ocean conditions recorded by overlying shale rove formation the data suggest that certain features of the global sulfur cycle such as a control by sulfate reducing prokaryotes and low mm concentrations of oceanic sulfate were maintained across this transition this suggests that the transition was associated with changes in the structure of the basin scale sulfur cycle during deposition of these sediments sulfide data from the iron formations are interpreted to reflect sedimentary sulfides formed from microbial reduction of pore water sulfate that was supplied through steady state exchange with an overlying oceanic sulfate reservoir the sulfide data for the euxinic rove formation shales reflect the operation of a sulfur cycle that included the loss of sulfide by a rayleigh like process we suggest that the prevalence of large and variable heavy isotope enrichments observed in rove formation sulfide minerals reflect a sustained and significant net loss of sulfide from the euxinic water column either as a result of a shallow chemocline and degassing to the atmosphere or as a result of a water column pyrite sink the inclusion of 36 s measurements in addition to 32 s 33 s and 34 s illustrates the mass dependent character of these sedimentary environments ruling out contributions from the weathering of archean sulfides and pointing to at least modest levels of sustained atmospheric oxygen 10 5 present atmospheric levels of o2

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

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

environmental control on diverse stromatolite morphologies in the 3000 myr pongola supergroup south africa a unique outcrop of partly silicified dolomite in the white umfolozi section of the pongola supergroup south africa indicates that stromatolites were diverse and adapted to a range of shallow tidal depositional settings 3000 myr ago composite columnar stromatolitic bioherms 0 7 1 6m high and 0 4 1 0m in diameter formed along the margins of a tidal channel they were flanked away from the channel by flat stratiform and small domical stromatolites growing in low energy tidal flat environments conical stromatolites 0 05 0 30m high and 0 03 0 10m in diameter accreted in high energy coarse grained carbonate sand along the bottom of the tidal channel the stromatolites probably formed through the activities of filamentous oxygen producing photoautotrophic cyanobacteria

evidence of tidal processes from the lower part of the witwatersrand supergroup south africa abstract a 1600 m succession of quartz arenites and associated shaley deposits comprising the hospital hill subgroup at the base of the witwatersrand supergroup is considered to have been deposited largely under the influence of tidal processes facies analysis indicates that deposition occurred in the following environments 1 marine shalf 2 shallow subtidal to intertidal 3 intertidal flat and 4 tidal inlet the presence of strong tidal currents implies that the witwatersrand basin was open to an ocean basin at least during the early stages of its evolution palaeocurrent trends and isopach data suggest that this probably lay to the southwest an area now occupied by the high grade natal namaqua metamorphic belt the contrast between the supermature quartz arenites of the hospital hill subgroup and the overlying gold bearing immature subgreywackes feldspathic quartzites and conglomerates of fluvial origin is believed to be a function of tidal reworking of sediments

multiple sulfur isotopes and the evolution of earth s surface sulfur cycle abstract the distribution of sulfur isotopes in geological materials reveals information about earth history and biogeochemical processes research during the last several decades has used sulfur isotope geochemistry as a tool to better understand microbial processes harrison and thode 1958 kaplan 1975 monster et al 1979 peck 1959 peck 1962 rees 1973 and sediment diagenesis berner 1969 berner 1982 canfield et al 1993b earth historians also realized this potential as there exists a rich record of environmental change within the sedimentary records canfield and teske 1996 claypool et al 1980 goodwin et al 1976 habicht et al 2002 kah et al 2004 monster et al 1979 shen et al 2001 strauss 1993 thode and goodwin 1983 these applications have championed the use of the two most abundant sulfur isotopes 32s and 34s and provide a rich introduction to what the sulfur isotope record has to offer see canfield 2004 canfield and raiswell 1999 within the last decade this information has been supplemented by new data derived from the less abundant isotopes 33s and 36s the measurement of all four stable sulfur isotopes multiple sulfur isotope geochemistry has expanded our understanding of biological evolution and activity atmospheric chemistry and transport crustal recycling and many more fields related to earth surface processes see farquhar and wing 2003 here i present a review of recent works in multiple sulfur isotope geochemistry with a focus on results that inform our understanding of biogeochemical processes and earth surface evolution

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

stratification and mixing of a post glacial neoproterozoic ocean evidence from carbon and sulfur isotopes in a cap dolostone from northwest china abstract to improve our knowledge about the geochemical and environmental aftermath of neoproterozoic global glaciations we analyzed stable isotopes 13 c 18 o 34 s and elemental concentrations ca mg s sr fe and mn of the 10 m thick zhamoketi cap dolostone atop the tereeken diamictite in the quruqtagh area eastern chinese tianshan available chemostratigraphic data suggest that the tereeken diamictite is probably equivalent to the marinoan glaciation our new data indicate that organic and carbonate carbon isotopes of the zhamoketi cap dolostone show little stratigraphic variations averaging 28 2 and 4 6 respectively in contrast sulfur isotopes show significant stratigraphic variations carbonate associated sulfate cas abundance decreases rapidly in the basal cap dolostone and 34 s cas composition varies between 9 and 15 in the lower 2 5 m in the overlying interval cas abundance remains low while 34 s cas rises 5 and varies more widely between 10 and 21 the range of 34 s py of the cap dolostone overlaps with that of 34 s cas but direct comparison shows that 34 s py is typically greater than 34 s cas measured from the same samples hypotheses to explain the observations must account for both the remarkable sulfur isotope enrichment of pyrites and the inverse fractionation we propose that cas and pyrite were derived from two isotopically distinct reservoirs in a chemically stratified basin or a basin with a sulfate minimum zone in this model cas was derived from shallow oxic surface waters with moderate sulfate concentration and depleted in 34 s due to the post glacial influx of sulfur from continental weathering in contrast pyrite was derived from anoxic bottom waters or a sulfate minimum zone with low sulfate concentration and 34 s enrichment due to long term syn glacial sulfate reduction the rapid shift in cas abundance and sulfur isotope composition within the cap dolostone is interpreted to reflect the mixing of the two reservoirs after initial deglaciation comparison with other post marinoan cap carbonates shows significant spatial heterogeneity in 34 s cas which together with strong temporal variation in 34 s cas points to generally low sulfate concentrations in post marinoan oceans

zircon ion microprobe studies bearing on the age and evolution of the witwatersrand triad abstract the ventersdorp and witwatersrand supergroups and the dominion group collectively referred to as the witwatersrand triad represent some of the oldest and economically most important volcano sedimentary basins within the kaapvaal craton of southern africa precise age constraints which are vital to models aimed at understanding the formation mineralisation and evolution of these basins have been hampered by analytical and geological problems these problems have been overcome by this ion microprobe study on zircons from volcanic rocks within the three basins felsic and mafic volcanics from the ventersdorp supergroup yield ages of 2709 4 ma and 2714 8 ma respectively constraining the timing of the closure of the witwatersrand basin a maximum age for the witwatersrand basin is indicated by the age of 3074 6 ma for volcanics from the underlying dominion group thus a period of c 350 ma was available for the accumulation of the full witwatersrand basin succession unfortunately dating within the witwatersrand basin itself is not complete and future work could show that extended time breaks may exist within the basin these new data show that previous age determinations on the ventersdorp witwatersrand and dominion basins were inaccurate and that the economically important witwatersrand basin must now be recognised as archaean

microbial fixation of methane carbon at 2 7 ga was an anaerobic mechanism possible 1 in earth s history the most extreme episode of 13c depletion in sedimentary organic matter occurred about 2 7 billion years ago this isotopic excursion is widely interpreted as resulting from increased burial of organic carbon derived from microbial fixation of 13c depleted methane modern microbial physiologies involve either oxygen or sulfate as electron acceptors in such processes until now the isotopic signal has been exclusively assigned to growth of aerobic methanotrophic bacteria and consequently interpreted as an indication for the presence of molecular oxygen in late archaean surface environments the alternative anaerobic pathway involving sulfate as the electron acceptor was dismissed because this process has been considered inefficient in producing biomass sufficient to account for significant fractions of 13c depleted carbon in some archaean rocks calculations based on recent findings at two modern sites now show however that anaerobic processes could account for the archaean signal

earliest microbially mediated pyrite oxidation in 3 4 billion year old sediments abstract pyrite fes2 oxidation in modern sedimentary environments is neither a purely chemical nor purely microbial process but it is significantly enhanced by the activity of microorganisms that use reduced forms of iron and sulphur in their metabolisms on the early earth where oxygen levels were thought to be

integrated pb and s isotope investigation of sulphide minerals from the early archaean of southwest greenland we present high spatial resolution secondary ion mass spectrometry sims measurements of pb and s isotopes in sulphides from early archaean samples at two localities in southwest greenland secondary pyrite from a 3 71 ga sample of magnetite quartz banded iron formation in the isua greenstone belt which has previously yielded unradiogenic pb consistent with its ancient origin contains sulphur with a mass independently fractionated mif isotope signature delta 33 s 3 3 parts per thousand this reflects the secondary mineralization of remobilized sedimentary s carrying a component modified by photochemical reactions in the early archaean atmosphere it further represents one of the most extreme positive excursions so far known from the early archaean rock record sulphides from a quartz pyroxene rock and an ultramafic boudin from the island of akilia in the godth a over circle bsfjord have heterogeneous and generally radiogenic pb isotopic compositions that we interpret to represent partial re equilibration of pb between the sulphides and whole rocks during tectonothermal events at 3 6 2 7 and 1 6 ga both these samples have delta 33 s 0 within analytical error and therefore show no evidence for mif sulphur these data are consistent with previous interpretations that the rock cannot be proven to have a sedimentary origin our study illustrates that sims s isotope measurements in ancient rocks can be used to elucidate early atmospheric parameters because of the ability to obtain combined s and pb isotope data but caution must be applied when using such data to infer protolith when information from geological context petrography and chronology i e by pb isotopes is combined and fully evaluated delta 33 s signatures from sulphides and their geological significance can be interpreted with a higher degree of confidence c 2005 elsevier b v all rights reserved

nonredox transformations of magnetite hematite in hydrothermal systems the transformation of magnetite to hematite or hematite to magnetite in nature has generally been considered a redox reaction and linked to a specific redox state of fluid however a nonredox reaction fe2o3 hm fe2 h2o fe3o4 mt 2h may have been the principal mechanism for the transformations of iron oxides in nature especially in hydrothermal environments for example the transformation of goethite and or hematite primary precipitates to magnetite in banded iron formations bifs probably occurred through nonredox reactions with fe2 bearing hydrothermal fluids during the accumulation of a bif sequence rather than through redox reactions involving organic matter during and or after the bif deposition the proposed mechanisms for the transformation of magnetite to hematite provides new exploration strategies for hematite rich secondary ores extending the target for orebodies to much deeper zones below the paleosurface another important implication of the proposed mechanism is that the presence or absence of magnetite and or hematite in geologic formations may or may not provide meaningful information on the redox state of fluid

oxidative forcing of global climate change a biogeochemical record across the oldest paleoproterozoic ice age in north america carbon isotope compositions of organic matter in fine grained siliciclastic units deposited above and below glacial diamictite at the base of the ca 2 45 2 22 ga huronian supergroup in ontario canada were studied to constrain relationships between profound fluctuations in the exogenic carbon cycle and dramatic climate changes at the beginning of the proterozoic eon in both drill core and outcrop sections the organic matter preserved in proximal lithofacies dominated by coarse grained sand and silt are enriched in 13 c relative to distal lithofacies dominated by argillites in the drill core sand dominated lithofacies of the mckim formation beneath the glacial diamictite of the ramsay lake formation have a narrow range of 13 c values 28 4 to 26 0 vpdb but organic matter in argillite dominated lithofacies of the outcrop section 40 km to the southeast is somewhat more 13 cdepleted with values ranging from 34 5 to 26 4 similarly sand dominated lithofacies of the pecors formation above the glacial diamictite in the drill core section with 13 c values of ca 28 are notably 13 c enriched relative to argillite dominated lithofacies which record values as low as 40 5 the sand dominated lithofacies of the pecors formation in the outcrop sections have 13 c compositions ranging from 34 4 to 27 9 the isotopic differences appear to be unrelated to organic carbon abundances so we suggest that these are controlled by environmental differences in proximal and distal settings the strong 13 cdepletion in the organic lean mckim and pecors argillites especially in the drill core section of the pecors formation is consistent with significant biological methane production and oxidative recycling by methanotrophs both before and after the ice age in shallow water environments stratified with respect to oxygen the rise of atmospheric oxygen and subsequent enhanced biogeochemical methane cycling in shallow water settings likely contributed to unstable climate conditions during the paleoproterozoic glacial epoch 2007 elsevier b v all rights reserved

chemical and carbon isotopic evolution of hydrocarbons during prograde metamorphism from 100 c to 550 c case study in the liassic black shale formation of central swiss alps abstract hydrocarbon distributions and stable isotope ratios of carbonates 13ccar 18ocar kerogen 13cker extractable organic matter 13ceom and individual hydrocarbons of liassic black shale samples from a prograde metamorphic sequence in the swiss alps were used to identify the major organic reactions with increasing metamorphic grade the studied samples range from the diagenetic zone 17 n alkanes suggests the occurrence of cracking reactions of high molecular weight compounds the isotopically heavier up to 5 6 c 13 n alkanes with metamorphism suggests progressive thermal release of kerogen linked fatty acid precursors and degradation of n alkanes changes of the steroid and terpenoid distributions are clearly related to increasing metamorphic temperatures the absence of 18 h 22 29 30 trisnorneohopane ts the occurrence of 17 h trisnorhopane 17 h 21 h hopanes in the c29 to c31 range and 5 h 14 h 17 h 20r c27 c29 steranes in the low diagenetic samples the occurrence of specific hydrocarbons e g n alkylcyclopentanes cadalene hydrogenated aromatic compounds in metamorphic samples points to kerogen degradation reactions most probably occurring in the presence of water and under reducing conditions the changes of hydrocarbon distributions and carbon isotopic compositions of n alkanes related to metamorphism suggest that the organic geochemistry may help to evaluate the lowest grades of prograde metamorphism

quadruple sulfur isotope analysis of ca 3 5 ga dresser formation new evidence for microbial sulfate reduction in the early archean abstract multiple sulfur isotope system is a powerful new tracer for atmospheric volcanic and biological influences on sulfur cycles in the anoxic early earth here we report high precision quadruple sulfur isotope analyses 32s 33s 34s 36s of barite pyrite in barite and sulfides in related hydrothermal and igneous rocks occurring in the ca 3 5 ga dresser formation western australia our results indicate that observed isotopic variations are mainly controlled by mixing of mass dependently md and non mass dependently fractionated non md sulfur reservoirs based on the quadruple sulfur isotope systematics 34s 33s 36s for these minerals four end member sulfur reservoirs have been recognized 1 non md sulfate 34s 5 2 33s 3 1 2 md sulfate 34s 10 3 3 non md sulfur 34s 6 33s 4 and 4 igneous md sulfur 34s 33s 0 the first and third components show a clear non md signatures thus probably represent sulfate and sulfur aerosol inputs the md sulfate component 2 is enriched in 34s 10 3 and may have originated from microbial and or abiotic disproportionation of volcanic s or so2 our results reconfirm that the dresser barites contain small amounts of pyrite depleted in 34s by 15 22 relative to the host barite these barite pyrite pairs exhibit a mass dependent relationship of 33s 34s with slope less than 0 512 which is consistent with that expected for microbial sulfate reduction and is significantly different from that of equilibrium fractionation 0 515 the barite pyrite pairs also show up to 1 difference in 36s values and steep 36s 33s slopes which deviate from the main archean array 36s 33s 0 9 and are comparable to isotope effects exhibited by sulfate reducing microbes 36s 33s 5 to 11 these new lines of evidence support the existence of sulfate reducers at ca 3 5 ga whereas microbial sulfur disproportionation may have been more limited than recently suggested

pyrite and organic matter in phanerozoic normal marine shales data have been obtained from our own chemical analyses and from the literature for the concentrations of organic carbon c and pyrite sulfur s in over 600 samples of cambrian to recent normal marine shales normal marine refers to deposition in oxygenated bottom water as evidenced by the presence of benthic fossils and or indicators of bioturbation all samples were selected to minimize 1 1 loss of c and or s due to weathering at the outcrop by emphasizing the use of drill core material 2 2 analytical errors and non diagenetic effects by avoiding sediments low in c or s content such as sandstones 3 3 fe limitation of pyrite formation by avoiding limestones cherts and euxinic shales 4 4 metamorphic loss of c relative to s by avoiding rocks obviously subjected to even low grade metamorphism our results indicate that 1 there is generally a good positive linear correlation between organic c and pyrite s for normal marine shales of all ages and 2 the mean cs ratio for normal marine shales has varied over time devonian to tertiary shales exhibit mean cs weight ratios 1 8 0 5 somewhat lower than quaternary sediments meancs 2 8 this we believe is due to preferential c loss relative to s during biogenic methanogenesis plus diagenetic heating distinctly lower mean c s values for the cambrian and ordovician 0 5 0 1 cannot be explained solely in terms of diagenetic c loss and instead must represent low original ratios the low original ratios we suggest were due mainly to the absence of bacterially refractory organic matter added to the marine environment by rivers at that time because the major source of such material vascular land plants had not yet evolved this along with a possibly lower degree of bioturbation contributed to enhanced pyrite formation and preservation and thus lower early paleozoic cs ratios

anoxic pyrite oxidation by water radiolysis products a potential source of biosustaining energy abstract radiolysis on rocky planetary bodies provides chemical species across redox gradients that can supply energy for microbial life in subsurface environments we investigated the oxidation of pyrite to aqueous sulfate so42 by water radiolysis products with concomitant production of molecular hydrogen h2 the production of h2 the only gaseous product recovered at the end of pyrite water irradiation experiments was found to be dependent on pyrite water ratios the yield of radiolytically produced so42 correlated with the total irradiation dose the effectiveness of radiation in oxidative dissolution of pyrite is determined by 1 redox reactions between radiolytically produced oxidants and pyrite and 2 the interaction between radiation and pyrite s crystalline structure radiolytic oxidation of reduced sulfur occurs with the oxidants ho hydroxyl radical and fe3 ferric iron involving two different pathways the radiolytic production of these two chemical oxidants is self sustaining in the presence of water and fe2 in the system radiolytic oxidation can produce significant sulfur isotope effects by preferentially bringing 34s into solution as sulfate and leaving a 32s enriched elemental sulfur layer on the pyrite surface experimental abiotic fractionations of sulfur isotopes between original pyrite and its sulfur oxidation products are significant and indicate that isotopically distinct sulfate is being produced during oxidation based on measured radiolysis constants for pyrite and radiation dose estimates for continental crust we show that radiolysis of water coupled to oxidation of metallic sulfides could be a significant source of sulfate in many geological environments implications of this work are broad impacting our assessment of the potential for life to exist in subsurface environments on earth as well as in extraterrestrial environments

sole marks and combined flow storm event beds in the brixton formation of the siliciclastic archean witwatersrand supergroup south africa abstract sole marks and associated storm event beds are described for the first time from the middle archean witwatersrand supergroup the sole marks are excellently preserved and include a variety of marks formed by combined flow turnabout curvilinear and low angle intersecting groove marks bipolar prod marks recurved flute marks and shallow scour hollows the sole marks are intimately associated with other sedimentary structures formed by combined flow or oscillatory flow such as wave ripple marks undulatory parallel lamination hummocky cross stratification and hummock and swale structures the storm event beds with sole marks were deposited in a transitional shelf setting and grade upwards into swaly and trough cross bedded orthoquartzite deposited on the inner shelf interbedded storm event beds display a variety of sole mark assemblages reflecting widely varying flow conditions in the storm generated bottom boundary layer oscillatory currents were mainly oriented perpendicular to paleoshore and were combined in some cases with offshore directed storm surge relaxation currents some sole mark assemblages specifically those with turnabout and low angle intersecting groove marks contain evidence for the presence of shore oblique or shore parallel geostrophic currents the storm event deposits in the witwatersrand supergroup are thus compared with models derived from odern storm deposition

mass independent isotope effects in archean 2 5 to 3 8 ga sedimentary sulfides determined by ion microprobe analysis we report sulfur isotope anomalies with 33 s the deviation from a mass dependent fractionation line for the three isotope system 34 s 32 s vs 33 s 32 s ranging up to 2 within individual archean sedimentary sulfides from a variety of localities our measurements which are made in situ by multicollector secondary ion mass spectrometry unequivocally corroborate prior bulk measurements of mass independent fractionations mif in sulfur and provide additional evidence for an anoxic atmosphere on the earth before 2 ga this technique also offers new opportunities for exploring ancient sulfur metabolisms preserved in the rock record the presence of mif sulfur in sulfides from a 3 8 ga fe rich quartzite from akilia island west greenland is consistent with a marine sedimentary origin for this rock copyright 2003 elsevier science ltd

methanotrophs regulated atmospheric sulfur isotope anomalies during the mesoarchean tumbiana formation western australia abstract the 2 73 billion year old tumbiana formation of the fortescue group in the pilbara craton western australia preserves one of the best records of the fortescue negative carbon isotope excursion with organic 13 c values as low as 60 the prevailing environmental conditions at this biological excursion are not well understood here we present an integrated carbon 12 c 13 c and multiple sulfur 32 s 33 s 34 s 36 s isotopes study of a pristine diamond drill core through the tumbiana formation collected at meentheena by the pilbara drilling project our results show centimeter to meter scale heterogeneities in sulfur and carbon contents and isotope compositions organic 13 c values vary at the meter scale and display a bimodal distribution with peaks at about 44 and 34 this bimodal distribution is interpreted to reflect variations in the contribution of methanotrophic metabolism to the biomass the 34 s v cdt values of sedimentary pyrite vary from 5 73 to 2 75 sulfur isotopes sulfur contents and s c ratios are variable suggesting a complex local biotic sulfur cycling sedimentary pyrite preserves mass independent fractionation of sulfur mif s with 33 s v cdt ranging between 0 25 and 1 64 average 0 47 corresponding to the characteristic dampened mesoarchean anomalies positive correlation between sulfide mif s and a 13 c depletion of organic matter argues for a causal link between methanotrophs activity and the preservation of mif s anomalies in the rock record

pyrite replacement of mollusc shells from the lower oxford clay jurassic of england replacement of originally aragonite mollusc shells by pyrite commonly occurs in the lower oxford clay petrographic studies show the shells to have constituted complex microenvironments in the sediment a range of replacement textures is found showing a variable amount of solution of the original aragonite three distinct textures were found in crushed pyrite replaced ammonite shells from heavily pyritized concretions 1 a texture reflecting the original shell structure due to the replacement of the organic shell matrix by pyrite 2 an ovoid texture seen at several stages of replacement reflecting processes occurring at discrete centres of sulphate reduction 3 euhedral crystals lining cracks and fractures in the shell three types of replacement are found in small gastropods and bivalves from shell bed some of which may relate to those seen in the ammonites 1 replacement of organic shell matrix by pyrite preserving good shell microstructure 2 replacement showing outwardly good preservation of morphological features but inwardly only the gross structure such as growth lines is preserved 3 replacement of the shell in a matrix of euhedral pyrite leaving only lines of carbonate inclusions marking the margins of the shell the replacement textures and types appear to be dependent on the initial structure of the shell and the access of iron and sulphate into the shell early stages of replacement appear to proceed by pyrite formation within the organic matrix of the shell with little or no solution of the carbonate this produces textures which faithfully mimic the original shell microstructure it is thought that the lack of carbonate solution is due to a limited availability of iron brought about by the less intensively reducing nature of the sediment later stages of replacement are promoted by the cracking and fracturing of the shell and are generally not as faithful to the original shell structure this is due to the greater availability of iron as the sediment becomes more reducing with burial

carbonate petrography kerogen distribution and carbon and oxygen isotope variations in an early proterozoic transition from limestone to iron formation deposition transvaal supergroup south africa the transition zone comprises campbellrand microbialaminated replacing cryptalgalaminate limestone and shale with minor dolomite conformably overlain by the kuruman iron formation of which the basal part is characterized by siderite rich microbanded iron formation with minor magnetite and some hematite containing units the iron formation contains subordinate intraclastic and microbialaminated siderite mesobands and was deposited in deeper water than the limestones the sequence is virtually unaltered with diagenetic mineral assemblages reflecting a temperature interval of about 110 degrees to 170 degrees c and pressures of 2 kbars carbonate minerals in the different rock types are represented by primary micritic precipitates now recrystallized to microsparite early precompactional sparry cements and concretions deep burial limpid euhedral sparites and spar cements precipitated from metamorphic fluids in close contact with diabase sills paragenetic pathways of the carbonate minerals are broadly similar in all lithofacies with kerogen intimately associated with them kerogen occurs as pigmentation in carbonate crystals as reworked organic detritus in clastic textured carbonate units and as segregations of kerogen pigment around late diagenetic carbonate crystals locally kerogen may also be replaced by carbonate spar carbon isotope compositions of the carbonate minerals and kerogen are dependent on their mode of occurrence and on the composition of the dominant carbonate species in a specific lithofacies integration of sedimentary petrographic geochemical and isotopic results makes it possible to distinguish between depositional early diagenetic deep burial and metamorphic effects on the isotopic compositions of the carbonate minerals and the kerogen in the sequence major conclusions are that deep burial thermal decarboxylation led to 13c depletion in euhedral ferroan sparites and 13c enrichment in kerogen organic carbon metamorphic sparites are most depleted in 13c carbonates in oxide rich iron formations are more depleted in 13c than those in siderite rich iron formation whereas the kerogens in oxide banded iron formations bif are more enriched this implies that the siderite rich iron formations were not derived from oxide rich iron formation through reduction of ferric iron by organic matter organic matter oxidation by ferric iron did however decrease the abundance of kerogen in oxide rich iron formation and led to the formation of isotopically very light sparry carbonates siderite and calcmicrosparite both represent recrystallized primary micritic precipitates but differ in their 13c composition with the siderites depleted in 13c by 4 6 per mil on average relative to calcmicrosparite this means that the siderites were precipitated from water with dissolved inorganic carbon depleted in 13c by about 9 per mil relative to that from which the limestones precipitated this implies an ocean system stratified with regard to total carbonate with the deeper water from which siderite rich iron formation formed depleted in 13c iron formations were deposited in areas of very low organic matter supply depletion of 13c may therefore derive not from degradation of organic matter but from hydrothermal activity a conclusion which is supported by 18o composition of the carbonate minerals and trace element and rare earth element ree compositions of the iron formations

deposition of banded iron formations by anoxygenic phototrophic fe ii oxidizing bacteria the mechanism of banded iron formation bif deposition is controversial but classically has been interpreted to reflect ferrous iron fe ii oxidation by molecular oxygen after cyanobacteria evolved on earth anoxygenic photoautotrophic bacteria can also catalyze fe ii oxidation under anoxic conditions calculations based on experimentally determined fe ii oxidation rates by these organisms under light regimes representative of ocean water at depths of a few hundred meters suggest that even in the presence of cyanobacteria anoxygenic phototrophs living beneath a wind mixed surface layer provide the most likely explanation for bif deposition in a stratified ancient ocean and the absence of fe in precambrian surface waters

textural and geochemical discrimination between xenotime of different origin in the archaean witwatersrand basin south africa abstract xenotime ypo4 of detrital diagenetic and hydrothermal origin within siliciclastic rocks of the archaean witwatersrand basin south africa has been identified on the basis of petrography and in situ ion microprobe shrimp age data the chemical composition of xenotime determined by in situ electron microprobe analysis can be correlated with its origin this allows the origin of any xenotime grain to be assessed by a non destructive microanalytical method prior to ion microprobe geochronology the main chemical discriminators are mree hree abundance normalised hree slope and eu anomaly and in some cases u and th contents igneous detrital xenotime 2800 ma is distinguished from diagenetic 2780 ma and hydrothermal

hydrogen based carbon fixation in the earliest known photosynthetic organisms thin carbonaceous laminations preserved in shallow water facies of the 3416 ma buck reef chert south africa have been interpreted to represent some of the oldest known mats constructed by photosynthetic microbes preservation of these mats within a unit containing facies deposited at water depths ranging from 0 m to 200 m provides an opportunity to explore the electron donors employed in early microbial photosynthesis the presence of siderite feco3 as a primary sediment lack of hematite fe2o3 and lack of cerium anomalies throughout the buck reef chert imply that the entire water column was anoxic despite the presence of photosynthetic organisms authigenic uranium ua u th 3 correlates inversely with siderite abundance suggesting that variations in carbonate rather than oxygen activity controlled uranium mobility the inferred lack of oxygen and ferric minerals and the presence of dissolved fe2 in the water column imply that h2o fe2 and h2s could not have served as primary electron donors for carbon fixation it is most likely that buck reef chert bacteria utilized h2 as the primary reductant for photosynthesis

the evolution of the global selenium cycle secular trends in se isotopes and abundances abstract the earth s surface has undergone major transitions in its redox state over the past three billion years which have affected the mobility and distribution of many elements here we use se isotopic and abundance measurements of marine and non marine mudrocks to reconstruct the evolution of the biogeochemical se cycle from 3 2 gyr onwards the six stable isotopes of se are predominantly fractionated during redox reactions under suboxic conditions which makes se a potentially valuable new tool for identifying intermediate stages from an anoxic to a fully oxygenated world 82 78 se shows small fractionations of mostly less than 2 throughout earth s history and all are mass dependent within error in the archean especially after 2 7 gyr we find an isotopic enrichment in marine 0 37 0 27 relative to non marine samples 0 28 0 67 paired with increasing se abundances student t tests show that these trends are statistically significant although we cannot completely rule out the possibility of volcanic se addition these trends may indicate the onset of oxidative weathering on land followed by non quantitative reduction of se oxyanions during fluvial transport the paleoproterozoic great oxidation event goe is not reflected in the marine 82 78 se record however we find a major inflection in the secular 82 78 se trend during the neoproterozoic from a precambrian mean of 0 42 0 45 to a phanerozoic mean of 0 19 0 59 this drop probably reflects the oxygenation of the deep ocean at this time stabilizing se oxyanions throughout the water column since then reduction of se oxyanions has likely been restricted to anoxic basins and diagenetic environments in sediments in light of recent cr isotope data it is likely that oxidative weathering before the neoproterozoic produced se oxyanions in the intermediate redox state se iv whereas the fully oxidized species se vi became more abundant after the neoproterozoic rise of atmospheric oxygen

a review of the geochronological constraints on the evolution of the kaapvaal craton south africa abstract all the published u pb geochronological data from zircon titanite sphene and monazite and pb pb evaporation data applicable to the palaeoarchaean to neoarchaean geology of the kaapvaal craton are employed to reconstruct the history and crustal architecture of the ca 3600 2500 ma cratonic basement in south africa only data interpreted as representative of the age of crystallisation or the 207 pb 206 pb ages from zircon xenocrysts have been considered in constructing graphs of cumulative probability versus age of rock formation in this manner it has been possible to identify the main magmatic events that have contributed to the assembly of the craton for convenience of data handling the kaapvaal craton has been subdivided into eastern central northern and western geographic domains these domains are not intended as discrete geological terranes although each one has its own geological and chronological character although consanguinity of events is also evident the oldest rocks so far recognised are located in the swaziland barberton areas where ages 3600 ma have been recorded the early stages of shield development are best exposed in the barberton mountain land where it is now apparent that continent formation took place by magmatic accretion and tectonic amalgamation of small protocontinental blocks at barberton several diachronous blocks formed between 3600 and 3200 ma have been identified each of which represents a cycle of arc related magmatism and sedimentation this phase of crustal development was followed by a period of mesoarchaean cratonic magmatism particularly prevalent between approximately 3100 3000 ma and marked by the development of a major crescent shaped juvenile arc that was accreted onto the northern and western margins of the evolving kaapvaal shield cratonisation was accomplished by the emplacement of major granitoid batholiths which thickened and stabilised the continental crust during the early stages of this cycle subsequent evolution of the craton between 3000 and 2700 ma was associated with continent arc collision during which time the witwatersrand basin and its correlatives were deposited as foreland sequences followed by episodic extension and rifting when the gaborone kanye and ventersdorp sequences were developed

lithofacies control on multiple sulfur isotope records and neoarchean sulfur cycles abstract triple sulfur isotope ratios 32 s 33 s 34 s were measured for 141 bulk rock samples from two agouron scientific drill cores gkp01 and gkf01 that recovered neoarchean successions of the transvaal supergroup south africa these two deep time cores are correlated to each other with 14 tie lines using volcanic and impact spherule layers in a sequence stratigraphic framework allowing us to evaluate both lithofacies and temporal controls over multiple sulfur isotope systematics the ca 2 5 ga giga annum before present basinal klein naute formation and the ca 2 6 ga peritidal boomplaas and vryburg formations yield an array of data characterized by 33 s 1 4 34 s these linear trends are found in both shallow water and deepwater facies but are characteristic to rocks with high iron content suggesting these may reflect isotopic compositions of aqueous sulfide elemental sulfur reservoirs in the neoarchean oceans data that deviate from this linear array are interpreted as resulting from additional inputs of sulfide from microbial sulfate reduction with or without contribution from sulfur disproportionation sulfate derived sulfur evolved to be either enriched or depleted in 34 s depending on the local depositional environment for example the reivilo formation in core gkf01 is characterized by abundant microbialite textures and shows an isotopic signature of closed system sulfate reduction rapid cementation of these carbonate fabrics may have attenuated the supply of sulfate to pore waters resulting in the progressive 34 s enrichments during bacterial sulfate reduction below the sediment water interface in contrast signatures of open system sulfate reduction are associated with slope facies dominated by granular dolostones preserved in the upper nauga formations in gkf01 and gkp01 the two different sulfur isotope patterns interpreted to reflect closed versus open system sulfate reduction are both found in the lower reivilo formation in both cores this lateral variation of isotope signals documents that observed 34 s shifts can be controlled locally and may not have temporal significance this study demonstrates critical importance of recovering sulfur isotope data from stratigraphically correlated drill cores to evaluate both geographical and temporal shifts of sulfur cycles and their links to the great oxidation event at the end of the archean eon

multiple sulfur isotopes of sulfides from sediments in the aftermath of paleoproterozoic glaciations geochemical evidence reported from paleoproterozoic sediments has long been used to evaluate the transition from the anoxic archean atmosphere to an oxygenated atmosphere sulfur isotopes 32s 33s 34s and 36s in sedimentary sulfides and sulfates are an especially sensitive means to monitor this transition such that the timing of the paleoproterozoic great oxidation event can be investigated using mass independently fractionated mif sulfur isotope systematics expressed as 33s here we report data from 83 individual analyses of pyrite pyrrhotite and chalcopyrite on a new suite of 30 different samples from finland south africa wyoming and ontario that span 600 my and follow one or several snowball earth events in the paleoproterozoic the samples were measured using a high resolution secondary ion mass spectrometry technique in multicollection mode that investigates multiple sulfur isotopes in microdomains 30 m within individual sulfide grains while preserving petrographic context we focused on sediments deposited in the aftermath of the paleoproterozoic glaciations between 1 9 and 2 2 ga to trace fluctuations in atmospheric o2 concentrations that were likely affected by an interplay of o2 sinks in the atmosphere and the upper ocean and continental crust and by the emergence and diversification of aerobic organisms our results demonstrate that mif sulfur isotopes are absent in sediments deposited after the period of protracted global cooling in the paleoproterozoic and independently confirm observations that mif ceased during this time we interpret our results by integrating 33s and 34s data in sulfides 13c data in carbonates and the estimated timing of glaciation events in the paleoproterozoic data strongly hint at the presence of microbial sulfate reduction and fluctuations in the concentration of dissolved seawater sulfate and or in 34ssulfate in the aftermath of glaciations and likely were affected by changing erosion rates and nutrient delivery to the oceans these changes modulated the population of primary producers especially oxygenic photosynthesizers and led to fluctuations in the abundance of atmospheric o2 co2 and ch4 our results support the interpretation that the world wide 13ccarb excursion observed between 2 25 and 2 05 ga karhu and holland 1996 was a period of significant accumulation of o2 in the atmosphere

earth s oldest reported glaciation physical and chemical evidence from the archean mozaan group 2 9 ga of south africa the pongola supergroup is a thick succession of archean 2 9 ga supracrustal rocks in the eastern part of the kaapvaal craton of southern africa its upper part the mozaan group 5000 m thick includes diamictites with a highly varied suite of clasts some of which are striated and faceted clasts in associated stratified siltstones are interpreted as ice rafted debris a glacial origin is also supported by geochemical investigation of diamictite matrix materials and associated mudstones plots of sio2 al2o3 and tio2 al2o3 suggest that these rocks underwent little chemical weathering an interpretation confirmed by calculation of a chemical index of alteration with low values typical of other glacial deposits the analyzed rocks are rich in fe average fe2o3 t is 24 wt like rocks of many other glaciomarine successions the diamictites and associated mudstones of the mozaan group have low th sc ratios suggesting preferential incorporation of mafic materials into the diamictite matrix material

flexural partitioning of the late archaean witwatersrand foreland system south africa abstract the witwatersrand basin is part of a retroarc foreland system formed during the late archaean in response to crustal thickening along the northern margin of the kaapvaal craton this foreland system may be partitioned into foredeep forebulge and back bulge flexural provinces the preserved sedimentary fill occupies the region of the flexural foredeep and displays a typical transition from underfilled deep and shallow marine to overfilled fluvial and alluvial fan phases loading in the witwatersrand thrust belt took place in relation to the oblique convergence of two compressional stress fields as a result the foredeep is restricted along the strike to a distance of the witwatersrand foreland system formed on a newly cratonized continental lithosphere which gave the basin a small flexural wavelength i e 490 km from the center of orogenic loading to the axis of the back bulge relative to most phanerozoic counterparts the forebulge unconformity may be associated with the lack of dynamic loading which is probably a common feature for all precambrian retro foreland systems due to the lower rates of subduction associated with the early stage of plate tectonic processes

spatial and temporal distribution of microbially induced sedimentary structures a case study from siliciclastic storm deposits of the 2 9 ga witwatersrand supergroup south africa abstract microbially induced sedimentary structures miss arise from the interaction of microbial mats with the physical sedimentary dynamics of shallow marine settings the structures occur in siliciclastic deposits of paleo archean age to modern where they record biostabilization and baffling trapping and binding of photoautotrophic microbenthos in the brixton formation witwatersrand supergroup south africa erosional remnants and pockets wrinkle structures and oscillation cracks include carbon and pyrite rich filament like textures that resemble modern trichomes of cyanobacteria c isotope ratios of 22 0 1 indicate potential photoautotrophy the miss occur at the turning points of regression transgression and are restricted to a specific sedimentary facies characterized by 2 20 cm thick fine sandstone beds predominantly composed of quartz the sandstone beds display ripple marks which record moderate hydraulic reworking this spatial and temporal distribution of miss in the brixton formation is consistent with occurrences of those structures in comparable environments throughout earth history

superheavy pyrite δ34spyr δ34scas in the terminal proterozoic nama group southern namibia a consequence of low seawater sulfate at the dawn of animal life sulfur isotope analysis 34 s of well preserved carbonates spanning an 10 ma interval of the terminal proterozoic nama group reveals that disseminated pyrite is consistently enriched in 34 s relative to coeval seawater sulfate as preserved in carbonate associated sulfate cas this observation is not consistent with the current paradigm for interpreting the geologic record of sulfur isotopes which assumes that pyrite 34 s 34 s pyr will be equal to or less than co occurring cas 34 s 34 s cas due to the kinetic isotope effect of bacterial sulfate reduction bsr that favors the lighter isotope of sulfur 32 s during sulfur oxygen bond breakage although the precise mechanism of pyrite sulfur isotope enrichment is debatable our combined observations of extremely 34 s enriched pyrite low bulk rock concentrations of sulfur from cas and pyrite and high frequency fluctuations in 34 s cas and 34 s pyr throughout the nama group carbonates point to very low concentrations of sulfate in portions of the terminal proterozoic ocean the additional occurrence of 34 s enriched pyrite in contemporaneous terminal proterozoic sections from poland and canada reveal that low seawater sulfate may have been widespread in the oceans at this time however the absence of such extremely 34s enriched pyrite from well preserved coeval carbonate sections in oman suggests that such conditions were not globally uniform low geographically varied concentrations of marine sulfate in terminal proterozoic time are consistent with elevated geographically varied concentrations of reactive nonpyritized iron in marine shales recently reported for this interval suggesting that high dissolved fe ii and low o 2 persisted in a range of marine facies as late as 543 ma tens of millions of years after the origin of animals yet prior to their major diversification in early cambrian time

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

multiple sulfur isotopes and the evolution of the atmosphere interest in multiple sulfur isotope analyses has been fueled by recent reports of mass independent sulfur isotope signatures in the geologic record a non zero multiple isotopic signature of sulfur 33s and 36s is produced primarily through photochemical reactions and it is an almost perfect tracer of the source of sulfur once the signature is passed on to a given sulfur reservoir it will be preserved unless there is addition of sulfur with a different 33s or 36s in the geological record this signature has been used to study the evolution of the earth s atmosphere and to trace movement of sulfur through geological systems early in earth s history recently small but significant mass independent signatures have been reported for some younger samples raising the possibility of additional applications of multiple isotope studies the purpose of this review is to introduce and discuss the implications of multiple isotope studies and to focus attention on these anomalous but not uncommon isotopic signatures

carbon isotopes as biogeochemical recorders of life over 3 8 ga of earth history evolution of a concept ever since pioneering studies in the late 1930s had shown that the conversion of inorganic carbon into biogenic substances entails sizeable redistributions of the stable carbon isotopes biologically mediated 13c 12c fractionations have come to be recognized as a common corollary of biochemical reactions meanwhile it is firmly established that the universal bias in favour of 12c characterizing biological materials primarily derives from a kinetic isotope effect that is imposed on the first carbon fixing enzymatic carboxylation reaction in the primary metabolism of co2 fixing autotrophic organisms this preference for 12c has turned out to be one of the most enduring relics of the ordered state of the biological precursor substances that may be preserved in fossil organics over billions of years with the currently known sedimentary record at hand it can be stated with confidence that biological carbon isotope fractionations have persisted throughout 3 8 ga of recorded earth history indicating that microbial prokaryotic and archaeoprokaryotic ecosystems had been prolific already on the archean earth while for the time span 3 5 ga the isotopic evidence is unequivocal the information encoded in the preceding record is commonly blurred by a metamorphic overprint this holds particularly for the metasediments of the 3 8 ga old isua supracrustal belt of west greenland which apart from widespread metasomatism have suffered amphibolite grade metamorphism it is known that 13c 12c exchange occurs in organic kerogenous rock constituents during both amphibolite and granulite facies metamorphism if a second carbon partner is available as either fluids or carbonate with isotopic re equilibration often only partially achieved due to the sluggish kinetics of the exchange reaction thermodynamic equilibria predict however that 13c 12c ratios in kerogen and graphite increase during this process hence high t exchange equilibria are always bound to drive 13c values in positive direction the lowermost values encountered being consequently the least exchanged and most pristine with the lowest values of reduced graphitic carbon obtained in early isua studies falling into the range 22 to 28 pdb we had straightforward evidence since the late 1970s that carbon constituents with the isotopic composition of biogenic matter were indeed present in the pre metamorphic isua suite it was therefore by no means surprising that the results of recent isotope work performed on apatite hosted carbonaceous microdomains in isua banded iron formation utilizing advanced techniques of instrumental microanalysis had prompted similar conclusions hence the mainstream of the sedimentary carbon isotope record can be best interpreted as the geochemical manifestation of the isotope discriminating properties of the principal co2 fixing reactions s in biological carbon assimilation suggesting an extreme degree of evolutionary conservatism in the biochemistry of autotrophic carbon fixation as a consequence biological modulation of the geochemical carbon cycle had been established at least 3 8 ga ago having been fully operative by the time of formation of the earth s oldest sediments

mass dependent fractionation of quadruple stable sulfur isotope system as a new tracer of sulfur biogeochemical cycles abstract sulfur isotope studies of post archean terrestrial materials have focused on the ratio 34s 32s because additional isotopes 33s and 36s were thought to carry little information beyond the well known mass dependent relationship among multiple isotope ratios we report high precision analyses of 33s and 36s values defined as deviations of 33s and 36s from ideal mass dependent relationships for international reference materials and sedimentary sulfides of phanerozoic age by using a fluorination technique with a dual inlet isotope ratio mass spectrometer measured variations in 33s and 36s are explained as resulting from processes involve branching reactions two or more reservoirs formed or mixing irreversible processes in closed systems rayleigh distillation amplify the isotope effect we outline how this new isotope proxy can be used to gain new insights into fundamental aspects of the sulfur biogeochemical cycle including additional constraints on seawater sulfate budget and processes in sedimentary sulfide formation the isotope systematics discussed here cannot explain the much larger variation of 33s and 36s observed in archean rock records furthermore phanerozoic samples we have studied show a characteristic 33s and 36s relationship that differs from those measured in archean rocks and laboratory photolysis experiments thus high precision analysis of 33s and 36s can be used to distinguish small non zero 33s and 36s produced by mass dependent processes from those produced by mass independent processes in archean rocks and extraterrestrial materials

new insights into archean sulfur cycle from mass independent sulfur isotope records from the hamersley basin australia we have measured multiple sulfur isotope ratios 34 s 33 s 32 s for sulfide sulfur in shale and carbonate lithofacies from the hamersley basin western australia the v 33 s values v 33 swn 33 s30 515un 34 s shift from 31 9 to 6 9x over a 22 m core section of the lower mount mcrae shale v2 5 ga likewise sulfide sulfur analyses of the jeerinah formation v2 7 ga yield v 33 s values of 30 1 to 8 1x over a 50 m section of core despite wide variations in v 33 s and n 34 s these two shale units yield a similar positive correlation between v 33 s and n 34 s in contrast pyrite sulfur analyses of the carawine dolomite v2 6 ga yield a broad range in n 34 s 3 2 to 16 2x but a relatively small variation and negative values in v 33 s 32 5 to 31 1x the stratigraphic distribution of n 33 s n 34 s and v 33 s in western australia allows us to speculate on the sulfur isotopic composition of archean sulfur reservoirs and to trace pathways in the archean sulfur cycle our data are explained by a combination of massindependent fractionation mif in the atmosphere and biological mass dependent fractionation in the ocean in the archean volcanic sulfur bearing gas species were photolysed by solar ultraviolet uv radiation in an oxygen free atmosphere resulting in mif of sulfur isotopes aerosols of s8 with v 33 ss 0 and sulfuric acid with v 33 s6 0 formed from the products of uv photolysis and carried mass independently fractionated sulfur into the hydrosphere the signatures of atmospheric photolysis were preserved by precipitation of pyrite in sediments pyrite precipitation was mediated by microbial enzymatic catalysis that superimposed mass dependent fractionation on mass independent atmospheric effects multiple sulfur isotope analyses provide new insights into the early evolution of the atmosphere and the evolution and distribution of early sulfur metabolizing organisms a 2003 elsevier science b v all rights reserved

the auriferous late archaean central rand group of south africa sea level control of sedimentation abstract most earth scientists agree that either or both eustacy and tectonism play an important role in controlling sedimentation in the case of the auriferous late archaean central rand group of south africa most early workers favoured a marine depositional environment for the gold placers transgressions and regressions used to explain vertical alternations of coarse and fine grained deposits were attributed solely to vertical movements of the basin floor with no reference to eustatic variations tidal indicators are regarded as unequivocal evidence for a basin having been connected to the ocean and their recognition is considered a preliminary requirement for investigation of sea level fluctuations unambiguous recognition of sea level fluctuations in the rock record is problematic in some cases especially in non fossiliferous deposits to facilitate recognition in such deposits the following criteria are proposed a presence of thick laterally continuous mudstones b alternating coastal marine and continental facies in the vertical profile c onshore offshore oscillating baylines d marine facies unconformably overlain by fluvial facies e turbidites subaqueous debris flows and submarine canyons f incised valleys the turffontein subgroup of the vredefort structure situated roughly at the centre of the preserved witwatersrand basin is subdivided into five formations rt1 through rt5 tidal bundles in rt3 some with mud draped foresets provide evidence for connection of the witwatersrand basin to the ocean during central rand times formation rt4 is interpreted as being shallow marine in origin and is unconformably overlain by a sandy fluvial succession rt5 thereby suggesting a regression and sea level fall in the heidelberg area in the northeastern part of the witwatersrand basin the lower part of the turffontein subgroup consists predominantly of sandstone with subordinate conglomerate mudstone and diamictite this succession also exhibits most of the characteristics a to e given above two deep scours that eliminate the rich carbon leader occur in parts of the carletonville goldfield the eastern scour has a fill comprising predominantly mudstone and displays several additional characteristics of incised valley systems such as a downstream increase in depth and typical lateral and vertical facies arrangements texturally mature fluvial units occurring at different palaeotopographic levels indicate possible multiple episodes of incision and fill suggesting lower order sea level fluctuations superimposed upon a higher order cycle the results of the case studies presented provide clear evidence for sea level control of deposition in the distal parts of the witwatersrand basin during central rand times however in proximal regions sedimentation was probably governed by source area tectonism